(Contemporary Food Engineering) Robert W. Field, Erika Bekassy-Molnar, Frank Lipnizki, Gyula Vatai - Engineering Aspects of Membrane Separation and Application in Food Processing-CRC Press (2017)

Engineering Aspects of
Membrane Separation
and Application in
Food Processing
Engineering Aspects of
Membrane Separation
and Application in
Food Processing
Edited by
Robert Field, Erika Bekassy-Molnar,
Frank Lipnizki, and Gyula Vatai
Cover image of spiral wound module provided courtesy of Alfa Laval, Business Centre Membranes,
Nakskov, Denmark.
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Library of Congress Cataloging-in-Publication Data
Names: Field, Robert W., editor. | Bekassy-Molnar, Erika - editor. |

Lipnizki, Frank, editor. | Vatai, Gyula - editor.
Title: Engineering aspects of membrane separation and application in food
processing / editors, Robert Field, Erika Bekassy-Molnar, Frank Lipnizki,
and Gyula Vatai.
Description: Boca Raton : CRC Press, 2017. | Includes bibliographical
references.
Identifiers: LCCN 2016045008 | ISBN 9781420083637 (hardback : alk. paper)
Subjects: LCSH: Food processing machinery. | Membranes (Technology) |
Membrane separation. | Membrane reactors.
Classification: LCC TP371 .E537 2017 | DDC 664/.02--dc23
LC record available at https://lccn.loc.gov/2016045008
Visit the Taylor & Francis Web site at

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Contents
Preface......................................................................................................................vii
Acknowledgments......................................................................................................ix
Editors........................................................................................................................xi
Contributors............................................................................................................ xiii
Section I Basic Principles of Membrane Processes
Chapter 1 Membrane Separation Processes: An Overview................................... 3

Robert Field and Frank Lipnizki
Chapter 2 Concentration Polarization, Fouling, and Its Mitigation..................... 41

Robert Field
Chapter 3 Activity-Driven Membrane Processes................................................. 67

Robert Field and Edit Marki
Section II A
pplication of Membrane
Separation in Food Processing
Chapter 4 Dairy Industry and Animal Products Processing Applications.......... 93
Geneviève Gésan-Guiziou
Chapter 5 Wine Production Using Membranes................................................. 149

Erika Bekassy-Molnar
Chapter 6 Fruit and Vegetable Juice Processing Applications.......................... 195

Gyula Vatai
Chapter 7 Membrane Processes for Sugar and Starch Processing.................... 241

Frank Lipnizki
v
vi Contents
Chapter 8 Vegetable Oil Production: Emulsification......................................... 269

Andras Koris
Chapter 9 Food Applications of Membrane Bioreactors................................... 299

Lidietta Giorno, R. Mazzei, Emma Piacentini, and
Enrico Drioli
Index....................................................................................................................... 361
Preface
Today, the dynamic development of membrane separation processes is striking; to
adapt an advertising slogan for beer, “membrane processes are reaching the parts
that other separation cannot touch.” In the last 15–20 years, they have moved from
being exotic to becoming for many processes the accepted standard separation
method. More and more segments of technical applications have been taken over by
the continuously growing repertoire of membrane-based processes.
While the group of membrane processes are but one of the numerous unit operation
systems available for separation in the food industry, they have an environmental
advantage over the conventional processes because they are less energy intensive
than the processes they replace. Their reducing cost has helped greatly in the
competition against conventional separation processes such as evaporation, distilla-
tion, extraction, and adsorption. These properties of modern membrane technology
make them suitable for applications in the different fields of the food industry such as
the alcohol industry, in animal product processing, in fruit and beverage processing,
the processing of vegetable products, etc.
This book is divided into two sections for easy reference. Section I is titled “Basic
Principles of Membrane Processes” and contains chapters on: Membrane Separation
Processes: An Overview; Concentration Polarization, Fouling, and Its Mitigation; and
Activity-Driven Membrane Processes. Section II titled “Applications of Membrane
Separations in Food Processing” contains chapters on: Dairy Industry and Animal
Products Processing Applications; Wine Production Using Membranes; Fruit and
Vegetable Juice Processing Applications; Membrane Processes for Sugar and Starch
Processing; Vegetable Oil Production: Emulsification; and Food Applications of
Membrane Bioreactors.
vii
Acknowledgments
Robert Field acknowledges with gratitude, first and foremost, the patience of his
fellow coeditors, and the enduring support and encouragement of his loving wife
Jun Jie Wu. Then looking back to his introduction to membrane processes over
25 years ago, he acknowledges the insight and inspirations he received from John
Howell who created the Membranes Applications Centre at Bath University, circa
1990.
Erika Bekassy-Molnar expresses her gratitude to Professor Zsolt Fonyo at the

Technical University of Budapest for his helpful inspiration and the unstinted
research laboratory facilities he provided for decades. She acknowledges all her
coauthor partners for the successful preparation of this book. Furthermore, she
thanks her husband Sandor and her daughter Eniko for their permanent support,
and especially her little grandson Daniel for the cheerful atmosphere in the house.
Frank Lipnizki would like to acknowledge Professor Robert Field for introduc-
ing him to membrane technology 20 years ago. Further, he would wish to thank
his colleagues at Alfa Laval (previously Danish Separation Systems) and Professor
(emeritus) Gun Trägårdh and Professor Ann-Sofi Jönsson at Lund University for
their excellent cooperation and sharing his excitement over membranes over the
years. Finally, he would like to thank his wife Olga plus his children Gustav and
Veronica for enriching his life.
Gyula Vatai would like to acknowledge Professor (emeritus) Miodrag Tekic from
University of Novi Sad for introducing him to membrane technology 30 years ago,
and for his excellent cooperation in the field of application of membrane technology
in the food industry and environmental protection. Further, he would wish to thank
his colleagues at MAVIBRAN Co. at Magyar Viscosa Rt, Hungary (now Zoltek
Zrt) for introducing him into secrets of membrane and module production. Finally,
he would like to thank his wife Terezia plus his children Csongor and Tunde for
enriching his life.
ix
Editors
Robert Field is an alumnus of the University of Cambridge where he earned MEng
and PhD degrees in chemical engineering. He is currently a professor of engineering
science at the University of Oxford and Fellow of Balliol College, Oxford. His work in
membrane science and technology has examined the physical phenomena governing
the performance, particularly limitations to performance, of both p ressure-driven
and activity-driven membrane processes. The greatest industrial impact of this
research continues to be in the evolution of strategies for fouling m
itigation in mem-
brane processes. He has made a world-leading contribution to the development of
critical flux theory for porous membrane processes, which has led to a revolution
in membrane operation because designers of these processes no longer seek high
fluxes by way of large driving pressures and high cross-flow velocity but tend to
select modest fluxes to reduce the energy usage and cleaning costs. The change of
mind-set can truly be described as a paradigm shift. There has also been significant
work in pervaporation and membrane distillation. He has served as vice president of
the European Membrane Society, and to date has written more than 100 papers and
edited or coauthored five books on the different aspects of membrane science and
technology. He also worked for a number of years in the membrane group at Bath
University and has been on sabbatical leave to MIT on three occasions.
Erika Bekassy-Molnar graduated from the Technical University of Budapest

(TUB), Hungary in 1962 as a mechanical engineer with specialization in chemical
industry. She then worked at the TUB, Faculty of Chemical Engineering as assis-
tant, associate, and full professor. Her academic qualifications include Doctor of the
TUB (1969), Specialist of Cybernetics (1970), Candidate of Chemical Sciences of
the Hungarian Academy of Sciences (HAS) (1989), PhD from TUB (1994), Dr Habil
from TUB (1994), and Doctor of the HAS (2004).
In 1995, she became the head of the Department of Food Engineering at Szent
Istvan University, Budapest and where she worked in the field of membrane science
and application. The main focus of her research is wine, fruit juice, and drinking
water production using different mild and cheaper membrane methods. Her research
has been published in 83 English and 33 Hungarian scientific papers and books, 89
international congress full papers, and 242 proceedings. In 2001, she was awarded
by the Ministry of Agriculture for the industrial applications of her patents. In 2009,
she received the Gold Merit Cross of the Hungarian Republic. Currently, she works
as a professor emerita at Szent Istvan University, Budapest.
Frank Lipnizki earned his BEng (Hons) in manufacturing and management from
the University of Bath, United Kingdom in 1995; diploma in mechanical engineer-
ing from the University of Bochum, Germany in 1996; PhD in chemical engineer-
ing from the University of Bath, United Kingdom in 1999; and post-doc in food
engineering from Lund University, Sweden in 2000. He is a business/product and
xi
xii Editors
a ssociated R&D manager at Alfa Laval—Business Centre Membranes, Denmark

since 2001, and an adjunct professor of chemical engineering at Lund University,
Sweden since January 1, 2014.
His main research interests are the integration and optimization of membrane
process for the food, biotech, and process industry. He has authored more than
30 publications in reviewed journals and books and more than 90 contributions in
international conferences and workshops on membrane technology.
Gyula Vatai qualified as a chemical engineer, with specialization in process

engineering, from the Faculty of Technology, University of Novi Sad, Novi Sad,
Yugoslavia in 1975. He earned his PhD in technical sciences from the Faculty of
Technology, University of Novi Sad, Novi Sad, Yugoslavia in 1986; candidate of
Chemical Sciences from the Hungarian Academy of Sciences in 1995; Dr Habil from
the University of Horticulture and Food Industry, Budapest in 1999; and Academy
Doctor of Agricultural Sciences degree from the Hungarian Academy of Sciences
in 2010. He is a university professor since 2000 and the head of the Department
of Food Engineering, Faculty of Food Science, Szent Istvan University, Budapest,
Hungary. He is one of the founders of the educational structure of the process
engineering branch. He is also the head of the Food Science Doctoral School,
teaching and s upervising PhD students.
He has made significant achievements in the elaboration of hydrodynamics and
mass transfer in bioreactors, liquid–liquid extraction, and membrane separation
processes. His research is focused on the application of membrane technology in
drinking water treatment, edible oil filtration, fruit juice concentration with c omplex
membrane processes, and waste water separation as well as modeling of mass trans-
fer in membrane separation processes. He has authored more than 200 scientific
papers, of which 130 papers are in English with more than 1000 citations. He is the
author of eight chapters in technical books (membrane applications) in English. He is
a member of several national and international research organizations.
Contributors
Erika Bekassy-Molnar Frank Lipnizki
Department of Food Engineering Alfa Laval Business Centre Membranes
Szent Istvan University Nakskov, Denmark
Budapest, Hungary
and
Enrico Drioli
Institute on Membrane Technology Department of Chemical Engineering
University of Calabria Lund University
Rende, Italy Lund, Sweden
Robert Field Edit Marki

Department of Engineering Science Department of Food Engineering
University of Oxford Szent Istvan University
Oxford, United Kingdom Budapest, Hungary
Geneviève Gésan-Guisiou
R. Mazzei
STLO, Science and Technology of
Institute on Membrane Technology
Milk and Eggs
University of Calabria
INRA, French National Institute for
Rende, Italy
Agricultural Research
Rennes, France
Emma Piacentini
Lidietta Giorno Institute on Membrane Technology
Institute on Membrane Technology University of Calabria
University of Calabria Rende, Italy
Rende, Italy
Gyula Vatai
Andras Koris Department of Food Engineering
Department of Food Engineering Szent Istvan University
Szent Istvan University Budapest, Hungary
Budapest, Hungary
xiii
Section I
Basic Principles of
Membrane Processes
1 Membrane Separation
Processes
An Overview
Robert Field and Frank Lipnizki
CONTENTS
1.1 Background........................................................................................................4
1.2 Introductory Remarks........................................................................................ 6
1.3 Membrane Processes.........................................................................................8
1.3.1 A Chemical Engineering Perspective....................................................8
1.3.2 Basic Concept of Membrane Processes.................................................9
1.3.3 Basic Modes of Operation................................................................... 15
1.4 Membrane Classification................................................................................. 16
1.4.1 Basic Classification of Membrane Processes...................................... 16
1.4.2 Microfiltration...................................................................................... 17
1.4.3 Ultrafiltration....................................................................................... 17
1.4.4 Reverse Osmosis.................................................................................. 18
1.4.5 Nanofiltration....................................................................................... 18
1.4.6 Dialysis................................................................................................ 19
1.4.7 Nonporous Membrane Processes......................................................... 19
1.4.8 Activity-Driven Nonwetted Membrane Processes............................... 19
1.5 Membrane-Related Aspects of Physical Chemistry........................................ 19
1.5.1 Osmotic Pressure................................................................................. 19
1.5.2 Vapor Pressure..................................................................................... 22
1.6 Membrane Materials, Type, and Structures.................................................... 22
1.6.1 Membrane Classification..................................................................... 23
1.6.2 Inorganic Membranes.......................................................................... 23
1.6.3 Polymeric Membranes.........................................................................24
1.6.3.1 Chemical Structure of Polymers...........................................25
1.6.4 Electrodialysis Membranes.................................................................. 27
1.6.5 Membrane Morphology....................................................................... 27
1.7 Membrane Modules.........................................................................................28
1.8 Membrane Systems.......................................................................................... 33
1.8.1 Basic..................................................................................................... 33
1.8.2 Overview of UF Diafiltration..............................................................34
1.8.3 Layout of Membrane Systems............................................................. 35
3
4 Engineering Aspects of Membrane Separation
1.8.4 Membrane Process Design.................................................................. 37

1.8.5 Prediction of Required Membrane Area............................................. 38
1.9 Summary......................................................................................................... 39
References................................................................................................................. 39
1.1 BACKGROUND
The food industry, which is a major worldwide industry, is going through a revolu-
tion. Changing lifestyles and expectations, such as demand for fewer additives, have
placed new demands on the industry, which can only be met by new technology.
At the same time, the producers in this very large industry have a further chal-
lenge, namely, that of the countervailing power of the retailer. Some years ago,
J.K. Galbraith forecasted that the rise of purchasing power by large conglomerates
would match the monopoly power of the producing industries. In the food industry,
this has already occurred, and even 25 years ago in the United Kingdom, five or six
major retailers controlled nearly 80% of the UK market (Field and Howell, 1989).
Thus, it is essential that producers design, install, and maintain first-class produc-
tion systems.
Process engineers have brought skills developed in highly automated and con-
trolled processing industries to the food industry. They have not attacked the prob-
lem by chemically processing food but, for example, by designing and developing
processes that allow the natural reactions that take place in food while it is being
cooked to occur in a controlled manner, thus ensuring that all the food is eventu-
ally cooked (or chilled) so that bacteria and other spoilage organisms are removed,
have access denied or are killed. At the same time, the dynamic development of the
membrane separation process is striking. In the last 15–20 years, they have moved
from having mostly niche applications to becoming in many cases the accepted new
standard for many separation processes. Even though membrane processes are a
relatively new type of separation technology, unknown to the general public, several
membrane processes such as reverse osmosis (RO), gas separation (GS), ultrafiltra-
tion (UF), and microfiltration (MF) are already applied extensively on an indus-
trial scale. Also, more and more segments of the technical industries are gradually
using the continuously growing repertoire of membrane-based processes. While the
growth in the applications of membranes for water treatment has been dramatic in
the last 20 years, the applications in the food and beverage industry has been steadier
and goes back somewhat further. Indeed, a food process engineering book from 1975
(Leniger and Beverloo, 1975) includes a short section on membrane processes within
a section on concentration for food preservation.
Concentration by membranes is now an energy-attractive alternative to evapora-
tion because membrane processes have, in general, a modest energy requirement
albeit a requirement of high-grade energy such as electrical energy. The membranes
operate at ambient temperatures, and beverages retain a fresh raw flavor. Such mem-
branes can often process juices to a marketable concentrate without further concen-
tration; see Chapter 5. Furthermore, their application for sterilization improves shelf
life. In the dairy industry, UF membranes are used to remove water prior to cheese
Membrane Separation Processes 5
or yogurt making and thus allow more of the solids present in the milk to reach the
final product and also retain flavor components that might be lost during heating; see
Chapter 4 for details. Moreover, membranes have an environmental advantage over
the conventional processes that they replace not only because they are less energy
intensive but as noted as early as 1976 by Meares (1976), they produce as waste
products only the unwanted components in their feed streams and, far from increas-
ing pollution, membranes can be used to control pollution by treating waste streams
from manufacturing processes. Bearing in mind mankind’s belated consciousness
about the need to conserve fuels and preserve its environment, the probability of
membranes playing an increasing role will continue and increase.
In the preindustrialization period, man used natural membranes from animals,
including intestines and stomachs, for filtration and storage. Indeed, Abbé Nollet
discovered the phenomenon of osmosis in natural membranes (Nollet, 1748) after
studying the storage of “spirits of wine” in vessels, the mouths of which were sealed
with pigs’ bladders. These vessels were immersed in water. As the bladder is more
permeable to water than wine, the bladder swelled and sometimes even burst, dem-
onstrating semipermeability for the first time. For the nineteenth century, Lonsdale
(1982) noted the key scientific works of relevance to membranes as being Fick’s work
on the laws of diffusion in 1855, the work of Graham in the 1860s on dialysis and gas
permeation, and that of Traube and van’t Hoff on osmotic pressure in 1860 and 1887.
Microporous membranes were studied by Zsigmondy and Bechold (who introduced
the term “ultrafiltration”) in the early 1900s. By the 1920s and 1930s, nitrocellulose
membranes were commercially available for laboratory use. The leading company
was Sartorius-Werke in Germany. In World War II, important applications emerged
in the area of public health with the key developments being in Hamburg. However,
German domination of the membrane industry passed directly to the United States
after World War II and contributed to their biotech boom; the reason being that
membranes can be used for sterilization and for separation under quiescent condi-
tions. Thus, in the 1950s, membranes started to find applications outside the labora-
tory (Böddeker, 1995). In the 1950s, ion-exchange resins became available in sheet
form for the first time and this led to the development of electrodialysis (ED), the
first membrane process to be operated at industrial scale for civilian use. Today, ED
is very widely used for de-ashing whey, where the desalted product is a useful food
additive, especially for baby food (Eykamp, 1999).
However, other potential membrane separation processes were largely noncompet-
itive at that time because fluxes were low due to membrane thickness and separation
performance was relatively poor. It is most important to ensure that the membranes
are sufficiently strong to withstand the operating pressures, but for decent fluxes,
the membrane needs to be thin. These conflicting objectives were not resolved until
the late 1950s and early 1960s when Loeb and Sourirajan developed the asymmet-
ric integrally skinned cellulose acetate (CA) RO desalination membrane. This is
arguably the key event that started academic and commercial interest in membrane
separations. Once they had shown that it was possible to make membranes that
were capable of desalting seawater with reasonable fluxes (a two order of magnitude
improvement on previous membranes), the concept of membrane separations was
rapidly taken up by commercial producers (Fane, 2008). Effective modularization
of membrane units followed and this was also a key advance. Thus, membranes are
a product of the second half of the twentieth century. More will be said about this
development in Section 1.6 on membrane materials.
In the second and main section of this book, the applications examined include
dairy industry and animal products processing (Chapter 4); wine production using
membranes where clarification and sterilization are important (Chapter 5); fruit
and vegetable juice processing applications (Chapter 6); sugar and starch process-
ing (Chapter 7); vegetable oil production (Chapter 8); and membrane bioreactors
for the enzymatic hydrolysis of whey proteins, pectin, and starch (Chapter 9). For
these applications, the reducing cost of membrane processes, as well as their other
advantages, has greatly helped in the competition against conventional separa
tion processes such as evaporation, distillation, extraction, and adsorption. The
reader familiar with membrane processes might like to read about applications in
Section II before returning to Section I on membrane processes, membrane charac-
teristics, and membrane fouling.
Membrane processes are already used in a wide range of applications and several,
particularly the pressure-driven ones such as UF and MF are already well estab-
lished in food and beverage processing on an industrial scale. These processes might
be labeled as membrane filtration but for reasons to be explained shortly, the term
“membrane separation” is to be preferred. Muralidhara (2010) has recently noted,
while writing about membrane applications in the food industry, that various micro-
filters account for around 60% of the current membrane market (and sales) with
UF and RO each having around 17%. The remaining 8% is shared between various
other membrane processes, including pervaporation (PV). In all these areas, except
PV, it was noted that there has been double digit growth over the last 30 years. PV
has a niche market in the drying of ethanol and isopropanol for reasons explained in
Chapter 3 and for some applications such as aroma recovery, it remains a “promising
technology” but development of applications in the food industry have not material-
ized to the extent originally expected.
1.2 INTRODUCTORY REMARKS

The 1960s saw the development of RO (asymmetric CA) and polytetrafluoroethylene
(PTFE) membranes together with new module types such as the first commercial
hollow fiber systems. Then, from the 1970s to the end of the century, a number
of additional membrane materials, including polyacrylnitrile (PAN), polyvinyla-
dinefluoride (PVDF), polysulfone (PS), polyethersulfone (PES), polypropylene, and
polycarbonate, as well as the thin-film RO membrane, were introduced and there was
continued innovation with regard to modules as well.
Membrane separation processes can be used for a wide range of applications
and can often offer significant advantages over conventional separation such as
distillation and adsorption since the separation is based on a physical mechanism.
Compared to conventional processes, no chemical, biological, or thermal change of
the component is involved for most membrane processes. Hence, membrane separa-
tion is particularly attractive for the processing of food, beverages, and bioproducts
where the processed products can be sensitive to temperature (putting distillation at
a disadvantage) and solvents (putting extraction at a disadvantage). Many advantages

have been cited for membrane technology (Luque, 1999), including
1. Lower cost
2. Higher selectivity and fewer undesirable by-products since no additives are
required
3. Simplicity compared with alternatives
4. Ability to have a continuous process
5. Energy consumption is lower generally (PV and membrane distillation
[MD] are the only membrane processes involving a phase change)
6. Separation can be carried out under mild conditions
7. Scaling up is easy
8. Membrane properties can be tailored to a specific application
Whether membrane processes are simpler than alternatives depends upon the
comparison being made and whether one is looking at the process per se or whether
one is including the cleaning of the equipment. With regard to bioseparations in the
pharma industry, it is correct to say that UF is simpler than the alternatives in the
industry, namely, chromatography, electrophoresis, and affinity separations. Also, in
comparison with these separation techniques, UF is a high-throughput process and it
can combine concentration and purification in one step. However, for the main parts
of the food and beverage industries, these separation techniques are irrelevant and
membrane techniques compete with traditional unit operations such as sedimenta-
tion, rotary vacuum filtration, and evaporation. Compared with these techniques,
membrane systems are readily cleaned and sanitized but overall the separation pro-
cess per se is not guaranteed to be simpler.
Linking to the above points are some disadvantages. Regarding point 7, scaling
up is easy because the membrane units themselves scale linearly and so the sav-
ings per unit of product that are generally found as one moves to a larger scale are
diminished in the case of membrane processes. The auxiliary items such as pumps
scale in the normal manner and so the overall plant cost for a membrane unit is not
linear. Overall capital costs of membrane processes scale with throughput to their
size raised to the power of 0.8, whereas for the process industries in general, the
index is 0.6. Thus, for a 10-fold increase in plant size, there is normally a 60% saving
compared with the cost that would be incurred if the scale-up were linear, but for
membrane plants, it is probably around 35%.
A second disadvantage is that membrane fouling alters the membrane perfor-
mance not only by changing the hydraulic characteristics (i.e., more pressure is
required for the same flux or there is less flux for the same pressure difference) but
also by changing the separation characteristics of the membrane. So what appears to
be simple may not be as simple as first thought.
Regarding point 1 on cost, there is generally a lower cost as far as operating costs
are concerned but probably a higher capital cost. As membrane costs have reduced
during the twenty-first century, and as energy costs will continue to increase, mem-
brane processes will increasingly find favor. Membrane lifetime has been a problem
in the past because membranes for some applications had a lifetime of less than
12 months. In the food industry today, polymeric membranes last typically 2–3
years, while ceramic membranes can last around 5 years.
While the ideal membrane process, like most ideal processes, offer simplicity,
the operation of membrane processes often requires know-how due to the complica-
tions of fouling. With process fluids and industrial timescales (as opposed to ideal
laboratory solutions and relatively short test times), fouling of membranes can be
considered to be inevitable. Membrane fouling is the combined effect of a number of
physical, chemical, and biological processes that all lead to a decrease in the perme-
ability of the membrane and a change in its separating characteristics. As a result of
the increasing resistance to fluid flow, a higher pressure is required if throughput is to
be maintained (or for the same initial pressure, throughput will decrease). The higher
resistance will also inhibit passage of molecules that were initially passing through
and this may or may not be important. Fouling is the main topic in Chapter 2. The
four main disadvantages of membrane processes are
1. Membrane fouling
2. Inherently low throughputs per unit area of membrane (and hence the need
to pack large areas into a given volume)
3. Low membrane lifetimes (but these are improving)
4. Lower economy of scale than traditional processes
1.3 MEMBRANE PROCESSES

Initially, membrane processes will be viewed as a set of unit operations for separa-
tion. Thus, after an introduction to this viewpoint, the processes of RO, UF, and MF
will be introduced. This is followed by a brief section on membrane materials.
1.3.1 A Chemical Engineering Perspective

Chemical engineering is the science and art of converting raw materials into use-
ful products, in a way that is economical, safe, and sustainable. It started in the
nineteenth century, with the insight of men like George E. Davis, who saw that put-
ting together a safe and efficient collection of equipment to make a chemical prod-
uct was not just a matter of applying some mechanical engineering know-how to a
laboratory-scale chemical process. The same epistemological approach can be used
when making/processing food, distilling whiskey, separating crude oil into useful
products, producing pure water or enriching uranium. So, what started as “chemical
engineering” is now frequently known as “process engineering” because the ideas
and methods are applied far more widely than in the chemical industries. The pro-
cesses used for separation have become more numerous as well as more widespread.
One of the “less common means” of separation used to be membrane processes but
now they can be considered mainstream.
At the heart of chemical and process engineering is the design and operation of
processes that change the thermodynamic state, composition, morphology, or other
characteristic of materials. The important constraint on any process is the specifica-
tion of the products that needs to be met. The specification will be set in terms of
purity and other features, including color, viscosity, appearance, and temperature.
Besides the desired products, there will be waste products and a plant design will
need to include consideration of how waste streams are to be handled (e.g., recycled,
converted to a useful by-product, or disposed of in some way).
While there are membrane reactors, this introduction will confine itself to mem-
brane separations and then the change is just one of composition with a feed stream
being separated into two streams—one that has passed through the membrane and
one that has been retained above it. So a membrane is a device that achieves a cer-
tain separation and is operated at a certain rate. A basic classification of membrane
processes is given shortly, followed by a brief examination of membrane materials
after which the various types of membrane modules are introduced. This chapter
concludes with a brief consideration of membrane systems.
1.3.2 Basic Concept of Membrane Processes

A membrane is a thin perm-selective barrier between two fluids. In over 95% of
applications of current industrial interest, the membrane is formed from a polymer
either by spinning fibers, or by coating tubes or flat sheets, or by casting a film. Some
might say that a membrane is a thin film-like porous structure separating two fluids
but it is not necessarily porous. As discussed later, RO membranes and GS mem-
branes operate on a solution-diffusion basis and are not truly porous. UF and MF
membranes have well-defined pores and can be viewed as thin filters that under pres-
sure allow some molecules and/or particles to pass while retaining larger material.
So, for these membranes, the concept of membrane separation is relatively simple; it
is one of size exclusion.
Membranes (Latin: membrana = thin skin) might be described as filters like a
coffee filter but some membranes separate molecules and for this reason the term
“membrane separation” is to be preferred to the term “membrane filtration.” This
is especially true for those membranes that do not have pores! In general, one can
divide membranes into two groups: porous and nonporous. The former group is sim-
ilar to classical filtration; the separation of a mixture is achieved by the rejection of at
least one component by the membrane and passing of the other components through
the membrane. In comparison to filtration, membrane processes can separate par-
ticles with diameters in the range of μm down to nm, while classical filtration is
commonly restricted to particle diameters greater than a few μm. As already noted,
the membranes need not be porous and this group will be discussed more in Chapter
3. However, it is important to note that nonporous membranes do not operate on a
size exclusion mechanism. Table 1.1 indicates how membrane processes can be clas-
sified while Figure 1.1 compares a number of membrane processes with conventional
processes on the basis of physico-chemical separation mechanism and size of spe-
cies being separated. Hemodialysis is one of the major applications for membranes
in terms of membrane area produced and also in terms of monetary value. However,
any discussion of this medical application will distract from our concentration on
those membrane processes of interest to the food industry.
As with conventional separation processes, a membrane separation process can
be evaluated by two important parameters—one linked to the degree of separation
TABLE 1.1
Classification of the Most Common Membrane Processes
Nonporous Porous
Pressure-driven a Reverse osmosis (RO) Ultrafiltration (UF), microfiltration (MF)
Partial-pressure driven or Gas separation (GS), Dialysis including hemodialysis,
concentration differenceb pervaporation (PV) membrane distillation (MD)
Electrically driven Electrodialysis (ED)
a For UF and MF membranes, separation performance is determined by size exclusion mechanism.

b The link between “activity,” which is a thermodynamic term, and these driving forces will be made later.
and the other to productivity. The latter is characterized by the parameter, permeate
flux, which indicates the rate of mass transport through unit area of the membrane
(i.e., amount per unit area per unit time). The former is characterized by a selectivity
measure. To explain the key concepts of flux and selectivity, it is useful to consider a
stirred cell. Although these systems, such as the Amicon® stirred cell, are mainly to
be found in the laboratory and are typically operated batchwise, one can conceptu-
ally consider them to be operated continuously. In Figure 1.2, the liquid feed enters
the top part of the cell and the retentate is withdrawn from the same chamber. Some
of the feed stream passes through the membrane and into the lower chamber. This
stream is called the permeate or filtrate. If the feed contains species A (say a protein)
and species B (say cells), the aim may well be to transfer as much of A through the
membrane as possible while retaining all of B above the membrane. If the concentra-
tion of A in the feed is CbA (where CbA is the concentration of A in the bulk solution)
and CpA is the concentration in the permeate, then the observed selectivity for A, SoA,
is defined as
C pA
SoA = (1.1)
CbA
Related to selectivity, one finds the concept of observed rejection coefficient, RoA,
which is defined as
C pA
RoA = 1 − (1.2)
CbA
The reason for mentioning “observed” rejection coefficient will be made apparent
in Chapter 2 when a contract between “observed” rejection coefficient and “intrin-
sic” rejection coefficient is made. In our example, the specification is for the com-
plete rejection of species B and so for component B, the expected value of RoB would
be unity. If in practice, this were not found to be the case, then either the specification
of the membrane would be wrong or either the membrane would have a pinhole or
the sealing of the edges of the membrane within the holder/module would be at fault.
Principal mechanism causing separation processes
Microfiltration
Cloth and depth filters
Size Ultrafiltration
Screens and strainers
Nano- Gel chromatography
filtration
Reverse
Diffusion osmosis
Dialysis
Ionic charge Ion exchange
bonding
Electrodialysis
Phase change Distillation, freeze separation
Membrane Separation Processes
Solubility Solvent extraction

Surface phenomenon Foam and bubble fractionation
Ultracentrifuges Hydrocyclones
Density Centrifuges
Clarifier gravity sedimentations
Particle size 10–4 10–3 10–2 10–1 1.0 10 102 103

(Microns)
Particle size 1 10 100 1000 10,000 100,000 106 107
(Angstroms)
Approximate 100 200 20,000 500,000

molecular weight
Ionic Macromolecular Micron Fine Coarse
range range particle particle particle
range range range
FIGURE 1.1 Applicability range of membrane and conventional processes. (After Rautenbach, R. and Albrecht, R. 1993. Membrane Separation
11
Processes. John Wiley, New York.)

Feed
In-cell
concentration Cb
Retentate, CR
Permeate, Cp
FIGURE 1.2 Stirred cell membrane system. With efficient stirring, Cb in the stirred cell is
the same as CR at the outlet.
Occasionally, one might find that the term “retention” has been used instead of
“rejection” and these can be considered to be interchangeable. A third term “reflec-
tion” is used in irreversible thermodynamic descriptions of membrane separations
as a measure of solute–solvent coupling. It is not relevant for the matters considered
in this book.
In addition to achieving an appropriate selectivity, one needs an appropriate pro-
ductivity, the main measure of which is volumetric flux, J, which is the throughput
per unit area of membrane. Typical units are liters per m2 per hour. One can readily
show that 36 liters per m2 per hour (which is a typical flux in many UF systems) is
equivalent to 10 μm/s. This clearly indicates the relatively low rate at which mem-
branes operate and the importance of packing a large membrane area within a given
volume in order to have reasonably sized equipment.
Qp
J= (1.3)
A
where Qp is the volumetric flow rate of permeate and A is the area of the membrane.
For a clean solvent, the flux depends linearly on both the membrane permeability
and the driving force, which is generally the pressure difference across the mem-
brane. However, the presence of solutes and particles alters this as we shall see later.
It is essential to ensure that the membranes are sufficiently strong to withstand the
operating pressures, but for decent fluxes, the membrane needs to be thin. These
conflicting objectives were resolved in the late 1950s and early 1960s when Loeb and
Sourirajan (1960, 1963) developed an asymmetric membrane that has a very dense
thin skin to achieve the separation and an underlying and integral substructure to
provide the mechanical support.
Feed Retentate
(A + B + solvent) (A + B + solvent)
Permeate
(A + solvent)
FIGURE 1.3 Schematic of a single stage in a membrane process. Note that the retentate will
contain all of the feed components.
For the stirred system shown in Figure 1.2, the volume of the feed solution above
the membrane is assumed to remain constant at the initial volume V0. If the rejec-
tion characteristics of the membrane remain constant, the concentration of species
A in the permeate stream remains as CpA = SoA · CbA. The point made by Figure 1.3
is that while the permeate can be free of species B, there will be species A and B in
both the retentate and the permeate streams. Thus, the feed stream to a membrane
module is split into two streams: (i) the retentate that is retained by the membrane
and (ii) the permeate that has passed through the membrane. The latter will contain
little or none of the larger molecules or particles but the former contains both the
material that has been rejected by the membrane, often on the basis of size, and also
a significant quantity of smaller material that would not pass through the membrane
but, as some have said, has yet to be given the opportunity to do so. However, as
an R value of zero (i.e., S = 1) corresponds to equal concentrations on both sides of
the membrane, retention of solvent will always lead to retention of at least a cor-
responding amount of small solutes unless the separation process is more than size
exclusion, which in UF and MF it is not. Thus, to achieve a low concentration of
solute in the retentate, it is necessary to wash the solute through by adding water
in a staged process. This is known as diafiltration, which is discussed at the end of
this chapter.
To achieve the flux, there has to be a driving force. The transport processes across
the different types of membrane are illustrated in Figure 1.4. Based on three differ-
ent types of separation mechanism, namely, (i) sieving mechanism, (ii) solution-dif-
fusion mechanism, and (iii) ion-exchange mechanism, there are three basic driving
1 2 3 +
– –
–
+ – –
–
Feed Permeate Feed Permeate Feed – – Permeate
–
+ –
FIGURE 1.4 Membrane separation mechanisms: sieving mechanism (1), solution-diffusion

mechanism (2), and ion-exchange mechanism (3).
forces: pressure differences, activity gradients, and electrical potential, giving three
essentially distinct transport processes. At a detailed level, the different driving
forces might sometimes act together and jointly influence the performance.
The pore diameters are between 0.1 and 2 μm for MF membranes and between
2 and 100 nm for UF membranes. Thus, the separation mechanism is based on the
pore diameter. Particles and molecules with a diameter greater than the pore diam-
eter cannot pass through the membrane. (As noted later, there will in any system be
a range of pore diameters about a mean pore size.)
The solution-diffusion mechanism is the basic principle for the separation of
nonporous membranes. The model was originally developed by Graham (1866) to
describe the gas permeation through rubber septa but is also relevant for the diffusion
of liquids, vapors, and gases. The solution-diffusion mechanism can be described in
three steps (Wijmans and Baker, 1995):
1. Partitioning of the components in the feed stream between the feed stream
itself and the upstream side of the membrane
2. Diffusion of the permeates through the membrane
3. Desorption of the permeate on the downstream side of the membrane
Based on the solution-diffusion mechanism, molecules of equal size or larger

molecules from smaller molecules can be separated because the quality of the sepa-
ration process depends not only on the diffusion through the membrane but also
on the solubility of the molecules into the membrane material and therefore on the
nature of the membrane material itself. For example, organic molecules such as ben-
zene are transported from one side of a rubbery membrane to the other at a greater
rate than water because organic molecules partition into the rubbery membrane to
a far great extent than water. Individual water molecules might on average diffuse
at a similar rate (or indeed faster rate) than benzene molecules but because there
are many more benzene molecules entering the membrane per unit time, the overall
transport of benzene is a lot greater.
The ion-exchange mechanism can be combined with both types of membranes:
porous and nonporous. This type of separation membrane rejects ions of similar
charge. Cationic exchange membranes are therefore made from static polyanions.
Anionic exchange membranes are made from static polycations. The quality of the
separation process is based on both the general membrane type as well as the ions
in the membrane. The first membrane process separating small molecules to reach a
practical scale in the commercial sector was that of ED when the sheet form of ion-
exchange resins became available in the 1950s. For desalination, it was in general
competition with RO around 40 years ago. But today, with regard to this application,
it is used to remove salts from brackish water, where feed salinity is around 0.05%–
0.5% but it does not compete with RO in the seawater desalination market. (Seawater
has a salinity of around 3.5%.) There is one paradoxical exception mentioned by
Eykamp (1999); in Japan, ED is used, by law, to concentrate seawater from 3.5% to
20% salt in order to produce essentially all of its domestic table salt. The ED pro-
cess with special membranes enables selective removal of divalent ions while also
achieving concentration of monovalent ions. Away from desalination, ED has some
applications in the removal of salts from food, dairy, and other products streams, and
some waste streams. By removing unwanted salts, it can prevent the buildup of total
dissolved solids in product streams.
1.3.3 Basic Modes of Operation

Today, pressure-driven membrane processes are operated in three different modes:
dead-end, cross-flow, and direct-flow. In the dead-end mode, one stream of the feed
enters the membrane module and only one stream, the permeate/filtrate, leaves
the membrane module. In the cross-flow mode, the feed flows tangentially to the
membrane surface, and there are two streams leaving the membrane module—the
retentate and the permeate (as shown in Figures 1.2 and 1.3). The dead-end mode is
employed mostly in MF for clarification and sterilization, where the feed is relatively
clean. Indeed, for air filtration, the buildup of a small amount of “cake” plus the
probable blockage of the odd oversized pore means that performance (measured in
terms of log removal of bacteria) improves after a little use. In most applications,
the cross-flow mode of operation has been adopted so that passage of the desired
material into the permeate is not inhibited by the continual buildup of material at
the membrane surface; the tangential flow provides a scouring action that limits the
accumulation of rejected species at the membrane surface and thereby the permeate
flux is maintained at acceptable levels. Schematic diagrams of dead-end mode and
the cross-flow modes are given in Figure 1.5. In the dead-end mode, the flow through
the membrane is orthogonal. Particles rejected by the membrane buildup form a
deposit layer (often called a cake layer) on top of the membrane surface. The thick-
ness of this cake layer increases with time and leads to a decreasing flux, assuming
a constant pressure operation. Thus, fluxes will asymptote toward zero. By contrast,
in cross-flow mode, the feed flow is parallel to the membrane surface and due to
the removal of material, the cake layer’s thickness is limited by a balance between
material arriving and being removed. Thus, the flux tends, in general, toward a finite
nonzero value. Direct flow is considered later in Section 1.7 on membrane modules.
(1) Feed (2)
Feed Retentate
Filter cake Membrane Permeate

Membrane
Permeate
FIGURE 1.5 Schematic comparison of (1) dead-end and (2) cross-flow modes.
In pressure-driven membrane separation, the driving force is of course the pres-

sure, or to be more precise the pressure difference between the upstream and down-
stream sides of the membrane; that is, to say between the feed and the permeate. This
pressure difference is referred to as transmembrane pressure (TMP). The pressure
on the feed side of the module will vary because of the cross-flow and the resulting
pressure drop in the module, and so TMP is given by
( PF − PP )in + ( PF − PP )out
TMP = (1.4)
2
where “in” refers to the feed inlet of the membrane module and “out” refers to the
feed outlet end.
1.4 MEMBRANE CLASSIFICATION

1.4.1 Basic Classification of Membrane Processes
Expanding Table 1.1 slightly, it is generally accepted that there are now four major
pressure-driven membrane processes—the classical ones being RO, UF, and MF.
To these there has been added nanofiltration (NF), which can be considered to be
loose RO or tight UF. Now, rather than mentioning a pore size for all of these types,
which is misleading, it is useful to divide membranes into two types based upon the
structure, namely, porous membranes and nonporous membranes. A schematic rep-
resentation of these two types was shown in Figure 1.4, which clearly suggests a siev-
ing mechanism for porous membranes. This is mainly correct for MF and UF where
charge effects are generally minor. However, charge effects have a more important
influence on NF performance, and their separation characteristics should never be
considered to be based only on size exclusion (i.e., sieving).
The IUPAC (1985) definition of pore sizes is as follows:
• Macropores >50 nm
• Mesopores 2–50 nm
• Micropores <2 nm
Using this definition, MF membranes contain macropores as the pore size range
is typically 0.05–2 µm, and UF membranes contain micropores. Some scientists
(e.g., Mulder, 1996) consider NF and RO membranes to be intermediate between
porous UF membranes and nonporous GS membranes noting that the term “nonpo-
rous” is rather ambiguous because in GS and PV membranes, pores are present at
the molecular level. Transport through these dynamic molecular pores is adequately
described in terms of free volume. It is thus more accurate to see porous membranes
as permanently porous membranes and nonporous ones as dense membranes with
nonpermanent pores but such a description is likely to be considered too wordy for
everyday use.
1.4.2 Microfiltration
MF is used in analytical procedures and in production. In the former case, it will be
a dead-end mode, while in the latter case, it will generally be in cross-flow or direct-
flow mode. Two exceptions of industrial interest are the use of the dead-end mode for
air sterilization and for final guard filtering on a bottling line. In these applications,
MF is used for the removal of microorganisms and the loading (amount of cells per
unit volume) will be extremely low. Other typical uses of MF are to remove suspended
solids (e.g., cells and cell parts) from a stream and to concentrate a feed stream. Apart
from the latter, the permeate is the product and it will be free of fragments (as well as
particles and cells), which is not always the case with conventional filters.
The main applications are
• Removal of particles from liquid and gas feed streams (e.g., MF in milk
processing to remove fat globules and bacteria)
• Removal of particles (polishing) from liquid product streams (e.g., bottling
of beer)
• Clarification and sterile filtration of heat-sensitive solutions/beverages (e.g.,
apple juice)
• Wastewater treatment (e.g., membrane bioreactors)
MF membranes are given an absolute rating typically based on the diameter of

the largest pore on the membrane’s surface. The TMP can be below 1 bar. While the
range is often quoted as being from 1 to 10 bar, operation in the lower half of the
range is now more common and operation below 1 bar should always be considered
for reasons explained in Chapter 2. In addition to pore size, MF membranes are
characterized by their permeability, which is generally described by the pure water
flux at a TMP of 1 bar. This permeability is rarely maintained with process fluids.
1.4.3 Ultrafiltration
UF membranes contain much smaller pores than MF membranes and thus UF
membranes are able to reject macromolecules in the range 103–106 Da, the actual
value depending on how they are manufactured. Solvents and low-molecular-weight
solutes will pass through the membrane while larger molecules are retained. The
molecular weight cut-off (MWCO) values are only approximate because first there
are a range of pore sizes in the membrane surface and second there is not a unique
relationship between the molecular mass of macromolecules and their size owing to
their size depending upon the macromolecules used, the solution pH, and its ionic
strength. The nominal rating is commonly defined as the molecular weight of the
smallest species that is more than 90% rejected.
UF permeability is generally described by pure water flux at 1 bar TMP but the
permeability in practice will depend greatly upon the degree of fouling and it can
be an order of magnitude or more smaller than the pure water permeability. Typical
TMPs for UF are 1–10 bar, typically in the upper half of this range. An example of
UF in the beverage industry is their use for the clarification of apple juice. While
polymeric membranes are more widespread today, ceramic membranes are an alter-
native that are becoming increasingly popular.
1.4.4 Reverse Osmosis
RO membranes exclude essentially all solute species, both organic and inorganic, and
very little but the solvent passes through into the permeate. The rejection coefficients
for RO membranes exceed 99%. The mechanisms of separation relate not only to
shape and size but also to ionic charge and in interaction between the species and the
membrane. Overall, the mechanism leads to a thermodynamically controlled partition
between the liquid streams and the membrane, analogous to solvent extraction, and so
the term “hyperfiltration” (which some use as a pseudonym for RO) is to be avoided.
Small neutral solutes may permeate to a small extent through RO membranes. Now,
it will be readily appreciated that the exclusion of small-molecular-weight material
necessitates a denser top layer (compared with UF) and that the resistance of this layer
to solvent flow will be relatively high. Furthermore, the exclusion of salts will lead to
a countervailing osmotic pressure opposing the applied TMP. Thus, the net driving
force for solvent flow is the difference between these two pressures. As seawater has
an osmotic pressure of 25 bar, the TMP in seawater RO units has to exceed this value
significantly and a typical value of the TMP is 40–60 bar.
An example of RO use in the beverage industry is their deployment for the con-
centration of juices. RO is chosen as sugars and flavors need to be retained. The
achievable upper concentration limit is strongly influenced by the osmotic pressure
of the juice, which increases with measuring concentration. As the product is the
retentate, a reduced residence time is preferred as it gives a better-quality product.
The implication of this is that a particular process design is to be preferred; feed-and-
bleed configurations with two or three stages are preferred to batch recycle systems.
The feed-and-bleed configuration will be described in Section 1.8.
1.4.5 Nanofiltration
This process is similar to RO in that there is significant rejection of ions but as
the rejection of sodium chloride is typically only 60%, it will be readily appreci-
ated that NF has capabilities intermediate between RO and UF. The more open NF
membranes are typically dense composite membranes, while the more closed NF
membranes are thin-film composite membranes. With regard to the rejection of other
ions, typical values would be 80% for sodium bicarbonate and 98% for MgSO4.
Values for glucose and sucrose can be around 95% as well. One application in the
dairy industry is the processing of salty cheese wheys.
The separation mechanisms in UF as well as MF are mainly that of size exclusion,
which is indicated by the nominal size-based ratings of the membranes. Electrostatic
interactions between solutes and membranes, which depends on the surface and
physiochemical properties of solutes and membranes, can be important for UF
(mainly, but not exclusively, through their influence on fouling) and are certainly
important for NF. So, NF separation characteristics should not be considered to be
based only on size exclusion (i.e., sieving) alone. Thus, in the membrane literature,
one finds use of the Nernst–Plank equation to describe the combined influence of
a concentration gradient and an electric field upon the movement of ions; it is an
extension of Fick’s law of diffusion to include the influence of electrostatics. It was
used by Van der Horst et al. (1995) to describe the NF of whey permeate from an UF
unit; with electrostatic interactions becoming important, the pH and ionic strength of
feed solutions become important. Owing to their low permeability (and the osmotic
effects due to the rejection of some ions and other solutes) TMPs in NF tend to be
higher than in UF and up to 20 bar is typical for NF operation.
1.4.6 Dialysis
Dialysis refers to a process driven by concentration differences, whereas for the
above processes of MF/UF/NF/RO, the driving force was a pressure difference.
Clearly, the membranes for dialysis need to be porous. If the process is being used to
separate colloids and/or large macromolecules from small solutes, then a hydrophilic
UF membrane would be selected; the former are excluded but the small molecules
can transfer through the pores. The process has been used for the removal of alco-
hol from beer. The absence of pressure-induced convective flow limits the flux (and
hence production rate) but the gentle conditions are ideal for sensitive compounds
and more applications might be anticipated in the biological and food industries
in addition to the major biomedical applications. It should be noted that the use of
dialysis in the food industry might be limited but as mentioned above, dialysis is the
largest membrane process from a turnover and membrane area point of view due to
its use in medical applications, for example, hemodialysis.
1.4.7 Nonporous Membrane Processes

Nonporous membrane processes of relevance to the food industry include GS,
osmotic distillation, and PV and all have niche applications or potential applications.
Further discussion of these dense membrane processes is left to Chapter 3, which is
on activity-driven membrane processes.
1.4.8 Activity-Driven Nonwetted Membrane Processes

There are not many membrane processes of this type and the one of potential rel-
evance to the food industry is MD. The membrane would be a hydrophobic MF
membrane and as the pores are not wetted by the aqueous feed only vapor passes
through the pores. Further discussion is left to Chapter 3, which considers all rel-
evant activity-driven processes.
1.5 MEMBRANE-RELATED ASPECTS OF PHYSICAL CHEMISTRY

1.5.1 Osmotic Pressure
An osmotic pressure arises when two solutions of different concentrations (or a pure
solvent and a solution) are separated by a semipermeable membrane, that is, one that
is permeable to the solvent but impermeable to the solute (Mulder, 1996). Consider a
Δπ
Membrane
Solution 2 Solution 1 Solution 2 Solution 1
FIGURE 1.6 Schematic illustration of osmotic pressure. The perm selectivity of the mem-
brane initiates a solvent flux that becomes zero once the hydrostatic pressure balances the
osmotic pressure.
dense membrane that has a high rejection coefficient for salt. Let it be placed, as shown
in Figure 1.6, between a column of water with no salt and one with a solute (say, some
salt or glucose). There is a natural tendency for solvent to diffuse through the mem-
brane. As its activity is higher on the pure solvent side (and crudely one can think that
the cause is due to there being more solvent molecules in contact with the membrane on
that side than the other side), then the net flux of solvent will be from the low (or zero)
concentration side to the high concentration side. The buildup of hydrostatic pressure
in Figure 1.6 produces a countervailing tendency and when there is no net transfer, the
pressure difference is said to be equal to the osmotic pressure difference of the two solu-
tions. If solution 2 is a pure solvent, then the pressure difference is the osmotic pressure
of solution 1. The corollary of this observation is that osmotic pressure is the pressure
that needs to be applied to a solution to nullify osmosis. Osmotic pressures of various
juices and syrups are given in Table 1.2; this shows how significantly large they are.
TABLE 1.2
Osmotic Pressures of Various Juices and Syrups
Concentration (°Brix)a Osmotic Pressure (Bar)
Sugar beet juice 20 34.5
Tomato paste 33 69
Citrus juice 10 15
Citrus juice 34 69
Citrus juice 45 103.5
Sucrose 44 69
Corn syrup 37 69
Source: Adapted from Sammon, D.C. 1976. The treatment of aqueous wastes and foods by mem-
brane processes. In Membrane Separation Processes (ed. P. Meares). Elsevier Science Ltd.
a One degree Brix equates to 1 g of sucrose per 100 g of solution. °Brix is a traditional measure in
the fruit juice, wine, sugar, and honey industries.

The equation for chemical potential is given in Chapter 3. Not wanting to distract
at this stage, it is simply noted that if solution 2 is in fact pure solvent, then
RT
π=− ln(ai,1 ) (1.5)
Vi
where Vi is the molar volume of component i and ai,1 is the activity of component i
in solution 1. Others might have written “phase 1” (rather than solution 1) as these
expressions from thermodynamics apply to gases as well as liquids but as we are
seeking to give the reader a feel for the concept of osmotic pressure, which only
applies to solutions, we have chosen to label accordingly.
Now, ideally the activity of component i is equal to its molar fraction but due to
nonidealities, activity coefficients are introduced and in general, one writes:
ai = γ i xi (1.6)

where γ refers to the activity coefficient and x to the mole fraction. Now, as the mole
fraction tends to 1, the value of the activity coefficient has to tend to unity as well.
Thus, for dilute solutions, the following is true:

( ∑x ) = − ∑x
ln(ai ) = ln( γ i xi ) ≈ ln( xi ) = ln 1 − j j (1.7)
where j refers to all of the components that are not i, which is taken to be the solvent.
Combining Equations 1.5 and 1.7
∑x
RT
π= j (1.8)
Vi
Now, Equation 1.8 can be shown to be equivalent to van’t Hoff’s equation. For
dilute solutions:
∑x = ∑∑n + n ≈ ∑n
n n j j
j (1.9)
j i i

Also, for dilute solutions, niVi = V and so, in the absence of any dissociation of
the solutes
∑n
RT
π= j (1.10)
V
It is therefore seen that the osmotic pressure is proportional to the molar concen-
tration of the dissolved material. However, if the solutes dissociate (as, for instance,
sodium chloride into sodium ions and chloride ions), then Equation 1.10 needs to be
modified to reflect the molar concentration of species in solution. In fact

π = RT (∑i n /V )
dj j (1.11)
where idj is the degree of dissociation of component j expressed as the number of

moles of species formed per mole of component j.
For sodium chloride, the value of idj is 2. Of course, salts may not fully dissoci-
ate, so if the fraction of the solute j that dissociates is α, and if it dissociates into m
ions, then
idj = αm + (1 − α ) = 1 + α(m − 1) (1.12)

Substantial deviations from van’t Hoff’s equation occur at high concentrations

and with solutions of macromolecules. The importance of this will be made evident
in the next chapter where the relationship between osmotic pressure, π, and concen-
tration will involve an exponential factor.
1.5.2 Vapor Pressure
Tabor (1991) gave a molecular interpretation of vapor pressure by supposing that
a quantity of liquid was placed in a sealed vessel and that the air in the top part of
the vessel was evacuated. Then, given that there is a distribution of thermal ener-
gies, some molecules in the surface layer will have sufficient energy to escape from
the attractive forces of its neighbors. Some of these will return and condense and
equilibrium will be achieved when the rate of condensation equals the rate of evapo-
ration. The pressure exerted by the vapor under these conditions is known as the
saturation vapor pressure or simply the vapor pressure. It increases with an increase
in temperature. It is generally taken to be independent of the presence (and hence
pressure) of other gases. Tabor (1991) includes a small section on the effect of exter-
nal pressure but in general one can assume that the other gases and the vapor in
question exert their partial pressures independently.
Vapor pressure will not feature in any equations until Chapter 3 but has been
included here in the introductory chapter partly because it is a basic physical chemis-
try concept and partly because of the link between osmosis and vapor pressure. This
need not detain us, but those interested in basic science should consult Tabor (1991).
1.6 MEMBRANE MATERIALS, TYPE, AND STRUCTURES

Some knowledge of membrane materials and module designs is fundamental to
understanding membrane technology and key points are covered in this and the next
section. The ideal membrane will have a high hydraulic permeability, appropriate
selectivity/sieving characteristics, good mechanical stability, and good chemical sta-

bility. The last point relates both to compatibility with substances being processed
and with cleaning chemicals. Additionally, the manufacturing process should be
straightforward such that there is excellent reproducibility.
1.6.1 Membrane Classification
Membranes can be classified regarding their origin, morphology, structure, and
preparation method as illustrated in Figure 1.7. The initial classification distinguishes
between biological membranes (such as cell membranes) and synthetic membranes.
With regard to synthetic membranes, they can in terms of membrane material be
classified into polymeric and or inorganic membranes. Synthetic liquid membranes
will not be considered. Polymeric membranes will, because of their importance, be
considered in more detail shortly.
1.6.2 Inorganic Membranes
The development of inorganic membranes is rooted in the World War II Manhattan
project of the 1940s, which had a need to enrich uranium235. While natural mined
uranium contains only 0.7% of the uranium isotope235, a concentration of 3.0% is
required for nuclear weapons and energy. A gas-diffusion process with inorganic
membranes was used to separate uranium235 from uranium238 (Rautenbach and
Albrecht, 1993). Subsequent commercial development of inorganic membranes was
very slow and was overtaken by that of polymeric membranes. Moreover, they are
generally only available for UF and MF applications as they have a porous structure.
However, compared to polymeric membranes, inorganic membranes show a high
thermal, chemical, and mechanical resistance and have therefore a longer life.
Now, according to Scott (1995), membranes for a specific application are gener-
ally selected based on a consideration of (i) their chemical resistance against the
feed and cleaning fluids; (ii) their mechanical stability; (iii) their thermal stability;
(iv) their long-term stability/lifetime; (v) their permeability; and (vi) specification
Membranes
Synthetic Biological Origin
Liquid Solid
Organic Inorganic Material
Dense Porous Morphology

structure
Asymmetric Symmetric Symmetric Asymmetric
Phase inversion Composite Phase inversion

Preparation
Sintering Stretching Track-etching
FIGURE 1.7 Classification of membranes. (Modified after Rautenbach, R. and Albrecht, R.

1993. Membrane Separation Processes. John Wiley, New York.)
for selectivity. One must add that an additional consideration is cost; the investment
costs for inorganic membranes are commonly much higher than for polymeric mem-
branes and this is generally only partially offset by their longer lifetime. The costs
for both are decreasing and the difference is closing.
In the food and beverage industries, the applications of inorganic membranes
are limited to UF and MF. Here, the relevant inorganic membranes have been com-
mercialized since the early 1980s. Nowadays, generally four categories of inorganic
materials are of interest in membrane technology: (i) ceramics, (ii) metals, (iii) car-
bon, and (iv) glass.
Ceramic membranes such as γ-alumina on α-alumina (i.e., top layer is γ-alumina),
zirconia on stainless steel and zirconia on porous carbon have a strong tolerance to a
wide limit of temperature and pH and hence last for a long time, provided they are not
subject to undue vibration. They are brittle but this does not impose a TMP restriction.
Metal membranes are commonly produced as tubular modules. These membranes
have a high thermal and pressure resistance but their chemical resistance is moder-
ate; for example, it is limited in the case of strong acids or alkalis. Applications of
metal membranes are restricted due to their high investment costs and the fact that
the pore sizes are commonly limited to MF ca. 0.2 µm. Graver Technologies have
developed stainless-steel cross-flow membranes for extreme process conditions that
are said to excel in applications with aggressive chemistries, at high viscosity, at high
temperature, and at high solids loadings. Interestingly, the pore size is in the UF
range being ca. 0.02 µm.
Carbon membranes are mainly produced as tubular modules. In the future, these
membranes could act as a suitable support structure for organic membranes due to
their high porosity. To date, their industrial applications are limited.
Glass membranes are relatively easy to manufacture as hollow fibers and have
been included for completeness; so far, glass membranes have not had any industrial
impact and glass membrane modules may not be commercially available.
1.6.3 Polymeric Membranes

Polymeric membranes are relatively cheap, easy to manufacture, and available in a
wide range of pore sizes, and they have been widely used in various process industries.
However, most have limitations that hinder their wider applications. One factor is foul-
ing and the consequent desire to clean membranes with high- or low-pH solutions and/
or chlorine at an elevated temperature. Cellulose acetate (CA) and polyamide (PA) have
been the workhorses of the RO industry but they have disadvantages when it comes
to cleaning. CA has a low temperature limit (30–40°C) and a narrow pH range (2–8,
preferably 2–6) but it has a relative tolerance to chlorine. By contrast, the family of PA
membranes, which are superior to CA membranes in terms of RO parameters such as
flux and salt rejection, are particularly susceptible to chemical attack by chlorine and
by oxidants in general. Membranes are commonly rated for their chlorine tolerance in
“ppm-hours,” simply the product of the concentration and the contact time, which still
allows for acceptable performance. This tolerance is temperature dependent.
For UF and MF, progress has been made and a wide choice is now available,
including solvent-resistant membranes. Polyvinylidene fluoride (PVDF) membranes
suffer fewer fiber breaks than other materials and have excellent chlorine resistance.
Polyether sulfone (PES) membranes are ideal for the formation of polymer blends
and are available in a hydrophilic form. Unlike CA, PES does not suffer from biode-
gradability and a low caustic tolerance. Also, PES membranes have sufficient chlo-
rine resistance for many applications.
As synthetic polymeric membranes are the backbone of membrane technology,
their key features will be introduced. These are
1. Molecular weight and number of repeating units

2. Chemical structure of polymers and stereoisomerism
3. Chain flexibility and interactions
4. Crystallinity and glass transition temperature
1.6.3.1 Chemical Structure of Polymers

During the polymerization process, chains of molecules of different lengths are cre-
ated, since every reaction step is stochastic. Thus, molecular chains, even if they are
principally linear, will not be of a uniform length. So, in addition to defining mean rel-
ative molecular mass for the chain, an indication of the spread of sizes is also desirable.
Membrane polymer can be divided into homogenous polymers, which consist
of one type of monomer, and copolymers, which comprise two or more repeating
units of monomers. Figure 1.8 also illustrates block copolymers, random polymers,
and grafted polymers. In a block copolymer, the blocks are of uniform size and are
(1) Homogenous polymer
(2) Block polymer
(3) Random polymer
(4) Graft polymer
FIGURE 1.8 Homogenous polymer and different types of copolymers.

R R R
Syndiotactic
R R R R
R R R
Atactic
R R R R
Isotactic
R R R R R R R
FIGURE 1.9 Stereoisomerism in polymers.
spaced uniformly. In random polymers, the structure is irregular. In grafted poly-

mers, the side chains are chemically distinct polymers from the main chain and were
not part of the monomer that was polymerized to make the main chain.
In some polymers, the main chain side includes significant side groups, the pack-
ing of which is important. As illustrated in Figure 1.9, there are three distinctly
different ways that these side groups can be arranged. This is referred to as stereo-
isomerism and the three forms are
1. Isostatic: All side groups are on the same side of the chain.
2. Atactic: Side groups are randomly arranged on either side of the chain.
3. Syndiotactic: Side groups are arranged on alternative side of the chain.
The isotactic structure encourages the formation of a crystalline structure, while

atactic polymers are commonly noncrystalline or amorphous. Chain flexibility and
the presence of saturated C─C bindings as opposed to unsaturated C═C double
bonds is also influential. Structural characteristics are strongly influenced by the
two different types of interaction forces that exist between the polymer chains. The
primary interaction forces can lead to covalent bondings between polymer chains
while secondary interaction forces (in order of their bonding strength) are dispersive,
dipolar and hydrogen bonding. Additionally the chains may be chemical crosslinked.
Generally, polymers can be divided into glassy (amorphous) and rubbery poly-
mers (elastomers), which is determined by the glass transition temperature. While
this property has hardly any influence on the permeability of porous membranes,
the glass transition temperature becomes an important parameter for the selection of
polymers for dense membranes and is discussed more in Chapter 3. Here, we simply
define the term “glass transition temperature.” The tensile modulus E of a polymer
is defined as the force per unit of cross-sectional area to obtain a given deformation.
Now, consider the determination of the tensile modulus, E, as a function of tempera-
ture. If a sufficiently large temperature span is taken, two different regions of the
graph can be distinguished as illustrated in Figure 1.10.
In the region of glassy state, the tensile modulus E is high and the mobility of the
polymeric chains is restricted. While in the rubbery state, the tensile modulus E is
Glassy
state
Log E
Rubbery
state
Tg T
FIGURE 1.10 Tensile modulus E as a function of temperature for an amorphous polymer.

(Adapted from Mulder, M. 1993. Basic Principles of Membrane Technology, 1st Edition.
Kluwer Academic Publishers Dordrecht, Boston.)
often three or four orders of magnitude lower than in the glassy state because the
chain mobility is higher. The temperature at which the transition from glassy to rub-
bery state occurs is the glass transition temperature Tg.
1.6.4 Electrodialysis Membranes
In an ED process, ionic species are induced to move by an electrical potential and
separation is facilitated by ion-exchange membranes. These membranes are highly
swollen gels containing polymers with a fixed ionic charge that selectively allow the
passage of either anions or cations and very little else. A range of different membranes
are commercially available. For cation-exchange membranes, the major building block
is sulfonated polystyrene copolymerized with divinylbenzene. Anion-exchange mem-
branes are based on quaternary amines and their common carrier are blends of poly-
styrene and divinylbenzene. These anion-exchange membranes have fixed cations but
these are chemically less robust than the corresponding groups in their cation-exchange
counterparts. Furthermore, most natural foulants are colloidal polyanions and they
preferentially adhere to the anion-exchange membrane (Eykamp, 1999). Ideally, the
membranes would be both mechanically robust and with a low electrical resistance.
The latter is favored by a high concentration of fixed charges but as this leads to a high
degree of swelling and hence poor mechanical stability, trade-offs are necessary.
1.6.5 Membrane Morphology
Having mentioned materials in some detail, we now turn to membrane morphology.
Given that the aim is to have as small a hydraulic resistance as possible (and hence
as high a flux as possible) without compromising the selectivity of the membrane, the
active layer needs to be as thin as possible. The initial way of resolving these conflicting
objectives was via the development of an asymmetric membrane with an integral skin
layer, which in the case of RO was a dense skin. A later method was interfacial polym-
erization. In the case of ED, the electrical resistance needs to be as small as possible.
In addition to the distinction between porous and nonporous, membranes can be

divided into (a) symmetric and (b) asymmetric membranes. The former have a simi-
lar morphological structure all across the thickness of the membrane. Clearly, such
membranes are not suitable for RO, rarely used in UF, and are mainly found as MF.
Symmetric membranes are produced by sintering in the case of metal membranes,
while for polymeric ones, the common preparation methods are stretching and track-
etching. For example, polytetrafluoroethylene MF membranes are typically formed
by bi-axial stretching while polycarbonate MF membranes have essentially uniform
pores that are formed by track-etching. In this process, a film of polymer is first
exposed to radiation by high-energy alpha particles such that a large number of spots
in the film are degraded. The film is then immersed in acid, alkali, or a solution of
hydrogen peroxide (depending on the polymer) in order to etch out the damaged
material, thus yielding the pores.
Asymmetric ceramic membranes can be made by slip casting several layers of
approximately uniform particles, of decreasing size, upon a porous support.
As shown above in Figure 1.7, both porous and dense polymeric membranes can
be produced with a symmetric or an asymmetric morphology. Asymmetric mem-
branes can be produced either by phase inversion from a single polymer or as a
composite structure. The main difference between phase inversion membranes and
composite membranes is that in case of composite membranes, the support structure
and the skin layer are produced from different materials with the skin layer being
added onto an already-produced porous support. With asymmetric membranes, the
selective skin layer at the feed-side surface largely determines the performance, both
selectivity and flux. The membrane body is there to provide mechanical support.
1.7 MEMBRANE MODULES

Membrane modules need to be packaged into a device or vessel and these devices are
simply called membrane modules. A membrane module can be defined as a manifold
assembly containing one or more membranes that separates the feed, permeate, and
retentate stream (IUPAC—see Koros et al., 1996). Today, there are many forms: the
five main ones being: (1) spiral-wound modules, (2) tubular modules, (3) capillary
modules, (4) hollow fiber modules, and (5) flat-sheet plate-and-frame/cassette mod-
ules. Basically, types (1) and (5) are based on flat sheets and the others have a cylin-
drical geometry. Schematic outlines of the various modules are given in Figure 1.11.
The various types have different hydrodynamic characteristics, different mem-
brane areas per unit volume, and hence different costs. They are applied in different
areas and Table 1.3 gives a rough guide on which membrane processes pair up with
which modules. The optimal module design for a given module type will depend on
the application. Hence, the module design and its optimization are two of the key
areas in membrane technology.
Tubular modules are assembled in a shell-and-tube arrangement. The membrane
tubes are usually made up of porous fabric or plastic support coated on the inside
with a selective polymeric membrane. For higher-pressure operation, the tubes can be
housed within a metal tube with drainage holes. The internal diameters of the tubes
are typically in the range 5–25 mm, and the tube lengths can be from 0.6 to 6.4 m.
(a) Plate–frame module

Permeate
Retentate Feed
(b) Hollow fiber module

Retentate
Tube side feed Shell side feed
Feed Retentate Permeate
Permeate Feed
(c) Spiral-wound module

Retentate
Feed
Permeate Module Retentate
Permeate
Feed
(d) GKSS-pocket module (30) Membrane stack Pressure vessel
Membrane
Retentate
Permeate
Feed
Permeate
Feed
Feed Membrane
Central
permeate feed spacer
Porous
pipe
permeate
Module spacer
housing
Permeate
Retentate
Retentate
Permeate
Membrane
FIGURE 1.11 Design of different membrane modules.

TABLE 1.3
Module Type and Membrane Processes
Modules
Tubular Capillary Hollow Fiber Plate–Frame Spiral-Wound
Processes Modules Modules Modules Modules Modules
Microfiltration ++ + +
Ultrafiltration ++ ++ ++ +
Nanofiltration + ++
Reverse osmosis + ++
Gas separation ++ ++ +
Pervaporation + ++ +
Electro dialysis ++
+ indicates applicable for the processes if certain requirements are met.

++ indicates generally applicable for the process.
Owing to their large internal diameters, tubular modules are capable of dealing with
the feed stream containing fairly large particles such as pulped fruit. They operate
under turbulent conditions; this helps to limit fouling and also improves the efficacy of
cleaning. Additionally, through the use of sponge balls, they can be cleaned mechani-
cally as well. However, pumping costs are high and tubular modules have the lowest
surface-area-to-volume ratio among all configurations. A typical packing density is
generally less than 80 m2 membrane area per m3 of module and so capital costs as
well as operating costs are high. In recent years, the capital costs have been reduced
for lower-pressure applications by eliminating the metal tubes with drainage holes and
simplifying the design.
Capillary modules are similar to tubular membranes in layout. The inner diam-
eter of capillary membranes is between 0.3 and 3 mm and for the smaller-diameter
fibers, the packing density can be up to 800 m2/m3. With these diameters, the flow
on the inside is laminar, which gives relatively poor mass transfer and hence limited
control of fouling. However, back flushing (see Chapter 2) is one option for fouling
amelioration. In MF and UF, these modules can be operated in the inside-out mode
with selective skin layers on the inner sides of the fibers or in the outside-in mode
with the selective skin layer on the outside.
Hollow fiber modules typically contain a bundle of individual fibers sealed together
at each end with epoxy. The bundle can be from around 0.1 to 1.2 m in length and the
inner diameter is around 200 μm (except that in RO they have been manufactured
as small as 40 μm when they are labeled hollow fine fibers). Hollow fiber modules
have the highest surface-area-to-volume ratio (up to 10,000 m2/m3) among all the four
membrane configurations but they operate in the laminar regime and are susceptible to
blockage by feed particles, when operated in the inside-out mode (and also to clogging
[see Chapter 2] when operated in the other mode). Hence, some form of pretreatment
of the feed to filter out particles larger than 40 μm is often required.
Plate-and-frame/cassette modules are conceptually the simplest, and are like a

filter press or plate heat exchanger. Though owing to the lack of rigidity of the mem-
branes, a net-like spacer is used on both the permeate and the feed sides of the mem-
brane. The feed flows through a rectangular channel and although the superficial
Reynolds numbers is in the laminar flow region, the spacing material ensures good
mixing and good mass transfer. The plate design allows easy replacement of the
membranes and easy scale-up to commercial size. The packing density is typically
between 100 and 400 m2/m3. Pretreatment of the feed to remove particles greater
than 150 μm is recommended for plate modules. With regard to packing density,
energy consumption, and cost, plate modules are intermediate between tubular mod-
ules and spiral-wound modules. It is still the only module commonly used for ED.
Although once commonly used for UF and MF, today, there are far fewer applica-
tions in these areas for this type of module. The exception is the processing of highly
viscous feed streams where they are definitely an option.
Spiral-wound modules are a clever way of packaging “flat-sheet” systems in a
cost-effective manner. They have a packing density of over 900 m2/m3. Every mod-
ule consists of at least two membrane pockets. Each of these pockets is an envelope
consisting of a pair of membrane sheets with the active membrane sides facing out
and separated by a spacer with a special weave. Three edges of the pair of mem-
brane sheets are glued together with the fourth edge left open. This fourth edge is
connected to a perforated central tube for permeate removal. On the outside, and
between each of the “envelopes,” there is the feed-side spacer with a thickness of
around 0.6–3 mm. In the United Kingdom, there is a cake called a Swiss roll and the
spiral-wound design can be viewed as being similar with the “jam” being equiva-
lent to the feed side. Just as the sponge layer of such a cake is rolled up, the whole
assembly of a spiral-wound membrane is rolled around the perforated central tube in
a spiral-configuration. See final illustration of Figure 1.11. Owing to the feed spacer,
the feed-side pressure drop of these modules is relatively high and precautions need
to be taken against feed-side blockages. Also, precautions against telescoping must
be taken; the extra pressure on the upstream feed end of the modules leads to this
undesirable tendency. One of the key advantages is low manufacturing costs.
In addition to the above module types, there are a number of specialist modules.
It was mentioned above in passing that capillary modules can be operated with an
outside-in configuration with the selective skin layer being on the outside. When
the fluid management is such as to ensure transverse flow across the membrane
surface, then these modules might well be classified as transverse flow modules.
The nature of transverse cross-flow is such that these modules have excellent mass
transfer characteristics on the “shell” side. The patented design of the Liqui-Cel
system is such that the liquid feed is forced to flow radially across the outside of
the array of hollow fibers, starting from a central distribution tube. The flow is then
around a central baffle and back toward a central outlet pipe in the second half of
the module.
Finally, we include direct-flow modules that are now ubiquitous wherever there
is UF/MF membrane water treatment. Cross-flow configurations are not suitable
for large-scale treatment of surface, ground and waste waters because of excessive
energy costs. Also, the feeds with the exception of some waste waters do not have
Forward flow
Feed
Membrane
Filtrate
Backwash
Backwash Backwash
Membrane
Filtrate
FIGURE 1.12 Direct-flow process schematic. (Courtesy of Pearce, 2011.)
a high solids loading. Around 1990, membrane technologists started to eliminate

cross-flow altogether and have, as part of the operating cycle, intermittent backwash.
See Figure 1.12. This semi-dead-end process is sometimes called direct flow and is
distinguishable from classical dead-end processes in that the buildup of foulants is
controlled by frequent (many per hour) backwashes, which may include air scour,
supplemented by less frequent (but still many per day) chemically enhanced back-
washes. These occur while the membrane module is on-line and are distinguishable
from cleaning-in-place (CIP) procedures, which are infrequent and occur off-line.
The elimination of cross-flow meant that the modules developed for water treatment
applications could have smaller channels and much higher packing densities than the
original UF/MF units (Pearce, 2011).
In water and waste water applications, there are two configurations to consider:
either (a) the feed is introduced into the inside of the fiber lumen, with permeate
being collected on the shell side, or (b) the feed is introduced on the shell side with
permeate being collected from the inside of the fiber lumen. Details can be found
in Pearce (2011) who mentions that the inside feed is suitable for PES fibers and
that because air scour is essential during the backwash of outside feed systems, this
necessitates the use of PVDF fibers (Figure 1.13).
Inside feed membranes
Raw water
Filtered water
Outside feed membranes
Key
Active layer
Membrane wall
FIGURE 1.13 Direct-flow configuration options. (Courtesy of Pearce, 2011.)
The elimination of cross-flow was previously unthinkable in the water industry

but now it seems to have been an obvious thing to have done. If backwash without
chemical enhancement works for certain food or drink applications, then direct flow
should be considered. In general, the direct-flow system would be difficult to work
with for most applications in the food and beverage industries, but now that it has
been established on a very large scale in the water industry, it might provide, in cer-
tain cases, an option worthy of exploration.
1.8 MEMBRANE SYSTEMS

1.8.1 Basic
In addition to the terms for selectivity and volumetric flux introduced earlier in
Equations 1.1 through 1.3, two other terms are basic for concentration processes.
These are volume concentration ratio (VCR) and yield (Y). The former is simply the
ratio of the initial feed volume to the retentate volume remaining at the end of pro-
cessing. If the membrane rejects all of the solutes of interest and VCR = 5, then the
concentration of the solutes will have increased fivefold. If the rejection coefficient of
a species, R, remains constant, then the following expression is valid for that species:
c = c0 (VCR ) R (1.13)
If the substance of interest is in the retentate, then the yield, Y, is by definition:
cR VR
Y= (1.14)
c0 V0
If Equation 1.13 is also valid because R is constant, then it follows that
Y = (VCR ) R −1 (1.15)
If the aim is to clarify, then the substance of interest is in the permeate. For this
situation, the yield (labeled Yp) cannot approach 1 if the process is a simple batch
process. From Equation 1.15,
(VCR )1− R − 1
Yp = 1 − (VCR ) R −1 = (1.16)
(VCR )1− R
Under these situations, it is useful to add the solvent to the feed to flush the desired
solutes through the membrane or to remove undesired solutes from a desired retained
solute. An example is the processing of whey, which contains water, protein, and lac-
tose. The process of diafiltration, described in the next section, dilutes the feed and
during the removal of the additional solvent, the concentration of lactose is reduced.
Without the addition of the extra solvent, the feed concentration would increase and
there would be additional fouling and a decrease in flux. The usual remedy is to
avoid overconcentration.
1.8.2 Overview of UF Diafiltration
When overconcentration is avoided by adding to the feed a volume of solvent equal
to the amount of permeate, this process of constant volume filtration is called diafil-
tration. Denoting the retentate concentration as c, the two basic equations are
dV
=0 (1.17)
dt
d (Vc)
= −(1 − R)Jc (1.18)
dt
Combining these two equations and integrating (and remembering that VR = V0),
the yield equation is
V 
Y = exp  p ( R − 1)  (1.19)
 V0 
where Vp is the volume of filtrate (= volume of solvent added to the feed).

Clearly, for component that one aims to retain it is desired for Y to be high, in
which case R has to be close to 1. Also Equation 1.19 is used to calculate the volume
of diafiltrate that is required to reduce the concentration of species i to a particular
value, then from Equation 1.19 and recollection of the definition of Y, one obtains:
V  (1.20)
cRi /c0i = exp  p ( Ri − 1) 
 V0 
If it is desired to reduce the concentration of ci to a particular value then for known

Ri Equation 1.20 can be used to calculate the required value of Vp. Fractionating two
solutes might well be desired (e.g., separate milk fats but lactose). Today, it is con-
sidered that the combination of diafiltration and batch concentration can be used to
fractionate two solutes whose retentions differ by as little as 0.2. Further details can
be found elsewhere, for example, Lipnizki et al. (2002).
1.8.3 Layout of Membrane Systems

The main systems where there is agitation of the feed either by stirring or cross-flow
range from the stirred cell (which is used at laboratory scale), through various batch
operations, to continuous stages-in-series operation incorporating diafiltration. The
membrane system consists, in general, of feed and product tanks, a pumping unit,
membrane modules, heat exchangers, and a control system. Given that in most appli-
cations there is a need to maintain a minimum cross-flow velocity, recirculation is
common. Membrane modules can be laid out in various configurations and for a
detailed discussion on the configuration of RO systems, the reader is referred else-
where (e.g., Wilf, 2007). Here, we restrict ourselves to simpler layouts.
For small-scale operations, a batch system based upon a stirred cell can be consid-
ered, but at industrial scale, it is not that common (Figure 1.14). More common is the
semibatch system shown in Figure 1.15. With the former process, the entire quantity
of feed to be treated is put into the feed tank prior to the filtering operation, whereas
with the semibatch system, fresh feed is introduced continuously (and therefore the
feed tank is smaller). In both cases, the retentate is returned to the feed tank until the
desired concentration is reached and then there is batch discharge of the concentrate.
As shown in Figures 1.14 and 1.15, the retentate is returned to an unpressurized
feed tank and therefore the pumping costs are high per unit of feed because the feed
to the membrane unit is pressurized from essentially atmospheric pressure for each
Retentate
Batch
tank
Permeate
Cross-flow
module
Recirculation
pump
FIGURE 1.14 Small-scale membrane filtration: Batch operation.

Feed
Retentate
Batch
tank
Permeate
Cross-flow
module
Recirculation
pump
FIGURE 1.15 Semibatch operation.
circulation. If a second pump is introduced as in Figure 1.16, then a “high volume-low

head” pump can be used for the maintenance of the circulation and a “low volume-
high head” pump can be used as the feed pump for introducing fresh feed into the
filtration loop. Note that the recycled material is at the product concentration. This
arrangement is the basis of the general feed-and-bleed system shown in Figure 1.17,
wherein the individual circulation loops are at increasing concentration and only
the last one is at the product concentration. The latter is certainly preferred at larger
scale because not only does it give a better balance between capital and operating
costs, but because of the reduced residence time, it will give a better quality product.
Feed Permeate
Loop 1
Feed
tank
Recirculation Ratio control

pump valve
Retentate
Feed
pump
FIGURE 1.16 Single-stage feed-and-bleed system.

Feed Permeate
Loop 1 Loop 2 Loop 3 R1, R2, R3 =

Feed Recirculation pumps
tank
Ratio control
R1 R2 R3 valve
Retentate
Feed
pump
FIGURE 1.17 Typical multistage feed-and-bleed system.
One example of the use of feed-and-bleed configurations is in the concentration of

juices; other applications will be found in later chapters.
1.8.4 Membrane Process Design

Before arriving at decisions on layout it is essential to have taken a systematic
approach to the process design including integration. There are eight basic steps:
1.
Definition of the Separation Problem: Check that a membrane process is
a suitable process for consideration through the clarification of overall aim
and specification, and a brief look at competitive technologies.
2.
Initial Membrane Screening: Different membranes are compared based
either on literature data or manufacturers’ data, supplemented by experi-
mental measurements as required.
3.
Analysis of Selectivity and Permeability: The main candidate membranes
are tested at bench scale, measuring flux and selectivity under different
process conditions, including various TMPs and concentrations. Realistic
hydrodynamic conditions are desirable. In order to reduce the number of
experiments, simulations may be used.
4.
Initial Process Layout and Economic Analysis: After the membranes have
been evaluated, an initial process layout can be formulated based on data
collected from the literature, experiments, and simulations. A first eco-
nomic analysis can then be made.
5.
Measurements at Pilot Scale: If the evaluation at step 4 is promising, then
the evaluation of actual modules at a pilot unit is considered necessary so
as to ensure that the results are transferable to large-scale units. A caveat
to this is made later in this section. Given the importance of hydrodynamic
conditions, the need to examine a number of operating cycles (including
cleaning), and the various fouling timescales (minutes, hours, and days as
discussed in the next chapter), a pilot-scale evaluation is essential.
6.
Consideration of Hybrid Process: From an economic analysis of the varia-
tion of recovery with cost for a stand-alone membrane system, a decision
on whether a hybrid process should be investigated has to be made. For
example, if the overall aim is to concentrate a feed, then the final concentra-
tion stage could potentially be made by evaporation with the use of a mem-
brane system for bulk dewatering. The addition of an extra step gives an
extra degree of freedom and this allows for some decoupling of the overall
separation and recovery objectives.
7.
Simulation and Economic Analysis of the Proposed System: Following the
previous steps, the full-scale unit can be simulated and o ptimized, although
extrapolation outside of the pilot tests is to be avoided. The economic evalu-
ation can then be updated.
8.
Improvement of the System with Focus on Plant Integration: The mem-
brane system will be part of an overall process and the potential for syner-
gies should be examined.
These elements will become clearer from a study of the other chapters.
Before closing this introductory overview, a few comments on sizing are
made in the next section.
1.8.5 Prediction of Required Membrane Area

A fundamental need is to have an accurate assessment of the required membrane
area. The models introduced in the next chapter, together with appropriate integra-
tion for a proposed layout, can form the basis of such calculations. The models are
grounded partially in theory. These models are particularly useful for assessing
the likely volumetric flux for a given TMP, and so are useful for concentration
operations where the product is the retentate. However, the nature of the fouling
phenomena will make most practical models for real feeds empirical and refinement
is required. Thus, in the previous section, a key step was step 5, evaluation at pilot
plant level.
While the models in Chapter 2 can be adapted through the incorporation of selec-
tivity data to give something useful for those applications where the product is the
permeate, there is a complication. This complication is that outside of the water
industry the desired product is not pure solvent but is solvent plus desired solutes.
Thus, the transmission of some solutes is essential. Transmission of solutes is harder
to model and therefore a simple empirical approach based on some initial experi-
mental data has its merits. Following Stürken (1994), the flux of the target compo-
nent through the membrane can be described, from previously acquired data, by
ji = a ⋅ win + b (1.21)

where ji is the mass flux of component i (and not the volumetric flux, J, introduced
in Equation 1.3), w is the weight fraction of the target component, and a and b are
constants determined by experiments. The values of a and b will depend upon
TABLE 1.4
Empirical Calculation of Membrane Area
Case Solution
m  w 
I J i = a ⋅ wi A = ln  i,F 
a  wi,R 
m  a ⋅ wi,F + b 
II J i = a ⋅ wi + b A= ln
a  a ⋅ wi,R + b 
III J i = a ⋅ win , n ≠ 1 A=
m
a ⋅ (1 − n)
(
ln wi1,−Fn − wi1,−Rn )
Source: Adapted from Stürken, K. 1994. Organophile Pervaporation: ein
Membranverfahren zur Aufarbeitung verdünnter wässrig-organischer
Lösungen. GKSS-Forschungszentrum Geesthacht GmbH, Geesthach.
hydrodynamic conditions and TMP and therefore equations of the form of Equation
1.13 will be valid for specific operating conditions only.
Now, given a constant feed mass flow rate m f , the following balance can be writ-
ten for component i:
m f ⋅ dw = −(a ⋅ win + b)dA (1.22)

Results of the integration for different cases are given in Table 1.4. It is reempha-
sized that since this approach is only an empirical one, the estimated flux is only
valid for the conditions covered by experiments and that extrapolation should be
avoided.
1.9 SUMMARY
The nature of membranes, both the material and the morphology, strongly influence
the efficiency of a membrane process. While the correct choice of a membrane is nec-
essary, it is not sufficient since the correct choice of operating conditions is also essen-
tial. Fouling dramatically reduces performance and is the subject of the next chapter.
Hydrophilic but of course chemically stable membranes are generally favored as these
foul less and thereby give a more stable performance. As the cost of membranes has
reduced dramatically, new design solutions, such as operation at reduced TMPs, have
emerged. Furthermore, new applications have and will become economically attractive.
REFERENCES
Böddeker, K.W. 1995. Commentary: Tracing membrane science. J. Memb. Sci. 100, 65–68.
Eykamp, W. 1999. Section 22, Alternative separation processes. In Perry’s Chemical
Engineers’ Handbook (eds D.H. Perry and D. Green). 7th edition, pp. 22-42–22-48
McGraw-Hill, New York.
Fane, A.G. 2008. Membrane separations—100 Years of achievements and challenges. In

AIChE Centennial Proceedings, 8pp. AIChE, New York.
Field, R.W. and Howell, J.A. 1989. In Process Engineering in the Food Industry: Developments
and Opportunities (eds Field and Howell). Elsevier Applied Science, London and
New York.
Graham, T. 1866. On the absorption and dialytic separation of gases by colloid septa. Philos.
Trans. R. Soc. 156, 339–439. Accessible at http://www.jstor.org/stable/108953.
Koros, W.J., Ma, Y.H., and Shimidzu, T. 1996. Terminology for membranes and membrane
processes (IUPAC Recommendations 1996). J. Memb. Sci. 120.2, 149–159.
Leniger, H.A. and Beverloo, W.A. 1975. Food Process Engineering. Reidel, Dordrecht and
Boston.
Lipnizki, F., Boelsmand, J., and Madsen, R.F. 2002. Concepts of industrial-scale diafiltration
systems. Desalination 144, 179–184.
Loeb, S. and Sourirajan, S. 1960. Seawater demineralisation by means of a semi-permeable
membrane. UCLA Engineering, Report No. 60-60.
Loeb, S. and Sourirajan, S. 1963. Seawater demineralisation by means of an osmotic mem-
brane. Adv. Chem. Serv. 38, 117.
Lonsdale, H.K. 1982. The growth of membrane technology. J. Memb. Sci. 10, 81–181.
Luque, S. 1999. Introduction and basic principles of membrane technology. In Membrane
Applications in the Food and Dairy Industry (eds. S. Luque and J. R. Alvarez). Servicio
de Publicaciones, Universidad de Oviedo, Oviedo, Spain.
Meares, P. 1976. Physical chemistry of transport and separation by membranes. In Membrane
Separation Processes (ed P. Meares). Elsevier Scientific Pub Co., Amsterdam, Oxford,
New York.
Mulder, M. 1993. Basic Principles of Membrane Technology, 1st Edition. Kluwer Academic
Publishers, Dordrecht, Boston.
Mulder, M. 1996. Basic Principles of Membrane Technology, 2nd Edition. Kluwer Academic
Publishers, Dordrecht, Boston, London.
Muralidhara, H.S. 2010. Challenges of membrane technology in the XXI century. In
Membrane Technology (eds Z.F. Cui and H.S. Muralidhara). Butterworth-Heinemann,
Oxford.
Nollet, J.A. 1748. Lecons de Physique Experimentale. Hippolyte-Louis Guerin and Louis-
Francios Delatour, Paris.
Pearce, G.K. 2011. UF/MF Membrane Water Treatment: Principles and Design, Water
Treatment Academy, Bangkok.
Rautenbach, R. and Albrecht, R. 1993. Membrane Separation Processes. John Wiley,
New York.
Sammon, D.C. 1976. The treatment of aqueous wastes and foods by membrane processes. In
Membrane Separation Processes (ed. P. Meares). Elsevier Science Ltd., Amsterdam.
Scott, K. 1995. Handbook of Industrial Membranes. Elsevier, London, New York.
Stürken, K. 1994. Organophile Pervaporation: ein Membranverfahren zur Aufarbeitung
verdünnter wässrig-organischer Lösungen. GKSS-Forschungszentrum Geesthacht
GmbH, Geesthach.
Tabor, D. 1991. Gases, Liquids and Solids. CUP, Cambridge.
Van der Horst, H.C., Timmer, J.M.K., Robbertsen, T., and Leenders, J. 1995. Use of nanofil-
tration for concentration and demineralization in the dairy industry: Model for mass
transport. J. Memb. Sci. 104, 205–218.
Wijmans, J.G. and Baker, R.W. 1995. The solution-diffusion model: A review. J. Memb. Sci.
107, 1–21.
Wilf, M. 2007. The Guidebook to Membrane Desalination Technology. Chapter 5 Balaban,
L’Aquila, Italy. ISBN 0-86689-065-3.
2 Concentration
Polarization, Fouling,
and Its Mitigation
Robert Field
CONTENTS
2.1 Background...................................................................................................... 41
2.2 Concentration Polarization.............................................................................. 43
2.3 Modeling Ultrafiltration in the Absence of Fouling........................................ 47
2.4 Modeling Ultrafiltration in the Presence of Fouling....................................... 50
2.5 Fouling: Its Nature and Key Influences........................................................... 54
2.6 Fouling: Amelioration and Cleaning............................................................... 59
References.................................................................................................................64
2.1 BACKGROUND
Before we can approach the subject of fouling in a meaningful way, it is important
to understand some of the ways in which membrane flux is reduced below that of
the corresponding pure water flux (or more generally, pure solvent flux) even when
there is no fouling per se. After due consideration of fundamental relationships, this
chapter includes methods of fouling analysis, and also a short section on cleaning.
In addition to fouling, which is the buildup of material (e.g., adsorbed macromol-
ecules, gelatinous layer, and/or deposited particles) on the membrane surface, there
is also concentration polarization. This is a natural consequence of the selectivity of
a membrane. This leads to an accumulation of particles or solutes in a mass transfer
boundary layer adjacent to the membrane surface. Dissolved molecules accumulat-
ing at the surface reduce the solvent activity (i.e., creates an osmotic pressure) and
this reduces the solvent flow through the membrane. The significance of this for juice
processing was emphasized in Chapter 1, and as noted by Baker (2004), the concen-
tration of some macromolecules near the membrane surface can reach 20–50 times
that in the bulk solution.
The creation of an osmotic pressure at the membrane surface is an inevitable
consequence of solutes not passing through the membrane and has nothing to do
with material adhering to the membrane or to deposit buildup. The process is revers-
ible, and with the elimination of transmembrane pressure (TMP), the flux will go to
zero and the concentration buildup will be rapidly dissipated. The buildup is called
“concentration polarization” and a mathematical analysis of this phenomenon will
be given shortly.
41
An appreciation of transport to the membrane surface, and the physical laws that
govern transport through the membrane will be developed after the equation for
concentration polarization has been derived. Together with the concept of concentra-
tion polarization, the application of basic transport equations enables us to have a
performance model that is applicable in the absence of fouling. Thus, when the terms
due to fouling are added, they can be placed in context.
It is imperative to distinguish a reduction in driving force across the membrane
(which is the effect of concentration polarization) from an increase in resistance due
to fouling of the membrane. Fouling is the buildup of material on the membrane
surface, in the mouths of the pores and within the pores of a membrane, as shown
schematically in Figure 2.1; the descriptors such as standard pore blocking and
cake filtration will be explained later when giving some mathematical expressions.
The various forms of fouling can also be categorized as follows:
Adsorption: It occurs when specific interaction between the membrane and

the solute or particles exists. A monolayer of particles and solutes can grow
even in the absence of permeation flux, leading to an additional hydrau-
lic resistance. If the degree of adsorption is concentration dependent, then
concentration polarization exacerbates the amount of adsorption.
Pore blockage: When filtering, pore blockage can occur, leading to a reduction
in flux due to the closure (or partial closure) of pores.
Deposition: A deposit of particles can grow layer by layer at the membrane
surface, leading to an important additional hydraulic resistance. This is
often referred to as a cake resistance, but the layers are likely to consist of
more than discrete particles. For example, high-molecular-weight material
may accumulate in the interstitial space between particles.
For certain macromolecules, the level of concentration polarization may lead to

gel formation in the immediate vicinity of the membrane surface, for example, a
(a) (b)
(d)
(c)
FIGURE 2.1 Some fouling mechanisms of porous membranes. Adsorption is not included.
(a) Complete pore blocking, (b) Internal pore blocking, (c) Partial pore blocking, and
(d) Cake filtration. (After Field, R. W., J. J. Wu. 2011. Modelling of permeability loss in mem-
brane filtration: Re-examination of fundamental fouling equations and their link to critical
flux, Desalination 283, 68–74.)
Concentration Polarization, Fouling, and Its Mitigation 43
solution of concentrated proteins can gel and form a layer of greatly reduced water
permeability. This layer is a separate phase from that of the solution and is the con-
sequence of excessive concentration polarization. Concentration polarization itself
(or more precisely the layer resulting from concentration polarization) is just another
name for the mass transfer boundary layer that arises when components are selec-
tively rejected by the membrane.
2.2 CONCENTRATION POLARIZATION

The term “concentration polarization” refers to the concentration boundary layer
adjacent to the membrane within which there is elevated concentration of all rejected
and partially rejected components (Figure 2.2). This is true for reverse osmosis (RO),
ultrafiltration (UF) and microfiltration (MF). Thus, for example, the minor compo-
nents that are rejected can be salt in RO, proteins in UF, or oil droplets in MF. These
are convected (i.e., carried by the flow) toward the membrane, creating a higher con-
centration of the minor component in the boundary layer. The concentration builds
up rapidly over a few seconds or less. This leads to diffusion back from the thin layer
of high concentration to the bulk of lower concentration. In steady state, which is
rapidly achieved, the back-diffusion of each rejected component balances the forward
convection of that component. In this steady-state, there is a concentration profile
from an elevated concentration at the membrane surface to the bulk concentration at
the outer edge of the mass transfer boundary layer. So, on starting up a membrane
process, the region that is very close to the membrane experiences a sharp increase
in concentration and this process is said to lead to concentration polarization. It is a
natural consequence of membrane selectivity. The extent of accumulation in this layer
and the thinness of it can be estimated from the expressions that are now developed.
Let the solvent be component 1. At steady state, the convection of component
1 to the membrane equals the amount going through the membrane. For compo-
nent 2, the amount of back-diffusion is equal to the difference between the amount
Bulk feed Boundary layer Premeate
Cm
JC J Cp
CB
dC Cp
D
dX
z δ 0 Membrane
FIGURE 2.2 Concentration polarization. For clarity, component subscript i has been omit-
ted. (After Mulder, M. 2003. Basic Principles of Membrane Technology. Kluwer, Dordrecht.)
of component 2 convected to the membrane and the amount going through the mem-
brane (j2). The terms are expressed per unit area per unit time and are thus mass
fluxes. A typical unit would be kmol/(m2 · s). Mathematically, these two relation-
ships are
Component 1
j1,con = j1 (2.1)

Component 2
j2,con = j2,diff + j2 (2.2)

In writing out these two simple equations, three assumptions were made: (i) the
process is at steady state, (ii) there is no chemical reaction, and (iii) the concentra-
tion gradient parallel to the membrane is negligible. In developing these equations
further, three more assumptions are made: (iv) density is constant, (v) the process
is one of Fickian diffusion, and (vi) the diffusion coefficient is independent of the
solute concentration. For a detailed discussion of this model, the stagnant film model
for concentration in membrane systems, the reader is referred to Zydney (1997).
Now, through the introduction of volumetric flux, J (which has units of m3/(m2 · s)
or L/(m2 · h)), one can write for a general component i:
dCi
JCi = JCi,p − D1i (2.3)
dz
where Ci,p is the concentration of component i in the permeate, and D1i is the diffu-
sion coefficient of component i with respect to component 1, the solvent. Equation 2.3
can be integrated. Taking the boundary layer thickness to be δ, the boundary condi-
tions are
z=0 Ci = Ci,m
z=δ Ci = Ci,B

This yields:
 D   C − Ci,p 
J =  1i  ln  i,m
 δ   Ci,B − Ci,p 
(2.4)

The subscripts B, m, and p refer to the bulk, membrane surface, and permeate,
respectively. From the above equation, it is seen that for every component i, the con-
centration at the surface is exponentially related to flux:
 Jδ 
Ci,m = (Ci,B − Ci,p )exp  (2.5)
 D1i 

The term Jδ/D1i is generally greater than unity for membrane processes involving
liquids and so the concentration boundary layer has an important influence on mem-
brane performance. In passing, it is noted that in the case of gas phases, this effect
is far less important due to the larger (about 105 higher) diffusion coefficient in gas
phases compared to liquid phases. It is also worth remarking that when Dji is small, the
boundary layer is thin. For macromolecules, Dji is very small and the boundary layer
is very thin. The resulting highly localized high concentrations are relevant to fouling.
The term D1i/δ in Equations 2.4 and 2.5 can be described as a mass transfer coef-
ficient but it is not a classical mass transfer coefficient in which the origin of the
material diffusing through the boundary layer all originates at z = 0. The mass trans-
fer boundary layer created in membrane system is also referred to as the concentra-
tion polarization layer as the average concentration within this layer is significantly
higher, due to the exponential relationship in Equation 2.5 than in the bulk. As there
is a distinct difference between the two regions, polarization is said to have occurred.
The curvature of the concentration profile depends upon the flux and so the rela-
tionship between the mass transfer coefficient ki,b(= D1i/δ) and those that can be cal-
culated from conventional chemical engineering correlations need to be treated with
care (Vasan and Field 2006). It can be shown that ki,b approaches a conventional
mass transfer coefficient as the flux through the membrane approaches zero (J → 0).
Having indicated the non-conventional nature of ki,b the subscript ‘b’ will be left out
from hereon. For systems with low fluxes as in reverse osmosis or electrodialysis,
or with ultrafiltration deliberately operated at low fluxes, the correlations linking
Sherwood number (which includes the mass transfer coefficient), Reynolds number,
and Schmidt number can be used. However, when there is moderate to severe con-
centration polarization and this can be related to a boundary layer Peclet number
[J/ki], caution should be exercised when using conventional correlations. In general,
the mass transfer coefficient should be obtained from experiments. For a solute that
is fully rejected, Equation 2.4 becomes:
C 
J = ki ln  i,m  (2.6)
 Ci,B 
Now, as (and this may seem surprising) Ci,m has been found to be approximately
constant, and so a plot of flux versus ln(Ci,B) is often found to give a straight line of
negative slope and this is taken to be ki, the mass transfer coefficient for component i.
The conventional chemical engineering correlations for mass transfer take the form:
d
d 
Sh = a ⋅ Re b Sc c  h  (2.7)
 L

where the dimensionless groups are as follows:
Reynolds number: Re = ρudh /µ

Sherwood number: Sh = (ki ⋅ dh ) /D1,i
Schmidt number: Sc = µ / ( D1,i ⋅ ρ) = ν /D1,i
Symbols have their normal meaning and are listed elsewhere. The term “hydrau-
lic diameter” is defined in general as:
4 ⋅ cross-sectional area of channel

dh = (2.8)
Wetted perimeter of channel
It is readily seen that for tubes, dh is simply the diameter of the tube.
The indices a, b, c, d in Equation 2.7 are dependent on the flow regime, which
is module dependent. It is not simply a case of determining whether the bulk flow
is laminar or turbulent because across a spiral-wound module, the bulk flow may
exhibit a pressure drop consistent with turbulent flow (created by the feed spacer)
but the mass transfer layer may be very thin (as noted above) and is effectively in
the laminar sublayer. The estimates for tubular and hollow fiber modules are likely
to be more accurate and appropriate values are given in Table 2.1. The coefficients
for laminar flow are for a hydrodynamic fully developed flow but with a developing
concentration boundary layer. If both profiles are developing, the correlation will be
different. For turbulent flow, the aspect ratio, dh/L, is irrelevant, which is why d = 0
in this case. An alternative set of values for turbulent flow are 0.04, 0.75, and 0.33.
This is mentioned to emphasize the approximate nature of the information given in
Table 2.1.
The above equations are for macromolecules. For particles, it has to be remem-
bered that their back transport is very much dependent on their size. In the smaller
size range of say <0.1 μm, the removal of particles relies on Brownian diffusion.
Shear-induced diffusion dominates for particle sizes between 1.0 and 10 μm and
between 0.1 and 1.0 μm; both Brownian diffusion and shear-induced diffusion
are important. A classical paper by Belfort et al. (1994) also included the iner-
tial lift mechanism for larger particles alongside shear-induced diffusion, but
20 years on, it is generally accepted that the latter mechanism provides the bet-
ter description for membrane filtration. For particles around 0.1–1.0 μm, charge
effects can also make a strong contribution to back transport—see Bacchin et al.
(2006).
TABLE 2.1
Indices for Estimating Approximate Values of the Mass Transfer Coefficient
via the Sherwood Correlation, Equation 2.7
Flow Regime a b c d System
Laminar 1.62 0.33 0.33 0.33 Hollow fiber
Turbulent 0.026 0.8 0.3 – Tubular
Laminar 1.62 0.33 0.33 0.33 Plate and frame
Turbulent 0.026 0.8 0.3 – Plate and frame
2.3 MODELING ULTRAFILTRATION
IN THE ABSENCE OF FOULING
For both microfiltration and ultrafiltration, the separation is achieved through a basic
sieving mechanism, with rejection of molecules whose size is greater than that of the
pores. Thus, if the effective driving force across the membrane is known, use can be
made of Darcy’s law, which states that flux is proportional to the applied pressure
difference. In Chapter 1, the TMP was defined as:
( PF − PP )in + ( PF − PP )out
TMP = (1.4)
2
where “in” refers to the feed inlet of the membrane module and “out” the feed out-
let because the pressure on the feed side of the module will vary between inlet and
outlet because of the flow channel pressure drop caused by the cross-flow. For the
present, we will simply refer to a local value and write TMP as ΔP. The importance
of osmotic pressure has already been mentioned and, so the effective pressure dif-
ference across a pore is
Effective pressure difference = ∆P − ∆π

where Δπ is the osmotic pressure difference between the feed side adjacent to the
membrane (i.e., at the mouths of the pores) and the permeate side. The osmotic
pressure on the permeate side will be close to zero but that on the feed side at the
entrance to the pores will be many times greater than that of the feed itself due to
concentration polarization. In general, the driving force that exists between the bulk
feed on one side and that on the permeate side (i.e., PF − PP) will be reduced by the
osmotic pressure difference that occurs due to solute rejection. The term ΔP − Δπ
represents the driving force across the membrane itself.
In the absence of any fouling, the following equation is the best one to describe
the volumetric flux, J:
∆P − ∆π
J= (2.9)
µRm
where Rm is the empirically measured membrane resistance.

The inclusion of the dynamic viscosity of the permeate, μ, as a separate term (as
opposed to its inclusion within Rm) is to be preferred because viscosity is tempera-
ture dependent. The separate term Rm is then a constant for a given structure. The
reciprocal of the term μRm is known as permeability but it is clearly temperature
dependent. So, if it is used, the temperature at which it is evaluated must be given.
If the flux of pure solvent is being measured, then the term Δπ is zero, and ΔP is
simply TMP.
45
40
35
30
Flux (μm/s)
25 Pure water
20 0.00002
15 0.00001
10 0.000005
5
0
0 200 400 600 800
TMP (kPa)
FIGURE 2.3 Typical variation of flux with TMP for various values of mass transfer coef-
ficient (m/s). Note the tendency to a plateau due to osmotic pressure effects.
For a solute that is fully rejected, Equations 2.4 and 2.9 can be combined to pre-
dict ΔP as a function of J if the osmotic pressure of the feed as a function of concen-
tration is known. For example, if the relationship were
π = bC 3 (2.10)

then the variation of required TMP for a given J would be
 3J 
∆P = µRm ⋅ J + bCi3,B ⋅ exp   (2.11)
 ki 

The importance of the second term is illustrated in Figure 2.3. No allowance has
yet been made for fouling and the curvature of the lines (other than the pure water
flux line, which is straight) is due to the buildup of osmotic pressure as a result of
concentration polarization. The osmotic pressure of the feed was taken to be 5 kPa.
Also, the dependency upon concentration was taken to be nonlinear, which is rea-
sonable for higher concentrations of macromolecules. To more accurately represent
osmotic pressure across a range of concentrations, an expression such as the follow-
ing is recommended:
π = aC + eC 2 + bC 3 (2.12)

The change from Equations 2.10 through 2.12 does not change the main mes-
sage, which is that osmotic pressure effects are a major influence upon the J–TMP
relationship. First, when the feed displays an osmotic pressure, the TMP required
for a given flux will rapidly increase beyond a certain flux, because of concentration
polarization. Second, the J–TMP relationship is seen to depend heavily upon the
mass transfer coefficient, k, because in Figure 2.2, the large differences are the result
of only a fourfold change between the highest and lowest values of k.
An alternative to Equation 2.9 is the following wherein Rcp is the resistance of the
concentration polarization layer:
∆p
J= (2.13)
µ( Rm + Rcp )

It was shown by Wijmans et al. (1985) that the two expressions (2.9) and (2.13)
are thermodynamically equivalent with the concentration boundary layer impeding
the flow of the solvent and thus “consuming” part of the overall driving force. While
the value of Δπ can be calculated through the solution of a set of equations, the value
of Rcp can only be inferred from experiments or from a calculated value of Δπ and
therefore the author has a preference for Equation 2.9.
If the solute is completely rejected, Equation 2.6 will link flux and Ci,m (provided
bulk concentration Ci,B and mass transfer coefficient ki are known), while Equation
2.9 links flux, Δp and Δπ (provided the membrane resistance and permeate viscos-
ity are known). The relationship between solute osmotic pressure and concentration
can be expressed by equations such as Equation 2.12, which enables one to relate
Δπ to Ci,m because it is an excellent approximation to make π(at m) = Δπ. Sufficient
information would now be available to plot flux as a function of TMP (as was done
to generate Figure 2.3) with the values of Δπ and Ci,m also being noted.
Before moving onto a consideration of the modeling of ultrafiltration in the pres-
ence of fouling, the question is asked, “Can one predict the nature of Rm from the
structure of the membrane?” If the membrane is considered to be a series of pores,
then the Hagen–Poiseuille equation can be used as a starting point. Assuming uni-
form capillaries, the membrane resistance can then ideally be described by
32 ⋅ τ ⋅ l pore
Rm = (2.14)
ε ⋅ d pore
2

where ε is the surface porosity, τ is the tortuosity of the capillaries, lpore is the length
of the capillaries, and dpore is the diameter of the capillaries.
When on the other hand the membrane can be compared to an arrangement of
near-spherical particles, as might be the case in ceramic membranes, the Carman–
Kozeny equation can be applied. The resistance can then ideally be described as
follows:
K ⋅ η ⋅ S 2 ⋅ (1 − ε)2
Rm = (2.15)
ε3 ⋅ l
where ε is voidage, K is a constant, l is the thickness of the porous layer, and S is

the specific area (surface area per unit volume). K and S depend upon the particular
nature of the structure; the finer the particles, the larger the S.
Although the resistance through most unfouled membranes cannot be described

by the idealized equations above as their structures do not conform to either of these
two idealized forms, the introduction of the equation does serve two practical pur-
poses. First, the last equation can be used to model some fouling layers. The very
strong dependency upon voidage and the specific area should be noted. Second,
Equation 2.14 shows the strong dependency of pore resistance to pore size. By recall-
2
ing that the cross-sectional area of a pore depends upon d pore and noting the form of
Equation 2.14, it is readily concluded that the flow-through pores with diameters of
D and d will be in the ratio D4:d4 if they are of equal length. So, pores differing by a
factor of 2 in diameter will permit very different volumetric flows. Hence, it will be
readily appreciated that the blocking of a few large pores will alter the overall flux
through a membrane significantly.
2.4 MODELING ULTRAFILTRATION
IN THE PRESENCE OF FOULING
Now that a sound basis has been provided by which the flow-through unfouled mem-
branes can be viewed, additional terms can be added to account for the additional
hydraulic resistances either due to material accumulation on the membrane surface
or material accumulation in the membrane pores. These phenomena are collectively
known as fouling. The schematic illustration of the difference in the effect of con-
centration polarization and of fouling upon flux is shown in Figure 2.4. It could be
noted, following Equation 2.4, that as the flux declines due to fouling, the degree of
concentration polarization (and hence its effect upon flux) will decrease. Thus, the
concentration polarization line in Figure 2.4 shows the effect of concentration polar-
ization with time, if there were no fouling.
Whether fouling is on the membrane surface or in the pores, it will affect the flux
relationship in different ways and this will be considered in a mathematical manner
later. At this stage, a threefold division of the overall fouling resistance is introduced.
Flux Concentration polarization
Fouling
Time
FIGURE 2.4 Schematic of the effect of concentration polarization and fouling on flux.
(Modified after Cheryan, M. 1986. Ultrafiltration Handbook. Technomic Pub. Co., Lancaster,
PA.)
These resistances can be considered to be in series with the membrane resistance.

Hence,
∆P − ∆π
J= (2.16)
µ( Rm + Rads + Rrev + Rirrev )
The first of the additional hydraulic resistances, Rads, is for the resistance due to
surface or pore adsorption that occurs independently of flux. This is measured by
contacting the membrane with the feed in the absence of flux (for say a few hours)
and then measuring a pure solvent flux at a known TMP. This enables a hydrau-
lic resistance to be calculated and the difference between it and Rm gives Rads. The
experiment can be repeated for other contact times.
The other terms in Equation 2.16 reflect the fouling that occurs during opera-
tion. The increased resistance that occurs during operation can be divided into a
reversible component, Rrev (i.e., one that occurs during operation but is not pres-
ent after switching from the feedback to pure solvent), and an irreversible compo-
nent, Rirrev, that reflects the deposition of material that is only removable (at best)
by a cleaning operation. This classification allows one to distinguish additional
resistances (such as adsorption) that are independent of the pressure and permeate
flux from fouling phenomena driven by the solvent transfer through the membrane.
Fouling of the latter type can be reversible (Rrev) or irreversible (Rirrev) when the
pressure is decreased.
Today, when considering fouling mechanisms, one should consider what insights
the concepts of critical flux, threshold flux, and sustainable flux bring to the problem
under consideration. The strong form of critical flux, Jcs, was developed to discrimi-
nate no fouling conditions, where Rm is the only resistance in Equation 2.16, from
fouling conditions where other resistances also apply. It has been defined by Field
et al. (1995) as the flux at which the flux–TMP curve starts to deviate from linearity
(Figure 2.5). So, if osmotic pressure effects are negligible (as was the case in the
original paper), one can simply write:
∆P
for J < J cs : J =
µRm
(2.17)
∆P
for J > J cs : J =
µ( Rm + ( Rrev + Rirrev ))
where at least one of Rrev or Rirrev is nonzero and when Rads is considered as
negligible.
For ultrafiltration, the critical flux should ideally be described in analogy to the
one for microfiltration but with due allowance for osmotic effects due to concentra-
tion polarization. Thus, the corresponding pair of equations is
(∆p − ∆π)
J ideal =
µRm
Pure water flux
Flux
Strong form
critical flux
Weak form
critical flux
TMP
FIGURE 2.5 Forms of critical flux as originally defined by Field et al. (1995).
∆p − ∆π
J actual = (2.18)
µ( Rm + ( Rrev + Rirrev ))
The ideal may apply at sufficiently low fluxes. Figure 2.5 also illustrates the weak
form of the critical flux hypothesis. Here, it is assumed that adsorptive mechanisms
between the membrane and some components in the feed create an additional resistance
Rads. This was assumed in the original paper to be something that occurred rapidly and
this resistance was taken to be independent of flux. In the absence of additional foul-
ing, a linear relationship between flux and TMP is maintained, the gradient being 1/
(Rm + Rods). Conditions enhancing foulant-deposited to foulant-in-suspension repulsion
have been found to give greater limiting flux values. Such observations agree well with
a theoretical model capturing both hydrodynamic and DLVO interactions (Tang et al.
2009). DVLO theory involves the balance between electrostatic repulsion and Van
der Waals attractions and this theory was originally derived by Derjaguin, Verwey,
Landau and Overbeek. When fouling is evitable, attention should be addressed to
whether foulant-deposited versus foulant-in-suspension repulsions can be enhanced.
For an advanced discussion of how the concept of critical flux has developed, see
Bacchin et al. (2006) and Field and Pearce (2011). The simplest definition of criti-
cal flux is the flux at which fouling is first observed for a given feed concentration
and given cross-flow velocity. It should be a design consideration for all pressure-
driven processes, even if the answer to the question is, “the flux at which zero fouling
occurs is too low to be of interest.” By asking the question and exploring the various
influences on the rate of fouling, one may well be led to the determination of break
points between low and high fouling regimes. The various influences include (i)
hydrodynamics (e.g., cross-flow velocity), (ii) choice of membrane, and (iii) pretreat-
ment of the feed to the membrane. The variation of the rate of fouling with flux may
well indicate break points in the curve of “rate of fouling versus flux” and this is at
the heart of the concept of threshold flux. There is a parallel with the concept of criti-
cal flux. The critical flux (if it exists) is the flux below which the overall resistance of
the membrane system does not change with time, but above it, fouling is observed.
The threshold flux is the flux below which the overall resistance of the membrane
system changes slowly with time and above it the overall resistance changes rapidly.
Unless the break point is obvious, then the definition has a subjective characteristic.
It has been suggested that an appropriate model might be:
Rate of resistance increase = α + β( J − J * ) for J > J * (2.19)

Rate of resistance increase = α for J ≤ J * (2.20)

where J* is the threshold flux, and α and β are constants for a particular system and
set of operating conditions.
As reported for the first time by Stoller et al. (2013), one main problem in using
Equations 2.19 and 2.20, even at constant operating conditions and constant feed-
stock, is that J* appears not to be a constant unlike Jcs in Equation 2.17. Since the
resistance increases at a certain rate with time, this condition must hold at threshold
flux conditions too. As a consequence, it can be determined that as the resistance
increases due to (slight) fouling, the threshold flux reduces too. This is particularly
important when working over industrial timescales.
In order to exploit the concept of threshold flux, a correct determination of the
evolution of J* as a function of time is required, and this is only possible if all the
parameters affecting Equation 2.19 are known. As detailed in a very recently pub-
lished handbook by Stoller and Ochando Pulido (2015), the knowledge of all the
parameters involved in Equation 2.19 can be very helpful in describing the option
for operation at subthreshold flux conditions. The data collected in this book permit
one to reach the correct design of membrane processes for a widespread range of dif-
ferent feedstocks, membranes, and operating conditions by taking into account the
changes of the threshold flux values J*(t) as a function of time.
Rather than just using the knowledge of an experienced designer, the conscientious
seeking of additional break points can be a useful heuristic toward the achieving of
an optimal design. Such a design must take into account capital and operating expen-
ditures (capex and opex). Field and Pearce (2011) consider that this leads to the deter-
mination of a sustainable flux. In preparation for an Oxford workshop on critical flux
10 years ago, an industrialist proposed that sustainable flux was the “net flux that can
be maintained using mechanical and chemical enhancing means to meet an operation
cost objective over the projected life of the membrane.” Thus, sustainable flux design
is a pragmatic concept for commercial operations in which there is controlled fouling,
which gives an optimal balance between moderate operating costs (opex) and moder-
ate capital costs (capex). Net flux was mentioned in the proposed definition in order
to allow for possible permeate consumption during backwash. Backwash efficiency
is particularly important in the water industry, which often employs high-frequency
backwash, but less important in other areas. Very-high-frequency, very-short-duration
Information on fouling: for example

• Does Jcrit exist? Design decisions influenced by:
Cost of energy, membrane costs,
• How does dP/dt (for constant cleaning regime, CO2 emissions.
flux operation) vary with flux?
Sustainable flux
FIGURE 2.6 The twin influences on the determination of a sustainable flux.
backwash, labeled “back-shock,” was considered for the microfiltration of beer

(Jonsson 1999), as mentioned again in Section 2.6.
Earlier, Bacchin et al. (2006) stated that “the sustainable flux is usually defined in
relation to a flux policy (that might be implicit rather than explicit) in which fouling
is minimized to avoid frequent cleaning.” Herein, the view is taken that the definition
should be explicit about the inclusion of economic factors. The concepts of critical
flux and threshold flux are dependent upon inter alia physico-chemical factors and
should influence the design of membrane equipment. Costs are also important and
the sustainable flux is the outcome of the design process and (insofar as it may be
changed subsequently) of operating experience. A summary of where the concept of
sustainable flux is positioned is given in Figure 2.6.
2.5 FOULING: ITS NATURE AND KEY INFLUENCES

While membrane processes apparently offer simplicity, the operation of membrane
processes often requires know-how due to the complications of fouling. With pro-
cess fluids and industrial timescales (as opposed to ideal laboratory solutions and
relatively short test times), fouling of membranes can be considered to be inevitable.
The implication is that the concept of a threshold flux is more meaningful than the
concept of critical flux as originally defined. (Many have used the term “critical flux”
when threshold flux would in retrospect have been more appropriate.)
Membrane fouling is the combined effect of a number of physical, chemical, and
biological processes, which all lead to an increase in the overall resistance to per-
meation. As a result of the increasing resistance to fluid flow, a higher pressure is
required if throughput is to be maintained (or if the initial pressure is maintained,
throughput will decrease). Fouling of membrane can be influenced by permeate flux,
pH, salt concentration (or more generally ionic strength), feed concentration, protein
aggregation, and protein denaturation and membrane type. As some potential effects
are concentration dependent, then concentration polarization is also influential. As
seen from Equation 2.6, the concentration at the surface depends upon exp(J/ki),
which indicates that the influence of the flux can be strong.
Also, the higher the flux, the stronger the shear in the mouths of the pores, and
although the velocity in the pore mouths is small, so is the diameter of the pores and
the net effect is a relatively strong rate of shear, which can lead to some molecules, of
essentially the same size as the pores, entering the mouths of the pores. Extensional
flow or elongational flow refers to “a flow where the velocity changes in the direc-
tion of the flow,” and polymeric molecules subject to such flow can be distorted.
Such flow pattern may occur at the entrance of pores in MF or UF due to the abrupt
changes in area. It has been shown that there exists a critical flow rate below which
a polymer can keep its coiled shape and above which the hydrodynamic force starts
to elongate a linear polymer chain in a good solvent from coil to stretch. Jin and Wu
(2006) have observed this first-order transition in a UF experiment. The relevance
here is to the fouling Equations 2.19 and 2.20 given above. In a number of situations,
one can readily imagine a flux being sufficiently high for it to generate the shear
rates that lead to foulants penetrating the pores and becoming trapped. This gives
a significant increase in resistance. Conversely, below the key flux, the fouling is
limited to surface accumulation of material and essentially all pores remain active
albeit with a secondary coating covering the pores. As illustrated in Figure 2.7, the
(a) (b)
(c)
(d) (e)
FIGURE 2.7 Snapshots of various degrees of polymer penetration (a) bulk, (b) = 28%,
(c) = 42%, (d) = 89%, and (e) bulk pore. (Reproduced with permission from Hermsen, G. F.
et al. 2002. Monte Carlo simulation of partially confined flexible polymers. Macromolecules
35(13), 5267–5272.)
extension of the polymer is greatest in the mouths of the pore and once it is within the
pore, there is a strong tendency for it to resume a globular shape, which reduces the
probability of it being carried through into the permeate. Furthermore, the extension
will expose internal areas and these may interact with the pore wall, thus enhancing
the probability of retention within the pore.
For microfiltration and ultrafiltration, the fouling can be very severe with the pro-
cess flux often being less than 5% of the pure water flux. Now, several parameters
influence the fouling rate such as
1. Nature and concentration of solutes and solvents

2. Membrane type
3. Pore size distribution
4. Surface characteristics and material of membranes
5. Hydrodynamics of membrane module
Roughly, three types of foulants have been distinguished: (i) organic precipi-
tates (macromolecules, biological substances, etc.), (ii) inorganic precipitates
(metal hydroxides, calcium salts, etc.), and (iii) particulates. A more comprehen-
sive list is given in Table 2.2, the last entry of which relates to biofilms that are
important in the water industries. In that industry, one of the problems does not
relate to foulants in the feed per se but biofilms that form from the constituents in
TABLE 2.2
Examples of Foulants and Fouling Modes in Membrane Processes
Foulants Fouling Mode
Large suspended particles Particles present in the original feed or developed due to aggregation
can form a cake layer and/or block module channels.
Small colloidal particles Colloidal particles can form dense fouling layers (e.g., ferric
hydroxide from brackish water can become a slimy brown fouling
layer). They can also block the mouths of membrane pores or
accumulate inside pores.
Inert macromolecules Gel or cake formation on membrane.
Adsorptive macromolecules Some macromolecules such as proteins are known to adsorb on to
surfaces on membranes, including within the structure of porous
membranes if not excluded by virtue of size.
Small molecules Some small organic molecules tend to have strong interactions with
polymeric membranes (e.g., antifoaming agents such as
polypropylene glycols used during fermentation fouls certain
polymeric ultrafiltration membranes).
Chemical reactions Concentration increase and pH increase can lead to precipitation of
salts and hydroxides.
Cations In addition to their role in scaling, certain cations such as calcium
can also facilitate macromolecular fouling through bridging.
Biological substances The growth of biologically active organisms such as bacteria and
their excreted extracellular material.
the feed. This is particularly important in water applications but it is just noted in
passing in this book.
Before turning to cleaning of foulants from membranes, it is both interesting and
informative to consider the four fouling mechanisms that can be observed for porous
membranes. As shown in Figure 2.1 above, these are (a) complete pore blocking, (b)
internal pore blocking, (c) partial pore blocking, and (d) cake filtration. These are not
self-exclusive and one may observe one or more acting sequential or simultaneously.
In Table 2.3, the different values of n, their phenomenological background, and
the relevant transport equations are given for when the mechanism is acting indepen-
dently of the other three. Column 3 is for dead-end filtration, that is, with no allow-
ance being made for cross-flow whereas some allowance for cross-flow is included
in the expressions in column 4. The phenomenological coefficients n and K depend
on the fouling mechanism that is happening. Choosing which expressions fits best
will be discussed shortly.
First, it is noted that the following differential equation can be used to summarize
column 3 of the table and it describes the influence of fouling on the flux through
the membrane in the absence of any cross-flow effect. From the equations listed
in Table 2.3, one can show that for dead-end operation, the relative flux (j = J/J0)
declines as follows:
dj
− ∝ j 3− n (2.28)
dt
This equation is based on a reworking of Hermia (1982) and is only applicable

to the initial time periods of cross-flow membrane operation. However, it does show
that the rate of flux decline (−dj /dt ) is higher for larger n. As j is less than unity and j
is decreasing with time, then just j on the right-hand side (which occurs for n = 2, i.e.,
complete pore blocking) is larger than j3 (which occurs for n = 0, i.e., cake buildup).
Clearly, the message is that one should avoid the blocking of pores, and pore penetra-
tion by appropriate specification of membrane pore size. In some operations, an UF
membrane might give better longer-term performance than an MF membrane even
though the latter gives a better initial performance; the majority of the solutes may
be rejected by the MF membrane but some minor components may slowly block the
MF membranes whereas they cannot penetrate into the UF membrane. Thus, over
the longer term, the UF performance is more robust.
For cross-flow filtration, the relative flux (j = J/J0) declines as follows:
dj  J *  2 − n
− ∝ 1 −  j (2.29)
dt  J 0 

where the flux J* is the steady-state flux for large t. The appendix of the paper by
Field et al. (1995) links the work of Hermia to cross-flow filtration and introduces
the concept of critical flux analytically but there is in fact no need to consider J* to
be a critical flux; it can be treated as an experimentally determined value identical
to the steady-state flux.
58
TABLE 2.3
Fouling Mechanisms, Phenomenological Background, and Equations for Constant TMP for Dead-End and Cross-Flow
Fouling
Mechanism n Phenomenological Background Flux Equation for Dead-End Flux Equation for Cross-Flow
Complete pore 2 Particles larger than the pore size J = J 0 ⋅ exp( K b ⋅ t ) (2.21)
J = ( J 0 − J * )exp(− K 2 t ) + J * (2.25)
blocking, block the pores.
see Figure 2.1a
Internal pore 1.5 Particles smaller than pore size enter −2 As for dead-end, that is, Equation 2.22
 1 
blocking, the pores and are either adsorbed J = J 0 ⋅  1 + ⋅ K s ⋅ ( A ⋅ J 0 )0.5 ⋅ t  (2.22)
 2 
see Figure 2.1b or deposited within the pore.
Particle pore 1 Any particle reaching a pore might −1
J = J 0 ⋅ (1 + K i ⋅ ( A ⋅ J 0 ) ⋅ t ) (2.23) J*
blocking, seal it over time. Particles might J=
*
  J0 − J  *
 (2.26)
see Figure 2.1c also bridge a pore or stick to the 1 −   exp ( − J K1t )
inactive part of the membrane.   J 0  
Cake filtration, 0 Formation of a cake on the
J = J 0 ⋅ (1 + 2 ⋅ K c ⋅ ( A ⋅ J 0 )2 ⋅ t )−1/ 2 (2.24) 1   J (Jo − J * )   1 1 
see Figure 2.1d membrane surface of particles, K0t =  ln ⋅ − J *  −   (2.27)
J *2   J 0 ( J − J * )   J J 0  
which do not enter the pores.
Source: Adapted from Field, R. 2010. Fundamentals of fouling, In K. V. Peinemann and S. P. Nunes (Eds.), Membranes for Water Treatment: Volume 4, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim, pp. 1–22.
Engineering Aspects of Membrane Separation
Often, initial fouling is of a pore blocking/pore filling nature before switching

to an n = 0 (cake formation) mode. Detecting the point of change from say n = 2
to n = 0 and the extent of the resistance increase up to this point is clearly of inter-
est. The method of integral analysis has not been the norm in cross-flow analysis
whereas dead-end filtration classical analyses use plots of t/V versus V to test for cake
formation (n = 0) and t/V versus t to test for standard blocking (n = 1.5). However, the
use of V and J (instead of J and dJ/dt) can be beneficially implemented for cross-flow
systems. From the full form of Equation 2.29, one can readily obtain:
J t
− dJ
∫ J 2−n ∫
= K n ( J − J n* )dt = K n (V − J n*t ) (2.30)
J0 0

The left-hand side of Equation 2.30 is a function of both J and n, and takes the
following forms:
Value of n 2 1.5 1 0
fn(J,n) J0 − J J 00.5 − J 0.5 ln(J0/J) 1/J − 1/J0
To plot fn(J,n) versus (V − J n*t ) requires an estimate of J n* but an alternative is

to plot fn(J,n)/t versus V/t. From the gradient and intercept of this plot, one obtains
Kn and J n*. The details are given in Field and Wu (2011) who showed that initially
it is useful to make an initial first visual check as to whether 1 or 2 consecutive
mechanisms apply by plotting fn(J,n) versus V. Given that food applications will
inevitably involve fouling, determination of the modes of fouling is vital during the
initial evaluation of membrane systems and during troubleshooting. As noted by
Mulder (2003), the phenomenon of fouling is very complex and difficult to describe
theoretically. Even for a given solution, fouling will depend on physical and chemi-
cal parameters such as concentration, temperature, pH, ionic strength, and specific
interactions (hydrogen bonding, dipole–dipole interactions). Nevertheless, reliable
values of flux decline are necessary for process design and the integral method has
the potential to be very informative in establishing the nature of the increase in
resistance.
Characterization of cleaned and fouling membranes can be very informative and
the reader is directed to the work of Chan and Chen (2004), Hughes et al. (2006),
and Rabiller-Baudry et al. (2002). In the next section, we first look at minimizing
fouling and then at cleaning, but a brief summary of the mechanical and chemical
resistances of common UF materials is given in Table 2.4 (Scott 1995).
2.6 FOULING: AMELIORATION AND CLEANING

Some of the approaches to prevent certain forms of fouling and to reduce fouling
generally are identical to the measures taken to reduce the intensity of a concentra-
tion boundary. Thus, flux should not be excessive and the value of the mass transfer
coefficient ki should be as high as reasonably possible. Increasing the mass transfer
TABLE 2.4
Robustness Overview of Common UF Membranes
Mechanical Operational Operational pH Tolerance to
Strength Temperature Limit (°C) Range Oxidative Chemicals
CA Good 30 4–8 Moderate
PAN Good 40 2–10 Moderate
PES Good 80 2–12 Poor
PS Good 75 1–13 Good
PVDF Good 40 2–10.5 Good
Ceramic Excellent >100 Essentially no limit Excellent
coefficient can be achieved through high flow velocities. Also, the use of various
kinds of turbulence promoters will reduce fouling. Although rotary module systems
may not seem attractive from an economic standpoint for large-scale applications,
they may be attractive for small-scale applications if fouling is an acute problem.
Improving the hydrodynamics can be achieved in a number of ways as indicated in
Table 2.5 under direct methods (Field 1996).
It may seem strange to have included cleaning in a list of fouling prevention mea-
sures but regular intermittent cleaning (e.g., chemically enhanced backwash) can
reduce the need for major cleaning-in-place procedures. It is suggested that in many
industries, the cleaning procedures might be viewed as consisting of two types.
There are those that are for regular maintenance and those that are for recovery.
So, well-adapted maintenance cleans prevent the need for excessive recovery cleans.
Under indirect methods, we have methods for conditioning the feed and methods
for conditioning the membrane. Fouling reduction starts in developing proper pre-
treatment, which is generally simple but can be overlooked. Pretreatment methods
TABLE 2.5
Approaches to Prevent and Reduce Fouling
Direct Methods Indirect Methods
Turbulence promoters (e.g., modified membrane Pretreatment by heat treatment, pH
spacers) adjustment, and filtration
Pulsed or reverse flow Treatment of the membrane surface
Rotating or vibrating membranes Preparation of more hydrophilic membranes
Stirred cells with rotating blades close to the membrane Generation of a dynamic membrane layer
Ultrasonic enhancement Selection of appropriate operating mode
Periodic back pulse with permeate or gas Selection of optimum operating conditions
Periodic cleaning
• Chemical cleaning
• Hydraulic cleaning
• Mechanical cleaning
for the feed solution can include heat treatment, pH adjustment, addition of com-
plexing agents (EDTA, etc.), and adsorption of surface active agents onto the active
carbon. Additionally, prefiltration, including premicrofiltration and preultrafiltration,
can be beneficial. When proteins are present, pH adjustment can be very important;
fouling is minimized at the pH value corresponding to the isoelectric point of the
protein, that is, the point at which the protein is overall electrically neutral.
The use of hydrophilic rather than hydrophobic membranes generally reduces
fouling and eases cleaning. Generally, proteins adsorb more strongly at hydrophobic
surfaces and are less readily removed than from hydrophilic surfaces. Negatively
charged membranes can also help, especially in the presence of negatively charged
colloids in the feed. Another method is to create a dynamic membrane layer that acts
as a precoat as used in classical filtration.
It is vital that membrane processes used for food and beverages are disinfected to
eliminate all pathogenic microorganisms. The food and dairy industries require that
their membranes be disinfected on a daily basis. The choice of the cleaning method
mainly depends on the module configuration, the type of membranes, the chemical
resistance of the membrane, and the type of foulant encountered.
The frequency with which membranes need to be cleaned can be estimated
from process optimization, but for hygienic reasons, long intervals cannot be
realized. It is interesting to ask whether the industry has fallen into the habit of a
once-per-day clean without exploring the benefits of more frequent cleans—not nec-
essarily full cleans but maintenance cleans, or partial cleans via back-flushing or
forward-flushing. Clearly, in the food industry, intermittent chemically enhanced
backwashes are not feasible but it is possible that the water industry now has things
to teach the food industry with respect to membrane operation whereas 20 years ago
it was the other way around.
Three cleaning methods can be distinguished: (i) hydraulic back-flush, (ii) physi-
cal cleaning, and (iii) chemical cleaning. Hydraulic cleaning methods include back-
flushing (only applicable to microfiltration and open ultrafiltration membranes, and
then subject to there being sufficient mechanical integrity). The anticipated outcome
of back-flushing is depicted in Figure 2.8. After a given time interval, the feed pres-
sure is released and the direction of the permeate flow is reversed. The flow from
Flux Pulsatile flow
Continuous flow
Time
FIGURE 2.8 Use of overall (net) flux through use of periodic backflush. (After Ghosh,
R. 2003. Protein Bioseparation Using Ultrafiltration: Theory, Applications, and New
Developments. Imperial College Press, London; River Edge, NJ.)
the permeate side to the feed side consumes permeate (which is why there is refer-
ence to net flux in the figure’s caption) but the fouling layer within the membrane
or at the membrane surface is reduced. Recently, a variant of this method has been
developed, the “back-shock” method (Jonsson 1999). Here, the time interval between
back-flushing has been reduced to seconds and its duration to tens of microseconds.
In this process, MF asymmetric membranes are used in the reverse orientation, that
is, with the porous support layer facing the feed and the skin layer facing the perme-
ate side. During the “back-shock,” the pressure is raised on the permeate side by a
relatively large amount but the skin layer is forced against not away from the support
layer. The porous structure retains the particles and then they are readily released
during the back-flow because the structure is open. The initial application was beer
filtration where transmission as well as flux is important. While this is unlikely to be
the case in many applications, the use of high-intensity but short back pulses is likely
to give the best clean for a given consumption of permeate.
Mechanical cleaning with oversized sponge balls can only be applied in tubular
systems but the use of an air scour is somewhat more general. Sponge balls are only
applicable to larger tubular membranes; they can effectively scrape deposits off the
membrane modules. Clearly, it is important to have avoided in-pore fouling. Their
usage has been limited in practice. Membrane relaxation with a forward flush is
the reduction of TMP to zero, which naturally allows the concentration polarization
layer to disperse, followed by pumping of the feed, or possibly demineralized water,
at a relatively high velocity. This is hydraulic cleaning. The addition of air scour
promotes higher turbulence at the membrane surface and can therefore improve the
efficacy of the clean. Distribution of the air can be a problem, use of compressed air
may damage the module, and the method is relatively complex. Its use is confined
mostly to the water industry.
The most important method for reducing fouling and restoring as near as possible
the initial state of the membrane is chemical cleaning. Now, cleaning of a material is
a process by which extraneous substances are removed from that material and with
regard to membrane cleaning, it would ideally result in a membrane that is not only
physically, chemically, and biologically clean, but is restored to its pristine state. In
practice, the criteria are (1) restoration of adequate flux (and separation characteris-
tic) without adversely changing the membrane surface properties, (2) dissolution or
dispersion of the foulants so as to prevent refouling of already cleaned surfaces, and
(3) disinfection of the wet surfaces. This needs to be achieved with chemicals that
are cost effective and compatible with both the membrane and other system compo-
nents, such as joints and spacers.
While the dedicated literature on membrane cleaning is less voluminous than
that on fouling, a number of studies are to be found in the literature, including, for
example, work on milk (Mohammadi et al. 2002), skimmed milk (Paugam et al.
2013), apple juice (Giorno et al. 1998), and tea concentration (Wu and Bird 2007).
In this introduction, we will confine ourselves to general comments. In practice,
chemical cleaning uses a number of chemicals either separately or in combination.
The concentration of the chemicals and the cleaning time are important especially
if the chemicals lead to some degradation of the membrane during each clean. The
five important categories of cleaning agents commonly are acids, alkalis, oxidants,
surfactants, and enzymes (Trägårdh 1989, Mohammadi et al. 2002). Commercial
cleaning products are often mixtures of these compounds with the actual composi-
tion being proprietary.
The acids to be considered include HCl, HNO3, H3PO4, and citric acid, the first
two being strong and the last two weak acids. Strong acids are incompatible with
some membranes and so the usage of weak acids is usually preferred. The acids can
act to dissolve inorganic precipitates and through acid-catalyzed hydrolysis breakup
certain macromolecules such as proteins. The alkalis give strong hydroxide solutions
and this promotes the rapid hydrolysis of proteins and polysaccharides into small
amides and sugars. Solutions of Na2CO3 are weakly alkaline, being a combination of
a weak acid and a strong base. Surfactants act as detergents and help to solubilize and
disperse deposits such as proteins. Additionally, they help to ensure complete wet-
ting, which is important when disinfecting a system. Furthermore, they act per se as
biocides. Enzymes are selective organic catalysts. For example, the enzyme protease
acts specifically on proteins, breaking it into smaller component parts by cutting
the molecular chain at specific points. Enzymatic cleaning has many advantages
over other types of cleaning agents and has been used industrially; see, for example,
D’Souza and Mawson (2005), who noted a number of advantages but also stated that
the cost efficiency was difficult to control. The advantages can be said to depend on
the type of membrane being considered for a given duty. As enzymatic reactions take
place at low temperature and mild pH, there is a slower degradation of membranes
and their life is prolonged. This is a particular advantage for those m embranes
that can withstand neither elevated temperature nor extreme pH. Enzymes are also
biodegradable.
Finally, it is noted that in the pilot evaluation of a membrane process, it is vital
to explore the performance over many operating cycles, including cleaning cycles,
being aware that there are various fouling timescales (minutes, hours, and days) and
that if feedstock is recycled during the evaluation period, then the amount of key
foulant per unit area of membrane may be very different from that of the proposed
full-scale plant.
List of Main Symbols

Symbol Definition Unit
A Area m 2
C Mass concentration kg/m3

D Diffusion coefficient m2/s
D Diameter m
J Solute or volumetric flux kmol/(m2 · s) or m/s
K Fouling constant –
k Mass transfer coefficient m/s
l Length, thickness m
t Time s
v Velocity m/s
z z-Coordinate m
Greek Symbols
Symbol Definition Unit
μ Dynamic viscosity Pa · s
ν Kinematic viscosity m2/s
ρ Density kg/m3
Dimensionless Numbers
Symbol Definition
Re Reynolds number
Sc Schmidt number
Sh Sherwood number
Subscripts
Symbol Definition
0 Standard, reference
b Boundary layer or complete pore blocking
blocked Blocked
c Cake filtration
con Convective
diff Diffusive
F Feed
h Hydraulic
i Component i or particle pore blocking
j Component j
M Membrane
s Internal pore blocking
REFERENCES
Bacchin, P., P. Aimar, R. W. Field. 2006. Critical and sustainable fluxes. Review: Theory,
experiments and applications, Journal of Membrane Science 281, 42–69.
Baker, R. W. 2004. Membrane Technology and Applications, Wiley: Chichester, 2nd edition.
Belfort, G., R. H. Davis, A. L. Zydney. 1994. The behavior of suspensions and macromolecu-
lar solutions in crossflow microfiltration, Journal of Membrane Science, 96(1–2), 1–58.
Chan, R., V. Chen. 2004. Characterization of protein fouling on membranes: Opportunities
and challenges, Journal of Membrane Science 242, 169–188.
Cheryan, M. 1986. Ultrafiltration Handbook. Technomic Pub. Co., Lancaster, PA.
D’Souza, N. M., A. J. Mawson. 2005. Membrane cleaning in the dairy industry: A review,
Critical Reviews in Food Science and Nutrition 45, 125–134.
Field, R. 2010. Fundamentals of fouling, In K. V. Peinemann and S. P. Nunes (Eds.),
Membranes for Water Treatment: Volume 4, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim, pp. 1–22.
Field, R. W. 1996. Mass transport and the design of membrane systems, Chap 4, In K. Scott
and R. Hughes (Eds.) Industrial Membrane Separation Technology, Blackie, London;
New York.
Field, R. W., J. J. Wu. 2011. Modelling of permeability loss in membrane filtration: Re-examination
of fundamental fouling equations and their link to critical flux, Desalination 283, 68–74.
Field, R. W., G. K. Pearce. 2011. Critical, sustainable and threshold fluxes for membrane
filtration with water industry applications. Advances in Colloid and Interface Science
164, 38–44.
Field, R. W., D. Wu, J. A. Howell, B. B. Gupta. 1995. Critical flux concept for microfiltration
fouling, Journal of Membrane Science 100, 259–272.
Ghosh, R. 2003. Protein Bioseparation Using Ultrafiltration: Theory, Applications, and New
Developments. Imperial College Press, London; River Edge, NJ.
Giorno, L., L. Donato, S. Todisco, E. Drioli. 1998. Study of fouling phenomena in apple juice clar-
ification by enzyme membrane reactor, Separation Science and Technology 33, 739–756.
Hermia, J. 1982. Constant pressure blocking filtration laws: Application to power-law non-
Newtonian fluids. Transactions of Industrial and Engineering Chemistry, 60, 183–187.
Hermsen, G. F., B. A. De Geeter, N. F. A. Van der Vegt, M. Wessling. 2002. Monte Carlo
simulation of partially confined flexible polymers. Macromolecules 35(13), 5267–5272.
Hughes, D. J., Z. Cui, R. W. Field, U. K. Tirlapur. 2006. In situ three-dimensional charac-
terization of membrane fouling by protein suspensions using multiphoton microscopy,
Langmuir 22, 6266–6272.
Jin, F., C. Wu. 2006. Observation of first-order transition in ultrafiltration of flexible linear
polymer chains. Physical Review Letters 96, 237801.
Jonsson, G. 1999. Membrane processes for beer production, Symposia on Membrane
Processes in the Food Industry, Université Paul Sabatier, Toulouse, France, pp. 10.
Mohammadi, T., S. Madaeni, M. Moghadam. 2002. Investigation of membrane fouling,
Desalination 153, 155–160.
Mulder, M. 2003. Basic Principles of Membrane Technology. Kluwer, Dordrecht.
Paugam, L., D. Delaunay, N. W. Diagne, M. Rabiller-Baudry. 2013. Cleaning of skim
milk PES ultrafiltration membrane: On the real effect of nitric acid step, Journal of
Membrane Science 428, 275–280.
Rabiller-Baudry, M., M. L. Maux, B. Chaufer, L. Begoin. 2002. Characterisation of cleaned
and fouled membrane by ATR-FTIR and EDX analysis coupled with SEM: Application
to UF of skimmed milk with a PES membrane, Desalination 146, 123–128.
Scott, K. 1995. Handbook of Industrial Membranes. Elsevier, Oxford.
Stoller, M., B. De Caprariis, A. Cicci, N. Verdone, M. Bravi, A. Chianese. 2013. About proper
membrane process design affected by fouling by means of the analysis of measured
threshold flux data, Separation and Purification Technologies 114, 83–89.
Stoller M., J. M. Ochando Pulido. 2015. The Boundary Flux Handbook: A Comprehensive
Database of Critical and Threshold Flux Values for Membrane Practitioners. Elsevier
ISBN 9780128015896.
Tang, C. Y., Y.-N. Kwon, J. O. Leckie. 2009. The role of foulant-foulant electrostatic interac-
tion on limiting flux for RO and NF membranes during humic acid fouling-Theoretical
basis, experimental evidence, and AFM interaction force measurement. Journal of
Trägårdh, G. 1989. Membrane cleaning, Desalination 71, 325–335.
Vasan, S. S., R. W. Field. 2006. On maintaining the consistency between the film model and the
profile of the concentration polarisation layer, Journal of Membrane Science 279, 434–438.
Wijmans, J. G., S. Nakao, J. W. A. Van Den Berg, F. R. Troelstra, C. A. Smolders. 1985.
Hydrodynamic resistance of concentration polarization boundary layers in ultrafiltra-
tion, Journal of Membrane Science 22, 117–135.
Wu, D., M. R. Bird. 2007. The fouling and cleaning of ultrafiltration membranes during the filtra-
tion of model tea component solutions, Journal of Food Process Engineering 30, 293–323.
Zydney, A. 1997. Stagnant film model for concentration polarisation in membrane systems,
Journal of Membrane Science 130, 275–281.
3 Activity-Driven
Membrane Processes
Robert Field and Edit Marki
CONTENTS
3.1 Introduction..................................................................................................... 67
3.2 Dialysis............................................................................................................ 68
3.3 Concept of “Activity”....................................................................................... 69
3.3.1 Activity and Activity Coefficients....................................................... 69
3.4 Polymers for Gas Separation and Pervaporation............................................. 70
3.5 Gas Separation and Pervaporation: Simple Solution-Diffusion Theory......... 73
3.6 Solution-Diffusion Theory and Its Link to “Activity”..................................... 76
3.7 Pore Wetting.................................................................................................... 78
3.8 Temperature Polarization................................................................................. 79
3.9 Heat Transport Process....................................................................................80
3.10 Membrane Distillation..................................................................................... 82
3.11 Osmotic Distillation.........................................................................................84
3.12 Concluding Remarks....................................................................................... 85
Nomenclature............................................................................................................ 86
References................................................................................................................. 88
3.1 INTRODUCTION
In the area of membrane technology, the conventional distinction is between porous
and nonporous processes, but in addition, one should always ask, “Is the process
pressure driven or ‘activity’ driven?” If we exclude electrically driven processes
from Table 1.1 in Chapter 1, it is seen that we have a 2 × 2 matrix. In Table 3.1,
the 2 × 2 matrix is reordered and expanded to include all of the processes that are
covered in this chapter. Below, we briefly consider dialysis and leave the main con-
sideration of the other process in corner A, namely, membrane distillation (MD), to
the end of the chapter.
In MD, the pores are not wetted with the two liquid streams being separated by
a hydrophobic membrane. There is continuity only for volatile components such
as water. This process is covered in Section 3.10; it is an activity-driven nonwet-
ted membrane process. At this stage, we note that for MD, the activity difference
takes the form of a partial-pressure difference, whereas for dialysis, it approxi-
mates to a concentration difference. Furthermore, thermal effects are significant
in MD and the process needs to be considered separately from other membrane
processes.
67
TABLE 3.1
Classification of the Most Common Membrane Processes into Groups A to D
Porous Membrane Dense Membrane (Nonporous)
“Activity”-driven Dialysis, including A Gas separation (GS) B
process hemodialysis Pervaporation (PV) and vapor permeation (VP)
Membrane distillation (MD)b Forward osmosis (FO)/osmotic distillation (OD)
Pressure-driven Nanofiltration (NF) C Reverse osmosis (RO) D

processa Ultrafiltration (UF),
microfiltration (MF)
a For UF and MF membranes, separation performance is determined by size exclusion mechanism, and
for NF by size and charge exclusion.
b In MD, pores are not wetted. The concentration difference across the membrane takes the form of
a partial-pressure difference.
As noted in Chapter 1, some membrane processes have nonporous mem-

branes that do not operate on a size exclusion mechanism. This is another part of
the 2 × 2 matrix—corner B. Those of relevance to the food industry include gas
separation (GS), osmotic distillation (OD), and pervaporation (PV), which have
either current niche applications or potential future applications. Interest in osmoti-
cally driven processes has reemerged in forward osmosis; osmotic distillation is dis-
cussed further in Section 3.11.
In Section 3.3, there is a brief introduction to the concept of activity and activity
coefficients. Then, after introducing the concept of “activity,” we concentrate on the
processes in box B. The processes in box C have been covered in the earlier chapters
and are not mentioned again until applications are covered in a later chapter. Reverse
osmosis, box D, is mentioned briefly because of the link to activity.
3.2 DIALYSIS
Dialysis, which we briefly discussed in Chapter 1, is to be found in corner A of
the table. The process depends upon mass transfer by diffusion from one side of a
wetted membrane to the other side. The two streams are typically aqueous and the
pores too contain water, so there is continuity of the liquid phase from one side to
the other. Pressure on both sides is low so that there is very little convective flow;
for pure dialysis, there is no convection. The porous membrane has two functions:
(i) it acts to provide interfacial area for the diffusing molecules and (ii) the pores may
act to exclude larger components of the feed. If the interfacial area per square meter
of membrane surface is a m2 per m2, then the flux of a component can be estimated
from
Dij
Flux = a(ci1 − ci 2 ) (3.1)
lM
Activity-Driven Membrane Processes 69
where ci is the concentration of component i, with the numbers 1 and 2 referring to

different sides of the membrane; Dij is the diffusion coefficient of component i with
respect to the solvent j; and lM is the thickness of the membrane.
Those who have read the earlier chapters may be wondering about the effect of
concentration polarization. As the fluxes are very low, the concentrations ci1 and ci2
can, to a first approximation, be taken to be bulk concentrations. In other words,
the resistance to mass transfer is principally due to the stagnant fluid in the pores
and not due to the mass transfer boundary layers on either side. Flow of the buffer
solution on the permeate side is important to maintain the concentration difference
and the hydrodynamics do affect the mass transfer but not to the same extent as
in say osmotic distillation. Thus, consideration of an equation more complex than
Equation 3.1 is generally not required for dialysis.
As membranes become cheaper, more applications might emerge in the biological
and food industries to go alongside the major biomedical applications. Separation can
be augmented by the application of pressure and there may be potential to explore
“mixed” or hybrid processes.
3.3 CONCEPT OF “ACTIVITY”

3.3.1 Activity and Activity Coefficients
Consider an ideal mixture of two liquid components A and B. If the average energy
of the A–B interactions within the mixture is the same as the average of the A–A and
B–B interactions, then it is an ideal solution and it follows that the enthalpy change
when A and B are mixed must be zero, that is, ΔmixHideal = 0. Also, the vapor pressure
of the solution obeys Raoult’s law (defined below), and thus the activity coefficient of
each component γi (which measures deviation from ideality) is equal to one. Raoult’s
law, which applies to ideal solutions, states that the vapor pressure of component i
above a mixture is equal to the product of the mole fraction of i in the liquid phase
and its saturated vapor pressure.
In most real systems (some are ideal), the activity coefficient γi is not equal to
unity and its value reflects the interactions between molecules that influence the
thermodynamic equilibrium of the system. The activity coefficient can be described
by a modification of Raoult’s law for real liquid mixtures as
pi
γi = (3.2)
xi pi0
where p refers to the vapor pressure, x the mole fraction in the liquid phase, and pi0
the saturated vapor pressure of component i. As noted in Chapter 1, the actual activ-
ity of component i is equal to its molar fraction multiplied by the activity coefficient,
that is, ai = γixi.
The activity coefficients depend on the molecular interactions in the mixture.
The forces of interactions between chemically different molecules are usually
greater than those found between molecules of the same chemical species. Now, the
lower the concentration of a solute in a mixture, the higher the probability that those
molecules will collide with molecules of a different chemical species. This is the rea-
son for the activity coefficient of say A in water being greater as the concentration of
A decreases toward zero—the value at infinite dilution. In contrast, the activity coef-
ficient of molecules at high mole fractions asymptotes to unity. Note that we have
been referring to activity coefficient; as mentioned above, ai = γixi and therefore as xi
tends to zero, ai will also tend to zero even though γi generally tends to a maximum.
When γi ≈ 1 over the whole range of concentration (0 ≤ xi ≤ 1), the behavior of
component i is essentially ideal. Now, the most common case for liquid mixtures
is γi > 1 and these liquids are said to show positive deviation from Raoult’s law. If
γi ≫ 1, the liquid mixture may display positive azeotropic behavior. A well-known
example of a positive azeotrope is that of a binary mixture of ethanol and water at
89.4 mole percent ethanol. At atmospheric pressure, pure ethanol boils at 78.4°C,
water boils at 100°C, but the azeotrope boils at 78.2°C. As this is lower than the
boiling point of either constituent, positive azeotropes are often called minimum
boiling mixtures. While this is correct, it is probably better to remember the alterna-
tive name, pressure maximum azeotropes, as this relates directly to Equation 3.2.
Negative deviations from Raoult’s law, γi < 1, are rarer. Negative azeotropes
display a maximum in boiling point. An example is nitric acid and water with the
azeotropic composition being around 68% nitric acid with a boiling point about 20°C
above that of water.
As azeotropic mixtures exhibit the same concentration in the vapor phase as that
in the liquid phase, this prevents separation via fractional distillation. We will return
to this point when considering pervaporation.
When it is important to obtain estimates of activity coefficients, various meth-
ods can be used. The most common are empirical models, based on quasi-chemical
theories, such as those due to Margules and van Laar, and more modern semiem-
pirical models such as UNIFAC and UNIQUAC. For engineering applications, the
UNIFAC method can be used for an initial estimation since it does not require any
experimental results. However, the older empirical models, based on quasi-chemical
theories, might be considered to give one a feel for what happens provided the
mixture is binary.
3.4 POLYMERS FOR GAS SEPARATION AND PERVAPORATION

A gas permeation membrane (GS), unlike cryogenic distillation, separates gas mix-
tures without a change in phase. Separation is achieved by virtue of differences in
diffusion (which is influenced by molecular size) and differences in gas solubility
in the membrane. The driving force for permeation is not the pressure difference
across the membrane per se; the driving force for each component is essentially
the partial-pressure difference of that component. Later, mention is again made of
activity but we can approximate this as being proportional to partial pressure. One
of the motivations for introducing GS is that it is a paradigmatic activity-driven
membrane process. The key difference between GS and PV processes is that the
latter have a liquid on the feed side and a particularly low pressure on the perme-
ate side. Overall, there are strong similarities with GS as well as key differences
(Section 3.5).
Rubbery polymers (elastomers), which have a glass transition temperature below

room temperature, have relatively high diffusivities that do not differ significantly
from one component to the next. Thus, if they are used to achieve a separation, then
there has to be significant differences in the components’ solubility in the polymer.
In hydrophobic PV, the aim is to remove relatively minor amounts of organics from
an aqueous phase and such processes benefit from two factors: (i) these organic com-
ponents have a high activity coefficient and (ii) they have a much higher affinity for
rubbery polymers than water. Thus, a polydimethylsiloxane (PDMS) membrane is
often the preferred choice. In hydrophilic pervaporation such as the dewatering of
alcohols the membrane of choice that emerged is a composite membrane with a
thin poly(vinylalcohol) (PVA) layer coated onto a poly(acrylonitrile) (PAN) support.
These membranes have a relatively high affinity for water.
Some recent work studying the use of membrane separation processes for produc-
ing wine with low alcohol content (Catarino and Mendes, 2011) has used a combina-
tion of membrane processes including PV. Various reverse osmosis and nanofiltration
membranes were used, in diafiltration mode, for removing ethanol from a 12 vol.%
red wine. Prior to this step, PV membranes from GKSS consisting of polyoctylmeth-
ylsiloxane supported by polyetherimide (POMS/PEI) were used to recover the aroma
compounds. Then, after the dealcoholization stage, the aroma compounds were added
back to the dealcoholized wine. Work in Hungary (Takács et al., 2007) with Tokaji
wine used pervaporation for the removal of alcohol and the results showed that the
working temperature plays the most important role in the production of low alcoholic
and alcohol-free wines by pervaporation. While the fluxes improved at higher temper-
atures, the separation efficiency and product quality deteriorated. Production rates at
an acceptable level of product quality implied a large investment cost mainly due to the
relatively high price of pervaporation membranes. However, a niche market for PV in
the wine industry might involve their use as an “electronic nose” (Schäfer et al., 2006).
While the introduction to the solution-diffusion process below is in terms of gas per-
meation (and it might be read as implicitly stating that high permeation is desirable), it
should not be forgotten that gas barrier properties of extruded films is of greater interest
in the food industry. In this area, blends may well play an increasingly important role. It
has been found (Boufarguine et al., 2013) that blending poly(lactic acid) (PLA) with a
small amount of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV; 10 wt%) using
multilayer coextrusion process increased both ductility and gas barrier properties of the
extruded films compared with the properties of neat PLA and also in comparison with
blends obtained using classical blending methods. The authors conclude that these new
PLA/PHBV blends are a promising material for applications such as food packaging.
Thinking specifically of GS, it will be noticed in the next section on solution-diffu-
sion theory that the solubility of gaseous components in the membrane (factor S) will
combine with diffusion (D) through the membrane to determine the p ermeability.
The relative permeability of two components will, together with feed composition,
determine the selectivity of separation. The permselectivity for a gaseous pair is a
specific characteristic of a membrane and generally varies inversely with gas perme-
ability. Indeed, an empirical upper bound relationship for membrane separation of
gases was published in 1991 and reviewed in 2008 (Robeson, 2008). On a log-log
plot of the permeability of the fast gas versus the separation factor, virtually all the
100
Present upper bound

Prior upper bound
Alpha O2/N2
10
1
0.0001 0.01 1 100 104
P(O2) barriers
FIGURE 3.1 Upper bound correlation for O2/N2 separation. (From Robeson, L.M. Journal
of Membrane Science 320(1–2), 2008, 390–400.)
experimental data points falls below a line of negative slope. So improvements in

permeability come at the expense of selectivity and vice versa. Therefore, to achieve
a high permselectivity, a membrane with an intrinsically low permeability must be
selected. An example of this is shown in Figure 3.1.
While opportunities abound to extend membrane markets for gas and vapor sepa-
rations, the leading researcher in this area has stated (Koros and Mahajan, 2000) that
the existing membrane materials, membrane structures, and formation processes are
inadequate to fully exploit these opportunities. It was noted at the turn of the century
that the current spectrum of applications of gas separation membranes were mainly
confined to nitrogen enrichment, oxygen enrichment, hydrogen recovery, acid gas
(CO2, H2S) removal from natural gas, and dehydration of air and natural gas (Koros
and Mahajan, 2000). This has not changed in recent years.
PV is a more complex process than GS and that is probably one of the reasons why
PV has not been adopted as much as its proponents had expected. In 1999, two of the
authors contributing to this book (Lipnizki et al., 1999) stated that in recent years,
PV has established itself as one of the most promising membrane technologies. They
went on to mention that PV offers potential solutions in a wide range of applica-
tions from the well-established dehydration of organic compounds to the recovery
of organic compounds from water and the separation of organic mixtures. However,
they did caution that within these applications, PV as a single process has to com-
pete with conventional processes such as distillation, liquid–liquid extraction, and
adsorption, which are reliable and whose cost can be readily calculated by i ndustry.
They went on to say that in many cases, PV alone may not suffice and that hybrid
processes should be considered. Indeed, where PV has been realized on an industrial
scale, it has been as a hybrid process, PV combined with distillation for dehydration,
or PV with a chemical reactor where the PV is used to remove water and shift the
equilibrium, so giving a higher conversion. With regard to the recovery of natural
aroma compounds in the food industry, PV has been considered (Lipnizki et al.,
2000a,b) but as far as we know, it has not been adopted.
3.5 GAS SEPARATION AND PERVAPORATION:

SIMPLE SOLUTION-DIFFUSION THEORY
One of the main reasons for introducing the solution-diffusion theory in modest
detail is to show that the performance of membrane systems is determined not only
by membrane properties but also by operating conditions. The nomenclature is
consistent with that of Ten and Field (2000) and initially we consider only GS.
Consider a dense membrane with a permeate pressure, P, on the one side and a
feed pressure, pf, on the other side (Figure 3.2). For a component i, its partial pres-
sure is pfxi on the feed side and Pyi, where xi and yi are the mole fraction on the feed
and permeate sides, respectively. Now, assume that the concentration of component i
within the membrane Cim at the feed and permeate interfaces is given, respectively, by
a
Cim = Si p f xi d
Cim = Si Pyi (3.3)

where Si is the partition coefficient that is taken to be the same for sorption/feed side
and desorption/permeate side.
Also assume that the diffusivity of component i in the membrane, Dmi, is constant.
Then the molar flux is given by
Qi = Dmi (Cim
a
− Cim
d
) = Dmi Si ( p f xi − Pyi ) = Pi ( p f xi − Pyi ) (3.4)

where P̂i is the permeability through the membrane for component i.
lm
Feed
xi Caim
yi
Cdim
Qi
µiF
µiP
Permeate
z
FIGURE 3.2 Schematic for pervaporation.

The corresponding equation for component j is
Q j = Pˆ j ( p f x j − Py j ) (3.5)

where P̂j is the permeability through the membrane for component j.

Defining αGS as the selectivity (= ( yi /xi /y j /x j )) and α*mem as the intrinsic selectivity
(i.e., the ratio of the permeabilities), then the division of Equation 3.4 by Equation
3.5 gives
1 − Pyi /p f xi
α GS = α*mem (3.6)
1 − Py j /p f x j

which clearly shows that the selectivity achieved depends not only on intrinsic selec-
tivity but also on the feed composition and the pressure ratio P/pf. Newer editions
of popular textbooks on separation processes have chapters on membranes, includ-
ing sections on gas permeation (Geancoplis, 1993; McCabe et al., 1993; Seader and
Henley, 1978) and the interested reader wanting further details is referred to these
books.
With PV, separation is generally achieved by applying a vacuum to the permeate
side of the membrane while the other side is liquid and heated to raise its vapor pres-
sure. (Also, there is energy transfer from the feed stream to the permeate.) The low
partial pressure of the permeating components can be achieved by having a sweep
gas, which might be preferred in analytical applications (e.g., electronic nose men-
tioned earlier) but the use of an inert carrier gas is unlikely to be feasible for process
applications.
Pervaporation involves simultaneous mass and heat transfer. The components on
the permeate side are in the vapor phase, so latent heat has to be provided. The
permeating components are in essence evaporated and also permeated through
the membrane, hence the term “pervaporation.” With distillation, the separation is
largely dependent upon vapor/liquid equilibria, but with PV, the separation is depen-
dent on the solubility and the diffusivities of the constituents in the membranes. This
process is not limited by the formation of azeotropes and overcoming azeotropes is
an area of application. While azeotropic distillation that involves the addition of a
third component can split azeotropes, and may do so relatively cheaply, it may well
be desirable to avoid the addition of the third component because traces of it will be
left in the eventual products.
When modeling pervaporation, three additional factors need to be taken into
account. On the feed side, there is a liquid and the corresponding vapor pressure
follows from Equation 3.2 and is pi = γ i xi pi0 . Second, the mass transfer within a
liquid boundary layer is much slower than that within a gas boundary layer and
therefore the concentration of the faster permeating components at the membrane
surface will be less than in the bulk. The reduction is not insignificant. Lastly, the
partition coefficient may well not be uniform for the two sides of the membrane
and the difference can be a factor of five (Ten and Field, 2000). A large value on
TABLE 3.2
Comparison between Pervaporation and Vapor/Gas Separation
Pervaporation Vapor/Gas Separation
Mass transport
J i = K i ( Pi sat γ i xi − Θi Pyi ) Pˆ i
equation Qi = ( p f xi − Pyi )
δm
Simple mass transfer equation but complicated by Simple mass transport
compound nature of Ki and activity coefficient equation
Partial vapor pressure as driving force if Θi = 1; Partial pressure as driving
otherwise, pseudo-vapor pressure as driving force force
Partition coefficient for sorption
and desorption are equal
Separation factor 1 − Pyi / ( p f xi )
1 − Θi Pyi / ( Pi sat γ i xb,i )
(selectivity) α PV = α VLE ε bl Emem
*
α GS = α*mem
1 − Θ j Py j / ( Pjsat γ j xb, j ) 1 − Py j / ( p f x j )
Affected by vapor–liquid equilibrium Affected by intrinsic

selectivity membrane
material, α*mem
Affected by intrinsic selectivity of membrane Affected by the ratio of partial
*
material, Emem pressure at the feed to the
one at the permeate
Affected by boundary layer effect, εbl Negligible boundary layer
effect
Affected by the ratio of the vapor pressure of the When P = 0, α GS = α*mem
feed to the partial pressure of the permeate if
Θi = 1
Otherwise, use of pseudo-vapor pressure required
When the driving force
When P = 0, α PV = α VLE ε bl Emem
*
. When the
approaches zero, there is no
driving force is diminished, αPV = αVLE,
separation at all
separation returns to vapor–liquid equilibrium
Source: Ten, P.K., Field, R.W. Chemical Engineering Science 55, 2000, 1425–1445.
Note: Qi, permeate flux of component i in gas/vapor separation; P̂i, permeability of component i for gas
separation membrane; pf, feed pressure for gas separation membrane; α*mem, the intrinsic selectivity
of the gas separation membrane, = Pˆ i /Pˆ j.
the permeate side acts to “exaggerate” the adverse effect of downstream pressure.
A summary of the differences between PV and GS is given in Table 3.2.
The table actually mentions vapor/gas separation as if they could be modeled
in the same way. Now, if the feed to a membrane of the type used for the dry-
ing of organic streams is a vapor, there will be no mass transfer boundary layer
effects and of course liquid-phase activity coefficients will be superfluous. VP pro-
cesses are used for the separation of saturated mixed vapors, with no change of the
phase involved. Thus, unlike PV, no heat addition equivalent to the latent heat is
required and the operation of the membrane unit can be treated as being isothermal.
(a) (b)
FIGURE 3.3 Fouling mechanisms of dense membranes. (a) Surface blocking, (b) Particle
blocking.
Compared with GS, the only factor that might need to be considered with VP is
whether the partition coefficient is the same on both sides or not. If it is, then the GS
expressions apply. If not, a slight modification is required. One application of VP is
the removal of contaminating organics solvents from air streams.
With the exception of reverse osmosis, the fouling of dense membranes has often
been neglected. Earlier observations (Lipnizki et al., 2004) have shown that fouling
can also have an effect on dense pervaporation membranes. For dense membranes,
two types of fouling can be identified: (i) surface blocking and (ii) particle blocking
(Figure 3.3). In the case of surface blocking, it is assumed that the blocked membrane
area is not available at all for mass transport and, therefore, the active membrane
area is reduced. One might also label this as surface blinding. The flux through
the partly blocked membrane can be described as a function of the theoretical flux
through the unblocked membrane by
( Atot − Ablock (t ))
J = J0 (3.7)
Atot
where J0 is the flux through an unfouled membrane, Atot is the total membrane area,
and Ablock is the membrane area blocked. The latter is a function of time.
The second mode of blocking does not involve blanketing of the surface. Instead,
it is envisaged that there are two effects: (i) a reduced active membrane area due
the particles and (ii) an increased diffusion path through the membrane as illus-
trated in Figure 3.3. The fouling of dense membranes will not be discussed further.
3.6 SOLUTION-DIFFUSION THEORY AND ITS

LINK TO “ACTIVITY”
At the fundamental level, the flux can be related to the gradient of the chemical
potential as
−Ci ⋅ Di ( z) d µ i
Ji ( z) = ⋅ (3.8)
R ⋅T dz
and it will be noticed that in Figure 3.2 there is continuity in the chemical potential
μi at the interfaces.
Now, the chemical potential can generally be described as a function of tempera-

ture, pressure, and composition:
p T
µ i (T ) = µ (T ) + RT ln a +
0
i
m
i
∫
pi0
Vi dp −
∫ S dT
Ti0
i (3.9)

With the assumption of constant pressure and temperature within the membrane,
the key term for PV and GS is the one involving the activity. So, by combining the
above two equations, one obtains
(
 d lnaim
J i = −Ci ( z) ⋅ Di ( z) ⋅ 
)  (3.10)
 dz 

With the assumption of a linear variation of the activity in the direction of the
flux, Equation 3.10 can be rewritten as
−C ( z) ⋅ Di ( z) ∆aim
Ji = ⋅ (3.11)
aiM ∆z
In this equation, aiM denotes the average activity coefficient in the membrane,
while ∆aim represents the difference in activity of component i between feed side
and permeate side. The difference Δz is the membrane thickness. Now, at the two
interfaces, there will be a very close approach to thermodynamic equilibrium

between the liquid feed phase just outside the membrane and the feed membrane
phase just inside. It follows that
At the feed side in PV:
aim, F = ai, F = xi, F ⋅ γ i, F (3.12)

At the permeate side:
P
aim, P = ai, P = yi, P ⋅ (3.13)
pi0
Hence, introducing Equations 3.11 and 3.12 into Equation 3.10 and replacing Δz by
the membrane thickness lM, the following expression can be derived:
Di,m ⋅ Ci,m 1 m
Ji = ⋅ (ai, F − aim, P ) (3.14)
aiM lM
An experimental estimation of Di,m, Ci,m, and aiM independent of each other is

difficult and fraught with inaccuracies. Thus, these parameters are combined into a
phenomenological permeability parameter P̂i , which has to be determined for every

system (component—membrane) of interest. Hence
Pi
Ji = (ai, F − ai, P ) (3.15)
lm
Recognizing that for a gas at low pressure, the activity is equal to the partial pres-
sure of the gas divided by the standard pressure, it is readily seen that Equation 3.15
is equivalent to those given in Section 3.5. With some membranes, it is difficult
to determine the actual thickness of the actual layer in which case it is useful to
work with the term “permeance,” which is P̂i /lm . So, when it is difficult to deter-
mine permeability and active layer thickness independently, one simply uses flux
and driving force to determine permeance.
The influence of the feed temperature on the permeability parameter P̂i can be
described by an Arrhenius-type equation:
E  1 1 
Pi (TF ) = Pi 0 exp  i  −   (3.16)
 R  T0 TF  

3.7 PORE WETTING

Some membrane processes (membrane distillation [MD], osmotic distillation [OD])
are only possible if a restrictive condition is fulfilled; the pores of the membrane
must not be filled with liquid.
Porous membranes made from hydrophobic polymers do not permit passage of
water until a critical pressure difference is exceeded. The critical pressure difference
depends on the interfacial tension, the contact angle, and the size and shape of the
openings in the membrane.
Water and aqueous solutions of inorganic substances have such high values of surface
tension (γL ≥ 72 × 10−3 N/m) that for a number of hydrophobic microporous membranes
with pores in the range of 1 μm or less (such as polypropylene [PP], polyvinylidene
fluoride [PVDF], and polytetrafluoroethylene [PTFE, Teflon]), this nonwetting condi-
tion is guaranteed in the absence of contaminants. However, when organic solutes are
present in an aqueous solution, the surface tension γL will decrease rapidly. If the con-
centration of organic material does not exceed a certain critical value, the membrane
distillation process can still be used. On the other hand, if the concentration of organic
material exceeds this critical value, the microporous membrane will be filled with liq-
uid. In this case, membrane distillation is no longer possible (Franken et al., 1987).
The properties of membranes suitable for membrane distillation should include
reasonably large pore size and narrow pore size distribution, limited by the mini-
mum liquid entry pressure (LEP) of the membrane. In MD, the hydrostatic pressure
must be lower than LEP to avoid membrane wetting. This can be quantified by the
Laplace equation in the following form:
2Bγ L
LEP = cosϕ < Pprocess − Ppore (3.17)
rmax
where B is a geometric factor, γL is the surface tension of the solution, φ is the contact
angle between the solution and the membrane surface, which depends on the hydro-
phobicity of the membrane, rmax is the largest pore size, Pprocess is the liquid pressure
on either side of the membrane, and Ppore is the air pressure in the membrane pore.
Thus, the higher the surface tension of the liquid, the larger the contact angle and the
smaller the pore radius, the greater the intrusion pressure.
Membrane wetting can occur under the following conditions:
1. The hydraulic pressure applied on the surface of the membrane is greater

than the LEP.
2. The foulant depositing on the membrane surface can effectively reduce the
hydrophobicity of the membrane, which has generally been found in a long-
term operation or in the treatment of high-concentration feeds such as those
found in brine crystallization.
3. In the presence of high organic content or surfactants in the feed,
which can lower the surface tension of feed solution and/or reduce the
hydrophobicity of the membrane via adsorption and lead to membrane
wetting (Rácz et al., 2014).
3.8 TEMPERATURE POLARIZATION

In general, the main resistances are located at the boundary layer within the
membrane and also on each side of the membrane.
Boundary layer resistance can be modeled by temperature polarization (TPC).
The TPC indicates the actual temperature difference across the membrane rela-
tive to the temperature difference between the bulk temperature of the hot and cold
channels:
∆T T −T
TPC = = Fm Pm (3.18)
∆Tmax TFb − TPb
The value of TPC is close to unity means the process is controlled by mass transfer
within the membrane. In contrast, if the value of TPC approaches zero, the transfer
process is controlled by heat transfer through the thermal boundary layers (Lawson
and Lloyd, 1997). In most MD processes, TPC neither approximates to unity nor to
zero and one needs to simultaneously solve the heat and mass transfer equations.
In many experimental and industrial MD systems, the bulk of the available
thermal gradient is lost in temperature polarization. Of the commonly used MD sys-
tems, tubular and hollow fiber membranes show the least temperature polarization.
Under normal operating conditions, the temperature polarization in osmotic dis-
tillation applications is quite small. It is interesting that the situation is exactly the
opposite for the process of membrane distillation, where a warm solution to be con-
centrated is separated via a microporous membrane from a cold liquid into which
condensation is to occur. In that case, a membrane of very low thermal conductance
is necessary to prevent heat flow by conduction from the warm to the cold liquid
stream.
3.9 HEAT TRANSPORT PROCESS

Gas and vapor transport through microporous membranes takes place principally
by molecular diffusion. For pores of diameter in the nanometer range, at ambient
temperature and gas-phase pressures of the order of the vapor pressure of water at
that temperature, the mean free path of gas molecules is significantly greater than the
pore diameter. Under these circumstances, molecular transport occurs by Knudsen
diffusion.
The only driving force for mass transfer is a water vapor pressure gradient.
However, OD and MD differ in the method by which this gradient is maintained.
In OD, the water vapor pressure of the “strip” stream is lowered, relative to that of
the feed stream, by using a concentrated aqueous solution of an osmotic agent as the
“strip” solution.
Membrane techniques where phase changes occur involve simultaneous
processes; both heat and mass transfer processes need to be considered. In these
processes, water vapor molecules transfer from the warm feed side to the condensa-
tion sides. Since both processes are involved, the heat and mass transfer profiles are
depicted as shown in Figure 3.4.
The heat transfer within the membrane occurs in both the matrix and its pores,
and can be summarized in three steps (Khayet and Matsuura, 2011):
1. Convection from the feed bulk to the vapor–liquid interface at the membrane
surface (i.e., the thermal boundary layer at the feed side):
QF = hF (TFb − TFm ) (3.19)
where QF is the heat flux and hF is the heat transfer coefficient at the feed side.
2. Evaporation and conduction through the microporous membrane:
Qv = J m ∆H v (3.20)
Bulk feed Membrane Bulk permeate
TFb
TFm
TPm
TPb
Jm
Mass flux
QF Qv QP
Heat flux
Qc
lm
FIGURE 3.4 Transfer profiles in MD.

km
Qc = (TFm − TPm ) (3.21)
lm
where Qv and Qc are the heat flux of vaporization and conduction, respec-
tively; Jm is the mass flux of vapor, ΔHv is the latent heat of vaporization, km
is the average thermal conductivity of membrane and vapor, and lm is the
membrane thickness.
3. Convection from the vapor–liquid interface at the membrane surface
to the permeate side (i.e., the thermal boundary layer of the permeate
side):
QP = hP (TPM − TPb ) (3.22)
where QP is the heat flux and hP is the heat transfer coefficient at the
permeate side.
The total heat flux (QT ), across the membrane, can be written as
−1
 
 1 1 1
QT = U ∆Tb =  + +  ∆Tb = Qv + Qc (3.23)
J ∆H
 hF hm + m v hP 
 TFm − TPm 

where U is the overall heat transfer coefficient and ΔTb is the bulk temperature
d ifference among the feed and permeate sides.
Under steady-state conditions, the heat transfer is represented by Equation 3.24:
Q = hF (TFb − TFm ) = hm (TFm − TPm ) + J m ∆H v = hP (TPm − TPb ) (3.24)
On the basis of Equation 3.24, the membrane surface temperatures (TFm) and (TPm)
can be estimated using the following equations:
 h 
hm  TPb + F TFb  + hFTFb − J m ∆H v
 hP 
TFm = (3.25)
 h 
hm + hF  1 + m 
 hP 

 h 
hm  TFb + P TPb  + hPTPb + J m ∆H v
 hF 
TPm = (3.26)
 h 
hm + hP  1 + m 
 hF 

Further, the heat transfer coefficient of the membrane (hm) can be determined
using Equation 3.27:
km (1 − ε)kg
hm = = εks + (3.27)
lm lm
where ε is the porosity of the membrane, and ks and kg are thermal conductivities of
the membrane and of the vapor that fills the pores, respectively.
The heat transfer coefficients of the boundary layers (hf and hp) can be calculated
using empirical correlations of dimensionless groups, namely, Nusselt number (Nu),
Reynolds number (Re), and Prandtl number (Pr):
Nu = aReb Pr c (3.28)

where a, b, and c are correlation coefficients dependent upon specific

hydrodynamic conditions.
3.10 MEMBRANE DISTILLATION

Membrane distillation (MD) is one of the emerging nonisothermal membrane
separation processes where a thermally driven transport of vapor through non-
wetted porous hydrophobic membranes is taking place. As in other membrane
separation processes, the driving force is the chemical potential difference

through the membrane thickness. Simultaneous heat and mass transfer occurs in
this process and, as will be explained later, different MD configurations such as
(i) direct contact membrane distillation, (ii) sweeping gas membrane distillation,
(iii) vacuum membrane distillation, and (iv) air gap membrane distillation can be
used for v arious applications (food, medical, desalination, environmental/waste
clean-up, water-reuse, etc.). The lower operating pressures than in the pressure-
driven processes, the lower temperatures than in the distillation, and the high
rejection factors achievable e specially during water treatment containing nonvol-
atile solutes may make MD more attractive than many other popular separation
processes; at least for some applications.
The possibility of using waste heat and/or alternative energy sources (such as
solar and geothermal energy) enables MD to be combined with other processes
in hybrid systems, making it a more promising separation technique for an
industrial scale.
The major drawbacks include membrane pore wetting, low permeate flow rate,
and flux decay as well as uncertain energetic and economic costs.
MD is a process mainly suited for applications in which water is the major
component present in the feed solution. MD is a thermally driven process, in which
only vapor molecules are transported through porous membranes. The hydropho-
bic nature of the membrane prevents liquid solutions from entering its pores due to
the surface tension forces. As a result, liquid/vapor interfaces are formed at both
entrances of the membrane pores.
The MD driving force may be maintained with one of the four following
possibilities applied on the permeate side:
1. An aqueous solution colder than the feed is applied in direct contact with
the permeate side of the membrane known as direct contact membrane
distillation (DCMD). The driving force is the vapor pressure difference
created by the temperature difference across the hydrophobic membrane.
This is the simplest configuration capable of producing reasonably high
flux.
2. Vacuum is applied on the permeate side of the membrane module by means
of a vacuum pump. This MD configuration is termed vacuum membrane
distillation (VMD). The applied pressure must be lower than the saturation
pressure of volatile molecules to be separated from the feed solution. In
this method, if needed, permeate is condensed in a separate device. This
configuration is useful when volatiles are being removed from an aqueous
solution.
3. In the sweeping gas membrane distillation (SGMD) configuration, a cold
inert gas flows on the permeate side and sweeps the vapor molecules away
from the membrane. The condensation takes place outside the module. It is
used when volatiles are removed from an aqueous solution.
4. In case of air gap membrane distillation (AGMD), an air gap is interposed
between the membrane and a condensation surface. The configuration has
the highest energy efficiency, but the flux obtained is generally low.
The modeling of mass transfer within the membrane pores has received the most
interest from MD investigators. Mass transfer in MD occurs by convective and d iffusive
transport of water vapor across the microporous membrane. The driving force for mass
transfer is the difference in water vapor pressure on either side of the membrane.
Mass transfer across the membrane is somewhat complicated and includes sev-
eral basic mechanisms; therefore, several MD models are available in the literature.
There are two basic approaches for modeling MD. The first one concerns the
modeling of the transport mechanism through the hydrophobic membrane. The sec-
ond is concerned with the overall modeling for predicting the permeate flux. A lin-
ear relationship between the mass flux (Jm) and the water vapor pressure difference
(ΔPv) across the membrane was suggested to describe the water vapor transport:
KM w
J m = C MD ∆Pv = ( Pvm1 − Pvm 2 ) (3.29)
RTm
where Jm is the water vapor mass flux, CMD is the membrane distillation coefficient
and can be a function of operating parameters and membrane structure, K is the
mass transfer coefficient, and Pvm1 and Pvm2 are the vapor pressures of water vapor
evaluated at the membrane surface temperatures TFm and TPm. The mass transfer
coefficient (K) may be reasonably estimated from a combination of Knudsen and
molecular diffusion theories. For pure liquid, the water vapor pressure at the liquid–
vapor interface can be calculated using the Antoine equation (Mengual et al., 2004).
3.11 OSMOTIC DISTILLATION

Osmotic distillation (OD), also known as osmotic evaporation, membrane evapora-
tion, or isothermal membrane distillation, is a separation process in which a liquid
mixture containing a volatile component is contacted with a microporous, nonwet-
table membrane whose opposite surface is exposed to a second liquid phase capable
of absorbing that component. This technique can be used to extract selectively the
water from aqueous solutions under atmospheric pressure and at room temperature,
thus avoiding thermal degradation of the solutions. OD is said to be nearing com-
mercialization for the concentration of beverages and other liquid foodstuffs, and
is under evaluation for the concentration of aqueous solutions of thermally labile
pharmaceutical products and biologicals. The process can also enable the s elective
removal of a single volatile solute from aqueous solution (for instance, ethanol
from wine and other ferments) using water as the extracting solvent. Low-alcohol-
content beverages have been produced in this manner with minimal losses of volatile
flavor and fragrance components. Osmotic distillation (OD) promises to become an
attractive complement or alternative to other low-temperature separation techniques
such as ultrafiltration (UF), reverse osmosis (RO), pervaporation, and vacuum freeze
drying.
In summary, OD is a membrane transport process in which there is a transfer of
volatiles between feed and stripping streams (most commonly aqueous solutions)
by means of vapor pressure differences. To affect this, a hydrophobic microporous
membrane module is used and any penetration of the solutions into the membrane
pores is thereby inhibited. The membrane thereby functions as the provider of a
vapor gap between the two liquid phases, across which any volatile component is
free to migrate by either convection or diffusion.
If the operating pressure is kept below the liquid entry pressure (LEP) (see
Section 3.7), the membrane cannot be wetted by the solutions. The difference in
solute concentrations, and consequently in water activity of both solutions, gener-
ates between the vapor–liquid interfaces a vapor pressure difference causing vapor
transfer from the dilute solution toward the stripping solution.
The water transport through the membrane can be summarized in three steps:
1. Evaporation of water at the dilute vapor–liquid interface

2. Diffusional or convective vapor transport through the membrane pore
3. Condensation of water vapor at the membrane–brine interface
The evaporative process requires the supply of the latent heat of vaporization at
the upstream meniscus; this can only be provided as sensible heat via conduction or
convection from the bulk upstream liquid, or via conduction across the solid phase
comprising the membrane. Conversely, at the downstream face of the membrane,
condensation of water vapor into the strip requires removal of the heat of condensa-
tion by the same mechanisms. Supplying or removing this energy by conduction/
convection from the bulk liquid phases would, of course, cool the feed and heat the
strip, thereby reducing the driving force for water transport (Hogan et al., 1998). For
successful operation of OD, it is essential that (i) liquid is prevented from penetration
into and passage through the membrane pores, and (ii) unimpeded vapor-phase trans-
port of volatile components from feed to strip solution can occur. The first require-
ment can be satisfied if the membrane surface is sufficiently hydrophobic such that
neither the feed nor strip solutions can wick by capillary forces into the pores, and
the surface tensions of the liquid phases are sufficiently high so that the LEP is well
in excess of the maximum pressure difference across the membrane that might be
encountered in operation.
The most suitable materials for OD membranes are apolar polymers with low
surface free energies. These include the polyolefins, particularly PE and PP, and the
perfluorocarbons, especially PTFE and PVDF. Microporous membranes fabricated
from these materials are available with pore sizes and pore size distributions in
acceptable ranges for this application. The maximum tolerable pore radius to pre-
vent liquid penetration is about 250 nm—corresponding to a pore diameter of about
0.5 micron. Commercially available microporous membranes fall well within this
range of pore dimensions. Membranes of smaller pore size than this, of course, will
withstand higher hydrostatic pressures without liquid intrusion (Kujawa et al., 2015).
During the concentration of aqueous solutions by OD, removal of water from
the feed and its transfer into the strip creates a polarization boundary layer at the
upstream membrane surface of increasing solute concentration and also one on the
strip side of decreasing concentration of salt. This reduces the transmembrane water
flux by depressing the vapor pressure of water over the feed solution contacting the
membrane and, conversely, increasing the water vapor pressure over the strip solu-
tion contacting the downstream membrane surface.
The selection of an osmotic agent for use on an industrial scale should prefer-
ably be in accordance with several basic requirements. It should be thermally stable,
nonvolatile, and have a steep positive temperature coefficient of solubility. These
properties allow the diluted strip solution to be reconcentrated to high levels (through
thermal evaporation) for reuse in the OD process without loss or danger of crystalli-
zation in the evaporator. Also, the osmotic agent should be biocidal, nontoxic, and of
food-grade quality. The latter requirements reflect the interest of the food industry,
in particular, for the production of fruit juice concentrates. Ideally, the osmotic agent
should also be readily available at low cost.
For the osmotic distillation process, mostly salt solutions (NaCl, CaCl2, K2HPO4,
potassium acetate) or some kind of organic solutions (polyethylene glycol, glycerol,
etc.) are used as an osmotic agent (Rácz et al., 2012).
However, neither of these salts conforms to all requirements. Sodium chloride has
a rather low temperature coefficient of solubility, while calcium chloride is sensitive
to precipitation in the presence of carbon dioxide; also, both are quite corrosive to
ferrous alloys at elevated temperature.
3.12 CONCLUDING REMARKS

In the 1980s, all types of membrane processes fell into the category of Less Known
Separation Processes but today the pressure-driven membrane processes can be con-
sidered to be mainstream. For the food industry, activity-driven processes remain in
the Less Known category but this may change. If one of these processes can produce
a superior product, in the same way that RO and UF for fruit juice concentration
produced a product superior to that obtained by evaporation, then that might create a
breakthrough. Also, an activity-driven process might contribute to a hybrid process,
combining a novel membrane process with a conventional process that is superior to
a straightforward conventional process.
NOMENCLATURE
As fluxes are modest; often, “per hour” is used instead of “per second.” This is also
true for some other terms so checking of units is important. Often cmHg was often
used for pressure; below, Pa has been used.
A interfacial area per square meter of membrane surface, m2 m−2

ai activity of component i
Ablock membrane area blocked, m2
Atot total membrane area, m2
B geometric factor
C concentration, kmol m−3
CMD membrane distillation mass transfer coefficient, kg m−2 h−1 Pa−1 or kmol m−2 h−1 Pa−1
Dij diffusion coefficient of component i with respect to the solvent j, m2 h−1 or m2 s−1
*
Emem intrinsic enhancement factor that applies at ultimate vacuum and in the absence of a
boundary layer
h heat transfer coefficient, J h−1 m−2 K−1 or W m−2 K−1
J flux, kmol m−2 h−1
J0 flux through an unfouled membrane, kmol m−2 h−1
Jm mass flux of vapor, kg m−2 h−1
k thermal conductivity, Wm−1 K−1
K mass transfer coefficient, m h−1 or m s−1
lm membrane thickness, m
M molar mass, kg kmol−1
Nu Nusselt number
p vapor pressure, Pa
Pe Peclet number
P̂i permeability of the membrane, kg m−2 h−1 Pa−1 m−1 or kmol m−2 h−1 Pa−1 m−1
Pi partial pressure of component i adjacent to the downstream surface of the membrane, Pa
pi0 saturated vapor pressure of pure component i, Pa
pf feed pressure in gas separation, Pa
Q heat flux, W
Qi molar flux in gas separation, kmol m−2 h−1
r pore size, m
R universal gas constant
Re Reynolds number
S partition coefficient
t time, h
T thermodynamic temperature, K
TPC temperature polarization

x mole fraction
y mole fraction of component in the permeate
z distance in direction of the flux, m
ΔHv latent heat of vaporization, J kmol−1
Greek letters
α*mem intrinsic selectivity of gas separation membrane or the ratio of the permeabilities of the
components through the membrane
γi activity coefficient of component i
γL surface tension of the solution, N m−1
δm effective diffusion transport distance of a component in the selective part of the membrane, m
ε porosity of the membrane
εbl effectiveness factor to account for relative importance of boundary layer resistance
φ contact angle between the solution and the membrane surface
μi chemical potential, J mol−1
Θ desorption factor
Subscript
b bulk condition of liquid feed
c conduction
F feed
g gas/vapor
GS gas separation
i solute or the targeted organic component in the separation
j component j, generally solvent
M membrane (see Section 3.6)
m membrane
m1 within membrane surface adjacent to feed side
m2 within membrane surface adjacent to permeate side
mb adjacent to feed side of membrane surface
P permeate
PV pervaporation
T total
v vaporization
VLE vapor–liquid equilibrium
Superscript
a sorption interface
d desorption interface
m membrane
sat saturated
REFERENCES
Boufarguine, M., Guinault, A., Miquelard-Garnier, G., Sollogoub, C. PLA/PHBV films
with improved mechanical and gas barrier properties, Macromolecular Materials and
Engineering 298(10), 2013, 1065–1073.
Catarino, M. and Mendes, A. Dealcoholizing wine by membrane separation processes,
Innovative Food Science and Emerging Technologies 12(3), 2011, 330–337.
Franken, A.C.M., Nolten, J.A.M., Mulder, M.H.V., Bargeman, D., Smolders, C.A. Wetting
criteria for the applicability of membrane distillation, Journal of Membrane Science
33, 1987, 315–328.
Geancoplis, C. Transport Processes and Unit Operations, 3rd ed., Prentice-Hall, 1993,
Englewood Cliffs, NJ.
Hogan, P.A., Canning, R.P., Peterson, P.A., Johnson, R.A., Michaels, A.S. A new option:
Osmotic distillation, Chemical Engineering Progress, July 1998, 49–61.
Khayet, M., Matsuura, T. Membrane Distillation. Principles and Applications, Elsevier,
2011, Amsterdam, The Netherlands, Oxford, UK.
Koros, W.J., Mahajan, R. Pushing the limits on possibilities for large scale gas separation:
Which strategies? Journal of Membrane Science 175(2), 2000, 181–196.
Kujawa, J., Guillen-Burrieza, E., Arafat, H.A., Kurzawa, M., Wolan, A., Kujawski,
W. Raw juice concentration by osmotic membrane distillation process with hydropho-
bic p olymeric membranes, Food and Bioprocess Technology 8, 2015, 2146–2158.
Lawson, K.W., Lloyd, D.R. Membrane distillation, Journal of Membrane Science 124(1),
1997, 1–25.
Lipnizki, F., Field, R.W., Ten, P.K. Pervaporation-based hybrid process: A review of pro-
cess design, applications and economics, Journal of Membrane Science 153, 1999,
183–210.
Lipnizki, F., Hausmanns, S., Field, R.W. Influence of impermeable components on the per-
meation of aqueous 1-propanol mixtures in hydrophobic pervaporation, Journal of
Membrane Science 228(2), 2004, 129–138.
Lipnizki, F., Olsson, J., Trägårdh, G. Scale-up of pervaporation for the recovery of natural
aroma compounds in the food industry. Part 1: Simulation and performance, Journal of
Food Engineering 54(3), 2002a, 183–195.
Lipnizki, F., Olsson, J., Trägårdh G. Scale-up of pervaporation for the recovery of natural
aroma compounds in the food industry Part 2: Optimisation and integration, Original
Research Article, Journal of Food Engineering 54(3), 2002b, 197–205.
McCabe, W.L., Smith, J.C., Harriott, P. Unit Operations of Chemical Engineering, 5th ed.,
McGraw-Hill, 1993, New York.
Mengual, J.I., Khayet, M., Godino, M.P. Heat and mass transfer in vacuum membrane distil-
lation, International Journal of Heat and Mass Transfer 47(4), 2004, 865–875.
Rácz, G., Kerker, S., Kovács, Z., Vatai, Gy., Ebrahimi, M., Czermak, P. Theoretical and
experimental approaches of liquid entry pressure determination in membrane distilla-
tion processes, Perioidica Polytechnica 58(2), 2014, 81–91.
Rácz, G., Papp, N., Hegedűs, A., Szabó, Z., Nyéki, J., Szabó, T., Stefanovits-Bányai, É.,
Vatai, Gy. Concentration of “Oblachinska” sour cherry juice using osmotic distillation,
International Journal of Horticultural Science 18(1), 2012, 31–34.
Robeson, L.M. The upper bound revisited, Journal of Membrane Science 320(1–2), 2008,
390–400.
Schäfer, T., Serrano-Santos, M.-B., Rocchi, S., Fuoco, R. Pervaporation membrane separa-
tion process for enhancing the selectivity of an artificial olfactory system (“electronic
nose”), Analytical and Bioanalytical Chemistry 384(4), 2006, 860–866.
Seader, J.D., Henley, E.J. Separation Process Principles, John Wiley and Sons, 1978,
New York.
Takács, L., Vatai, Gy., Korány, K. Production of alcohol free wine by pervaporation, Journal
of Food Engineering 78(1), 2007, 118–125.
Ten, P.K., Field, R.W. Organophilic pervaporation: An engineering science analysis of
component transport and the classification of behaviour with reference to the effect of
permeate pressure, Chemical Engineering Science 55, 2000, 1425–1445.
Section II
Application of Membrane
Separation in Food Processing
4 Dairy Industry and
Animal Products
Processing Applications
Geneviève Gésan-Guiziou
CONTENTS
4.1 Dairy Industry.................................................................................................94
4.1.1 Introduction.........................................................................................94
4.1.2 Characteristics of Milk and Wheys.....................................................96
4.1.3 Membrane Separations Applied to Milk............................................. 98
4.1.3.1 Removal of Bacteria and Spores........................................... 98
4.1.3.2 Fractionation of Fat Globules.............................................. 104
4.1.3.3 Standardization and Concentration of Milk Proteins......... 105
4.1.3.4 Fractionation of Milk Proteins............................................ 109
4.1.3.5 Fractionation of Individual Caseins.................................... 113
4.1.4 Membrane Separations Applied to Whey and Derivates.................. 114
4.1.4.1 Concentration and Demineralization of Whey................... 114
4.1.4.2 Concentration of Serum Proteins........................................ 117
4.1.4.3 Fractionation of Individual Serum Proteins....................... 118
4.1.4.4 Fractionation of Peptides.................................................... 119
4.1.5 Treatment of Effluents and Technical Fluids..................................... 120
4.1.5.1 Recovery of Process Waters............................................... 121
4.1.5.2 Clarification of Brine.......................................................... 121
4.1.5.3 Recycling of Cleaning Solutions......................................... 122
4.1.5.4 Treatment of End-of-Pipe Wastewaters.............................. 123
4.1.6 Conclusions and Future Trends......................................................... 123
4.2 Egg-Processing Industry................................................................................ 124
4.2.1 Characteristics of Hen Egg (White, Yolk, and Whole)..................... 125
4.2.2 Concentration and Stabilization of Egg White and Whole Egg........ 126
4.2.2.1 Concentration Before Spray Drying or Storage in
Liquid Form........................................................................ 126
4.2.2.2 Stabilization........................................................................ 128
4.2.2.3 Types of Filtration Systems................................................. 128
4.2.3 Extraction of Egg-White Proteins...................................................... 129
4.2.4 Conclusions and Future Trends......................................................... 129
4.3 Other Sectors................................................................................................. 130
4.3.1 Seafood Processing Industry............................................................. 130
4.3.1.1 Recovery of Proteins from Surimi Production................... 131
93
4.3.1.2 Treatment of Other Effluents.............................................. 134

4.3.1.3 Fractionation and Concentration of Protein
Hydrolysates...................................................................135
4.3.2 Animal Products Industry: Blood and Gelatin.................................. 136
4.3.2.1 Blood................................................................................... 136
4.3.2.2 Gelatin................................................................................. 140
References............................................................................................................... 142
Over the past 30 years, the worldwide market for membrane operations in the food
industry has increased to a market volume of about €800–850 million (Lipnizki,
2010). It has therefore become the second biggest market for membranes after water
and wastewater treatment. This chapter will give an outlook of potential membrane
applications in dairy and animal products processing. The first part of this chapter
will focus on the dairy industry, the largest and most developed membrane market in
the food sector, which has most successfully been able to put membranes to work for
the benefit of the industry and its customers. The dairy sector encompasses a large
variety of different products and membrane processes, and this chapter will give an
overview of the most familiar and successful applications implemented throughout
the processing chains (from product reception to wastewater treatment). The chapter
will then present other established applications in the egg processing industry and
other animal products processing, such as seafood, blood, and gelatin processing.
4.1 DAIRY INDUSTRY

4.1.1 Introduction
In the food sector, the dairy industry has undoubtedly developed the most advanced
extraction/separation procedures for concentration and fractionation molecules from
milk and its derivatives. Processing each of the milk products (fluid milk, dried
milk, cheese, etc.) is traditionally characterized by different operations of separa-
tion. The oldest operation is the standardization of milk fat content by centrifugal
separation. But for more than 40 years, membrane filtration has been established as
a common unit operation. The application of membrane operations to milk process-
ing improves the separation options that are industrially applied today, enhancing
the separation specificity (e.g., spores, somatic cells) and efficacy when compared to
traditional technologies. It also enables the production of new, value-added-products
for totally new and exciting applications.
The key membranes technologies in the dairy industry today are pressure-driven
membrane processes such as microfiltration (MF), ultrafiltration (UF), nanofiltra-
tion (NF), and reverse osmosis (RO). Electrodialysis has only a small market. Based
on their applicability range and specific membrane pore and cut-off it is possible to
theoretically separate every milk component as shown in Figure 4.1. Pressure-driven
membrane processes principally separate constituents according to molecule size rel-
ative to the pore size of the membrane, but it is practically experienced that apart from
size, other properties of molecules such as charge, structure, shape, propensity to
Dairy Industry and Animal Products Processing Applications 95
Removal of bacteria from

skimmed milk MF 1.4 µm
25
Ions
Serum
Protein concentration UF proteins
(10–50 kg/mol)
Casein
micelles
15
Number (log)
Fat
10
Separation casein micelles/

soluble proteins, MF 0.1 µm Microorganisms Somatic
cells
0
–2 –1 0 1 2 3 4 5 6
Size: diameter in nm (log)
FIGURE 4.1 Approximate particle sizes of milk constituents for which separation by means
of membrane filtration can be applied.
form gel, etc., play decisive roles in this respect and make membrane operations still
complex because the various factors influencing separation results are not predictable.
The use of membranes commenced in the late 1960s with the MMV process
named after its inventors (Maubois, Mocquot, Vassal) and operated for the con-
centration of milk proteins. Membrane technology was also applied at this time to
whey processing allowing the production of refined proteins and commercial usage,
thus transforming a waste by-product from cheese production into valuable prod-
ucts. From then, the development of membrane applications in the dairy sector has
been more or less tightly linked to the progress in membrane operations: asymmetric
organic membranes in the late 1960s, composite inorganic membranes in the early
1980s, and porous ceramic membranes with multi-channel configuration in the early
1990s, which enabled the industrial application of the concept of uniform transmem-
brane pressure (UTP concept). The “UTP concept” was developed to reduce fouling
phenomena and improve separation results by achieving an uniform transmembrane
pressure over the entire length of the membrane by means of pumping the permeate
(Sandblöm, 1974).
Among the membrane operations applied in the dairy sector, UF and RO are
the oldest membrane processes. UF is the most widely used process, with mem-
brane area installed specially for the concentration of the proteins contained in milk
and wheys. The membrane area of RO is mainly used for whey concentration and
has stabilized over the years. NF and MF have been developed since the mid-1990s
at industrial scale, NF for the simultaneous concentration and demineralization of
whey, and MF mainly for the removal of bacteria and spores from milk and for the
selective separation of casein micelles from soluble proteins, which is a promising
technology for further protein fractionation.
4.1.2 Characteristics of Milk and Wheys

The average composition of cow’s milk is given in Table 4.1 and Figure 4.1. Cow’s
milk is a complex fluid, with a constant pH around 6.7 at ambient temperature. It is
mainly composed of lactose, fat, proteins, and minerals, but many other small spe-
cies are present in the soluble phase of milk (urea, vitamins, etc.).
Cow’s milk contains about 40 g/L of lipids. More than 95% of the mass of lipids
in milk is present in the form of spherical milk fat globules, with a diameter ranging
from 0.15 to 15 μm and a volume mean diameter around 4.0 μm. The milk fat glob-
ules have a core–shelf structure: they are naturally surrounded by a native biological
membrane (milk fat globule membrane, MFGM) which is mainly composed of phos-
pholipids that are polar lipids with some membrane-specific proteins and neutral
lipids, glycolipids, cholesterol, etc. The core of the globule is mainly composed of
triglycerides.
Proteins (32–35 g/L expressed as nitrogen, N × 6.38) correspond to about 95%
of the total nitrogen of the milk and are classically divided into two main groups.
First, the caseins (∼20 kg/mol) are insoluble at their isoelectric point of pH = 4.6 at
TABLE 4.1
Average Composition of Cow’s Milk
Size (μm) or Molecular
Concentration in Weight (g/mol
Components Whole Milk (g/L) [or Dalton]) Association State
Water 870–875 Solvent
Fat 34–44 0.15–15 μm (average Separated phase
4.0 μm)
Proteins 32–35
Caseins 25–28 0.05–0.5 μm Aggregates = micelles
Serum proteins 5–7 14.2–150 kg/mol Mono-oligomers
α-lactalbumin 1.2 14.2 kg/mol
β-lactoglobulin 5.4 18.4 kg/mol (dimer in
milk 36.8)
Immunoglobulins 0.5–1.0 150–1000 kg/mol
Bovine serum albumin 0.4 66.3 kg/mol
Lactoferrin 0.2 80 kg/mol
Lactoperoxidase 0.03 78 kg/mol
Lactose 48–50 342 g/mol Solution
Ashes (minerals) 8–9 Solution
Calcium 1.25 28% in soluble phase
Phosphorus 0.95 44% in the soluble phase
temperature >8°C; 92% of the caseins are generally associated into large globular
aggregates, called casein micelles. The structure of the casein micelles is still not
totally elucidated (Dalgleish, 2011), but casein micelles can be described as roughly
spherical particles, with outer diameters ranging from 50 to 500 nm (mean diameter
∼100–150 nm). They are made of four distinct caseins, αs1, αs2, β, and κ in propor-
tion of 3:1:3:1, and 8% in mass of calcium and phosphate, often called the colloidal
calcium phosphate. The minerals contained in casein micelles are in equilibrium
with the aqueous phase. Thus changing external conditions of milk such as pH and
temperature cause alterations in the mineral equilibriums that induce modifications
in the structure and stability of casein micelles (due to the colloidal calcium phos-
phate), and then changes in fractionation processes performances.
The second group of proteins are constituted by the serum proteins, also called
whey proteins or soluble proteins because they do not precipitate in the ionic envi-
ronment of milk when rennet is added or acidification occurs down to pH = 4.6.
The main serum proteins are β-lactoglobulin (∼3.2 g/L), α-lactalbumin (∼1.2 g/L),
bovine serum albumin, BSA (∼0.4 g/L), immunoglobulins (∼0.7 g/L), and minor
proteins like lactoferrin or lactoperoxidase (Table 4.1).
Whey is the liquid co-product of cheese-making. At a first glance it can be con-
sidered as the aqueous phase of milk corresponding to milk free of casein micelles
and fat. Whey contains approximately 65 g/L dry matter. It is constituted mainly of
lactose (∼50 g/L), nitrogen matter (mainly serum proteins ∼6 g/L), ashes (minerals
∼6 g/L), and fat (0.3 g/L) (Table 4.2). The composition of whey depends on the type
of cheese produced, and more particularly on the heat treatment applied to the milk
and methods used for the removal of the casein micelles. Two main types of wheys
exist “sweet” whey and “acid” whey (Table 4.2), but industrially the different com-
binations of coagulation operating conditions (temperature, heating time, nature of
starters, etc.) give rise to various types of wheys. Sweet whey is produced from ren-
netted cheese, such as mozzarella or cheddar. It is obtained after the destabilization
of casein micelles by enzymatic hydrolysis of the κ-casein using rennet. The final
TABLE 4.2
Approximate Composition of Sweet and Acid Wheys and Permeate of
Skimmed Milk MF Using a 0.1 µm Mean Pore Membrane (“Ideal” Whey)
Sweet Whey (g/L) Acid Whey (g/L) “Ideal” Whey (g/L)
pH 6.4 4.6 6.6
Dry matter 66 64 61
Nitrogen matter 6.2 5.8 7.5
Non-nitrogen matter 0.37 0.40 1.8
Lactose 52.3 44.3 48
Ashes 5.0 7.5 –
Fat 0.2 0.3 0.0
Source: Adapted from Marshall, K. R. 1982. Developments in Dairy Chemistry-1, ed. P. F. Fox, New
York: Applied Science Publishers.
pH of sweet whey is closed to the initial milk pH, that is to say around ∼6.0–6.6; its
mineral content is similar to that of milk, and it contains the soluble glycomacrope-
ptide portion of the κ-casein that is released in the serum phase under the action of
chymosin, the principal enzyme present in calf rennet.
Acid whey is produced from lactic acid fermentation for fresh cheese or from the
chemical acidification of milk down to the isoelectric point of the caseins (about 4.6).
Acid whey has a higher mineral content than sweet whey because of the release of
minerals from the casein micelles (mainly calcium and phosphate) into the serum
phase under acidic conditions. Its final pH is also very acidic, close to 4.6 (Table 4.2).
Finally milk is a relative complex fluid, but despite its complexity, milk compo-
nents are relatively well separated according to their size, as shown in Figure 4.1.
Milk and wheys are then relatively appropriate for membrane fractionation. For
example, Figure 4.1 shows that it is possible to separate bacteria from skimmed
milk provided the fat was previously removed because the size distribution of fat
globules is similar to that of bacteria. It is also possible to separate casein micelles
from serum proteins provided that milk is not heat treated because heat denaturation
of serum proteins leads to change in size by aggregation of serum proteins between
each other and association between them and casein micelles.
4.1.3 Membrane Separations Applied to Milk

The potential applications of membrane separation in skimmed milk processing are
given in Figure 4.2.
4.1.3.1 Removal of Bacteria and Spores

Several operations can be carried out in order to minimize health hazards and con-
trol bacterial growth during milk processing. Heat treatment with various combina-
tions of time and temperature (such as pasteurization 72°C for 12 s) are frequently
used at industrial scale, but this almost always affects the flavor, functionalities of
Skimmed milk
Removal of bacteria Standardization Fractionation of Concentration Concentration

by MF 1.4 µm of proteins by UF proteins by MF 0.1 µm of protein by UF by RO
Casein micelles Serum proteins
Ice cream
Drinking or Concentration (UF/Diaf) manufacture
cheese milks
Protein standardized Cheese-making Whey protein Milk protein

milks concentrates/ concentrates
isolates
FIGURE 4.2 Main applications of the membrane technologies in milk processing.

Raw whole milk
Sludge Centrifugation 50–60°C

(bacteria/spores)
Cream Skimmed milk
1.4 µm microfiltration Retentate

35–55°C, VRR = 20
1.4 µm microfiltration
Surplus cream Retentate
Heat treatment 35–55°C, VRR = 10
Heat-treated Microfiltered skimmed milk

cream
Mixing, homogenization
Microfiltered whole milk
FIGURE 4.3 Schematic representation of process for MF of whole milk. Dotted lines rep-
resent options for the treatment of retentate. VRR: volume reduction ratio.
the milk components, and cheese-making properties. Centrifugation (often referred

as bactofugation because the commercial equipment manufactured by Tetra Pak has
the trademark BactofugeTM) is also used for the removal of bacteria and spores from
minimally pasteurized milk because it efficiently removes spores as their density is
higher than that of bacteria. However the decimal reduction is generally low (∼1 log)
and significant protein loss is observed, reaching 2.5%–12% according to the types
of machine used (Gésan-Guiziou, 2010a). In that context MF which is a nonthermal
preservation technology has been increasingly applicable for the removal of bacteria
from milk.
Figure 4.3 illustrates the MF process generally used with different options for the
treatment of MF retentate.
Today MF is classically and specifically applied to skimmed milk, because the
size ranges of fat globules and bacteria overlap (Figure 4.1). In the case of whole
milk, fat would be concentrated with bacteria and would lead to difficulties of valo-
rization. It can be noted that a recent patent (Fauquant et al., 2009) shows that MF
using a 0.8 or 1.4 µm mean pore diameter membrane can make it possible to remove
bacteria from milk containing fat, provided the fat was previously homogenized in
order to adjust the size of the fat globules. In that patent it is claimed that the bacteria
are correctly retained (<1 and 10 cfu/10 mL for 0.8 and 1.4 µm membranes, respec-
tively), fat and proteins are highly transmitted (95% and 90%, respectively), and
membrane fouling is low for a 10-h production run.
Following separation of the cream, the skimmed milk is treated in the MF plant
(Figure 4.4). This separation is classically performed with a multichannel ceramic
FIGURE 4.4 Commercial MF system for the removal of bacteria from milk. (Courtesy of
GEA, France.)
membrane with a pore diameter of 1.4 µm in order to retain bacteria and let the pro-
teins pass through the membrane.
The temperature of the separation ranges from 35°C to 55°C. In order to achieve
good separation, high crossflow velocity (or wall shear stress) in combination with
low transmembrane pressure, ΔP are required. Thus in order to overcome membrane
fouling phenomena, MF plants in dairies operate using either the hydraulic concept
of UTP or specific ceramic membrane with linear hydraulic resistance. The UTP
system was developed by Alfa-Laval (Bactocatch® system) (Figure 4.5). This con-
cept involves circulation by pumping of the permeate co-current of the retentate in
order to create a pressure drop in the permeate side similar to the pressure drop in the
retentate side (Sandblöm, 1974; Gésan-Guiziou, 2010a) (Figure 4.5).
Pre Pro
Retentate
Permeate
Ppe Ppo
Transmembrane pressure
0
Length of membrane
FIGURE 4.5 Principle of UTP system. P: pressure; r: retentate; p: permeate; e: entrance;

o: outlet.
By doing so, the pressure difference is the same at each point along the mem-
brane, which leads to a homogeneous transmembrane pressure along the membrane
length, according to
retentate pressure drop = permeate pressure drop  Pre-Pro = Ppe-Ppo

 Pre-Ppe = Pro-Ppo
 ΔPe = ΔPo
 transmembrane pressure at the entrance = transmembrane pressure at
the outlet of the membrane
with ΔP the transmembrane pressure, Pr and Pp the retentate and permeate pres-
sures, respectively; e, entrance; o, outlet.
This results in a processing mode, where, in contrast to conventional crossflow
systems, deposit formation can be controlled through high levels of wall shear stress
without simultaneously creating high convective transportation of deposit-forming
material toward the membrane surface (high ΔP).
In order to create a large pressure drop on the permeate side, the compartment is
filled with plastic balls (Bactocatch system, Alfa-Laval) or membranes are placed
into small stainless-steel tubes in order to reduce the external space between the
housing and the membrane porous media (Invensys APV).
Ceramic membranes with linear hydraulic resistance were more recently com-
mercialized in order to obtain homogeneous filtration performance all along the
membrane length. This avoids a permeate circulation loop and extra investments and
running costs due to the permeate pump. This new conception of membrane consists
in creating an inhomogeneous membrane, having a higher hydraulic resistance (or
lower permeation) at the membrane entrance where the local transmembrane pres-
sure (ΔPe) is high, and a low resistance (or higher permeation) at the membrane
outlet where the local transmembrane pressure (ΔPs) is low. The gradient of mem-
brane resistance is established during membrane manufacture such that the mem-
brane resistance is inversely varied according to the linear decrease of static pressure
in the retentate side. Two main commercial membranes are proposed (Figure 4.6):
GP Membralox® membranes from Pall-Exekia (GP for permeability gradient) with
a continuous variation of the porosity of the membrane support (Figure 4.6a) and
Isoflux membranes from Tami-Industries with continuous variation of the thickness
of the selective front layer of the membrane (Figure 4.6b) (Skrzypek and Burger,
2010). More recently, Applexion patented a new concept of membranes but, to our
knowledge this membrane has not yet been used industrially (Tregret et al., 2008).
All these membranes are obviously constructed for well-defined hydrodynamic con-
ditions, and consequently must be used for well-defined applications.
By combining such a system (UTP or membrane with linear resistance) and high
crossflow velocity (6–9 m/s), permeation fluxes are high, from 400 to 650 L/h/m2
for around 10 h of production with a volume loss of 5% at a volume reduction ratio,
VRR of 20 or 0.5% with a second MF step at VRR = 200 (Figure 4.3). Total solids,
protein, and fat of skimmed milk are largely transmitted: 99.5%, 99%, and 63% of
transmission, respectively (Maubois and Ollivier, 1997). The decimal reduction of
(a) Retentate
Selective membrane layer
Membrane support with a
gradient of porosity
Permeate
(b) Retentate
Selective layer with a gradient
of thickness
Membrane support
Permeate
FIGURE 4.6 Schematic depiction of membranes. (a) With a gradient in the porosity of the
membrane support; (b) With a gradient in the thickness of the selective layer of the membrane.
bacteria ranged from 2 to 3 log with the first ceramic membranes (Malmberg and
Holm, 1988; Trouvé et al., 1991) and reaches 3–4 log with the currently used 1.4 μm
Sterilox or GP membranes. Morphology of bacterial cells and cellular volume obvi-
ously influence the membrane retention properties (Gésan-Guiziou, 2010a).
By using membranes with smaller pore size (0.5–0.8 μm) Lindquist (1998)
observed an increase in bacteria removal up to 2 or even 3 log compared to 1.4 µm
membrane, with only a slight decrease of casein micelles permeation. In such a pro-
cess, somatic cells, coming from the bovine mammary gland (leucocytes, macro-
phage, and epithelial cells) are also totally retained and thus microfiltered milk is
not degraded by their thermostable enzymes. MF is then more efficient than bactofu-
gation, and contrary to heat-treatment procedures, it not only curbs the activity of
bacteria but it physically removes bacteria, spores, dead cells, and other impurities
from the milk altogether.
Finally, in order to adjust the desired protein/fat ratio corresponding to the final
product, the microfiltered milk was mixed with cream, previously subjected to a
conventional high heat treatment. Since less than 10% of the milk is heat-treated
at high temperature, the sensory quality of the milk is significantly improved. The
MF retentate, which contains most of the bacteria and somatic cells and some large
casein micelles, can be discharged separately for other suitable applications, blended
with cream and similarly heat-treated or fed back to the cream separator for repeated
separation, where a significant number of bacteria, spores, and somatic cells are
removed with the separator sludge (Figure 4.3).
The 1.4 μm MF process has been used increasingly for the treatment of drinking
and cheese milks.
For drinking milk, the objective is to produce value-added milk with a higher
purity and longer shelf life compared to milk treatment by conventional heat-treat-
ment processes.
Several products have been offered to consumers. France is the only country
that has officially allowed the commercialization of extended shelf life (ESF) MF
raw milk. Skimmed milk is mixed with the requested amount of heated cream
(95°C–20 s); the mixture is homogenized and aseptically filled. The authorized shelf
life at 4–6°C is 3 weeks. In France, Marguerite® milk is considered to be raw milk
because no pasteurization is applied. However in most countries, to meet current
regulatory requirements, whole milk produced using MF and intended for the drink-
ing milk market, undergoes a final pasteurization step (72°C, 15 s). The shelf life
of the product is then greatly enhanced: 20–32 days compared with 6–18 days for
normal pasteurized milk.
The product has been well received in the market place because of improvement
in flavor and storage ability. Several tens of MF systems (10–20 m3/h) are currently
running in Europe and in North America for the manufacture of drinking milk. In
Europe, microfiltered–pasteurized milk is produced by different dairy companies
(te Giffel et al., 2006): Parmalat and Granolaro in Italy and Arla with Cravendale
PureFiltre in the United Kingdom. Microfiltered milk with a shelf life of 23 days has
captured 11% of the market in the United Kingdom.
MF could also be used with a smaller pore size of 0.5 or 0.8 μm instead of 1.4 μm.
With such a low pore size, the decimal reduction is higher than 13 on Clostridium
botulinum, a value that means sterility of the product. After mixing with ultra-high
temperature (UHT) cream, homogenization at 80°C, a heat treatment limited to
95°C–6 s is applied with the only purpose of inactivating endogenous milk enzymes.
The obtained milk called Ultima milk was recognized as sterile milk. It is stable
for more than 8 months at room temperature. Its organoleptic quality was judged as
similar to that of an high heat short time (HTST) pasteurized milk and much bet-
ter than the current UHT milks. Until now, to our knowledge, this Ultima product
was not so much produced. Some applications have recently been developed in the
United Kingdom.
Sometimes in some dairy plants, the MF 1.4 μm is substituted by the 0.8 μm mem-
brane for the production of ESL MF pasteurized in order to extend storage ability.
In addition to use in the drinking milk sector, MF pretreatment of skimmed milk
can be expanded to all skimmed milk used for the production of milk derivatives
such as low-heat milk powder, milk protein concentrates, or micellar casein powder.
In some plants for instance, use of 1.4 μm MF has been extended as a pretreat-
ment in the production of UHT milk in order to decrease the intensity of heat treat-
ment (decreased to 140°C–4 s or less) with consequently a less cooked taste and
an improved storage capability coming from the removal by MF of thermoduric
enzymes present in dead bacterial cells and somatic cells.
This process is also used for cheese milks to remove somatic cells and spores,
particularly the Clostridium species which survives a normal pasteurization and
causes problems mainly in semi-hard and hard cheese manufacture. Traditionally,
the natural content of these spores has been controlled by the addition of nitrates
and other additives to prevent the “late blowing” of semi-hard and hard cheeses
which seriously damages the cheeses. The high removal of spores by MF makes the
suppression of the addition of nitrate and the production of natural products without
additives possible. The MF pretreatment of milk can then be carried out either at
50°C or at 35°C with some specific adaptations of the running parameters in order to
give cheese-makers the possibility to avoid all the detrimental effects of heat treat-
ment on the non-fatty fraction of the used milk.
Due to the high retention of bacteria and spores, the French regulatory authori-
ties, in 2002, permitted the provisional use of MF milk for the making of protected
designation of origin (PDO) raw milk cheese. Some cheeses are currently produced
by MF, especially those using raw milk (JO, 2007). However, microfiltered milk has
been described as “too clean” by cheese-makers. The process then requires knowl-
edge about the microbial system composition that should be added to the treated
milk for obtaining the typical ripening of cheeses.
4.1.3.2 Fractionation of Fat Globules

MF was also proposed to fractionate the fat globules according to their size. The
fractionation of native fat globules is industrially attractive because the native fat
globule membrane has very interesting functional and health properties, mainly
attributed to its content of phospholipids. Centrifugation is classically used for the
separation of milk fat from the skimmed milk, but despite its widespread application
and its good efficiency, this technology cannot separate the native milk fat globules
according to their size. Homogenization of milk is also classically used for the pro-
duction of many dairy products. But homogenized fat results in a reduction of the fat
globule size and a disruption of the native globule membrane: the homogenized fat
droplets are covered by caseins and serum proteins, that promote their interactions
with the cheese casein matrix, affect the structure of the rennet gel, and decrease
product functionality.
Separation of milk fat into small and large globules was proposed using a ceramic
MF membrane under hydrodynamic conditions which cause no damage to the native
fat globule membrane (Goudédranche et al., 2000; Michalski et al., 2006). It is pos-
sible using an MF operation or a cascade with or without diafiltration to prepare
native fraction of different fat globule size ranging from an unstable large fat droplet
with a size of about 6.6 μm to a very stable fat droplet with a size of about 1.6 μm
(Figure 4.7) (Lopez et al., 2011). This process appears to be more efficient than grav-
ity separation in selecting native milk fat globules of different sizes.
The feasibility of the process was shown but to our knowledge, no industrial
application has been developed. The development of industrial applications will
(a) (b) (c)
10 µm 10 µm 10 µm
FIGURE 4.7 Fractionation of milk fat globules as a function of their size using crossflow
MF: Images of (a) milk fat globules in whole milk (mean diameter: 4.2 μm), (b) small milk
fat globule fraction (mean diameter: 1.6 μm), and (c) large milk fat globule fraction (mean
diameter: 6.6 μm). (Adapted from Lopez, C et al. 2011. Food Chemistry 125:355–368.)
depend on the profits associated with the new interesting products. Fractionation of
native fat globule can lead to products that are more appreciated by consumers and
this should further drive the development of the cream in milk. It is actually claimed
that the use of the small globule fraction in cheese production yields smoother and
finer texture, probably because of the interaction of the fat globule membrane with
the cheese casein matrix, and the differences in triglycerides content of the fat glob-
ules according to their size (Michalski et al., 2007). Small globules also lead to high
water bonding capacity, which can be useful in butter technology in order to improve
the spreadability of the product. Moreover, it has recently been shown that the lower
the fat globule, the higher the enzymatic accessibility, and the better the hydrolysis
of small fat globules by both gastric and pancreatic enzymes (Berton et al., 2012).
Indeed for a given concentration of fat, the lower the fat globule, the higher the glob-
ule number, the higher the phospholipids content, and the higher the specific surface
of the globule (Lopez et al., 2011).
4.1.3.3 Standardization and Concentration of Milk Proteins

In the beginning of the 1970s, the UF operation was directly introduced into cheese-
making processes. Since then, UF has become the most widely used membrane
process for milk protein enrichment/standardization and concentration (Mistry and
Maubois, 2004). The objective of milk UF is to concentrate all the milk proteins
(serum proteins and casein micelles) and fat (if present) and simultaneously to let the
lactose and minerals pass through the membrane. UF is used in two main applica-
tions: the standardization of milk proteins and the concentration of milk proteins,
both largely used in cheese-making procedures. Regardless of the applications, the
membranes used for the production of milk protein concentrates are normally of spi-
ral wound configurations, and to a lesser extent tubular ceramic membranes both with
a cut-off of 10–50 kg/mol operated at a transmembrane pressure of 200–400 kPa with
permeation flux of 30–120 L/h/m2. Plate and frame systems may be used, especially
for the last loops of UF plants when high viscous concentrates are treated.
UF can be performed at temperature either around 50°C or 10°C. At “high” tem-
perature (∼50°C), permeation fluxes are higher, but this temperature favors both
the mineral precipitation of calcium phosphate in the membrane pores and bacteria
growth in the final retentate. In order to limit bacteria development in spiral wound
membranes a process duration of 6 h is generally not exceeded in these conditions. At
“low” temperature (9–12°C), and especially with organic spiral wound membranes,
no calcium phosphate precipitation is observed and fouling is mainly due to the
adsorption and accumulation of proteins at the membrane surface. A process duration
of 10–12 h is classically observed with no or little bacteria growth. A longer duration
can be operated provided the final retentate was heat treated prior to further use.
RO is sometimes but rarely applied to milk for its concentration: the flux is small,
the maximum concentration attainable is low, and this technology is not as attractive
as UF in cheese and yoghurt manufactures. However, milk RO is sometimes used
as a first step in the manufacture of powder to increase the capacity of evaporation
plants and to reduce transport costs, as it is more extensively done for whey RO. It is
also used in ice-cream manufacturing, since all the solids are retained in the concen-
trate and 70% of the water is removed.
4.1.3.3.1 Standardization of Proteins

The protein content of milk collected by dairy plants is subjected to natural and
substantial variations during the seasons due to various factors: stage of lactation,
feeding and breed of lactating cows, weather, etc. Such variations in the composition
of incoming milk unfortunately result in non-efficient use of machinery in dairies
and difficulties in control of the continuous cheese-making processes. Moreover, at a
low protein content the rennet-induced coagulum is weak and leads to relatively high
losses of caseins as “fines” in whey. Adjustments of processing parameters are then
required by cheese-makers.
For nearly 40 years now, UF has been used for the total protein standardization
of cheeses. Drinking milk with a higher protein content than normal is also now
common in various countries, such as the United States and Australia (Jelen, 2011).
In order to adjust the level of proteins, UF slightly concentrates the protein content
up to a VRR of 1.7. Such standardization results in a constant milk composition all
year round and offers the possibility of increasing the protein content in milk without
the need of adding milk powders, casein, or whey protein concentrates (WPCs). In
addition to the improvement of process productivity, these levels of concentration
provide economic benefits in terms of reduced requirement for coagulating enzymes
and starters, as well as slight increase in cheese yield, attributed to reduced losses of
fat and caseins in whey and better retention of serum proteins in the aqueous phase
of cheese (Mistry and Maubois, 2004).
UF, with VRR of around 1.5, is also used into manufacture of yoghurt and related
fermented products in order to increase the protein levels without the addition of milk
powders (Tamine and Robinson, 2007). UF results in a better yoghurt gel strength
compared with those obtained with the addition of milk powders or concentration by
vacuum evaporation. UF is also preferred to RO because of the reduced level of lac-
tose in the processed milk. One can notice that, by comparison with cheese-making,
the increase of protein level by UF is not accompanied in the yoghurt manufacture
by a yield improvement: the high heat treatment classically applied to the milk (typi-
cally 80°C–10 min) leads actually to the attachment of denatured serum proteins
with casein micelles, resulting in the concentration of serum proteins with casein
micelles after heat treatment.
The milk UF permeate can be used to adjust the protein content in concentrated
and dried dairy products as approved, in that context, by the Codex Alimentarius
Commission. However, to our knowledge, no country in the world has modified
its legislation to allow protein standardization (i.e., dilution) using UF permeate
of regular market milk. Such a practice is forbidden in the EU, even if published
research indicated undistinguishable sensory and technological properties in UHT
milks obtained after blending with the UF permeate down to 3.2–2.6 g/100 g protein
(Jelen, 2011).
4.1.3.3.2 Concentration of Proteins in Cheese Manufacture
Numerous cheese varieties have been made from medium-concentrated retentates
obtained with UF in what is largely known as the MMV process after the investiga-
tors Maubois, Mocquot, and Vassal who originally developed this process in 1969
(Maubois, 1981) (Figure 4.8). In this approach, cheese is made by using specially
Traditional process
for cheese-making Ultrafiltration, MMV process
Milk Milk
Rennet Ultrafiltration
starters
Coagulation
“Pre-cheese”
Rennet
Curds
starters
(precipitate)
Draining
Ripening
Ripening
Cheese Whey Cheese Ultrafiltrate
FIGURE 4.8 Schematic representations of traditional ways of making cheese and MMV
process (with protein concentration corresponding to the final protein composition of the
cheese).
designed equipment able to cut and handle the firm gel resulting from the coagula-
tion of the retentates, eventually diafiltered with pure, salted, or acidified water.
In a traditional cheese-making process (Figure 4.8), the milk after heat treatment
and adjustment of its fat content to the required value, is treated with an enzyme
(rennet) and/or acid (bacteria) that coagulate the casein fraction of the milk. Fat
and casein are then concentrated in the curd to form cheese while lactose ions,
serum proteins, vitamins, and sometimes casein particles are lost in the whey frac-
tions. MMV process using UF is completely different (Figure 4.8). The general idea
behind the MMV process is to concentrate all the milk proteins (casein micelles and
serum proteins) and simultaneously to remove the excess water, part of ions, and
lactose by an initial UF step carried out at the native pH of the milk, prior to coagu-
lation (induced by addition of enzymes (rennet) and microorganisms). Thereby UF
results in the reduction or elimination of the need to separate the whey from the curd
(Figure 4.8). The drive behind the development of membrane filtration-based cheese
processes is the desire to obtain a continuous process with increased yield compared
with conventional cheese-making.
Three categories of protein concentration level obtained using the MMV process
can be distinguished: preconcentration (1.2 < VRR < 1.7); intermediate concentra-
tion (1.7 < VRR < 5), and total concentration (VRR ∼5–7).
The preconcentration of cheese milk can be used for most cheese types, such
as Cheddar, cottage cheese, and Mozzarella. It can be used to standardize cheese
milk and manipulate its mineral composition, resulting in a specific quality of the
final product. The preconcentration allows the capacity of the cheese vats and whey
draining equipment to be increased, but the cheese yield is not significantly improved
because the protein concentration is poorly increased.
The concentration of milk at higher concentration (VRR > 1.7) leads to further
advantage in terms of cheese yield. A distinction must be made between retentates
concentrated to an intermediate level (1.7 < VRR < 5) in which some serum proteins
are retained and syneresis still takes place, and concentration to the total solid con-
tent in the final cheese (VRR ∼5–7), also called pre-cheeses. In the latter, the cheese
can be manufactured without the need for a cheese vat, very little whey drainage is
observed, and maximum yield is obtained (case of Figure 4.8).
Intermediate concentrated retentates have been applied to numerous cheese vari-
eties, ranging from soft to hard, such as Camembert, Feta, and Brie.
The total concentration (“pre-cheeses” concept) was first applied to Camembert
manufacture, but many applications have been successfully developed for various
type of cheeses; Quarg, cream cheese, Ricotta, Mascarpone, and Feta, the manu-
facture of which being unquestionably the greatest success worldwide of the MMV
process. By using UF to prepare pre-cheese, Feta can be cast directly in tins as
final packaging material, resulting in a very simple production method and a yield
increase of more than 20% without any whey drainage. This means that the payback
period for the investment in the processing equipment becomes very short indeed.
The advantages of the MMV process are numerous. The overall cheese yield is
about 10%–30% higher than in the traditional process due mainly to the retention of
serum proteins. Enzyme usage is generally reduced. The MMV process eliminates
the need for the large storage tanks traditionally used for heating and cooking the
curds, resulting in a saving in both capital investment and energy costs. In addition,
it is possible to use the MMV process to convert much of the cheese production in
a continuous operation, leading to significant advantages in terms of overall capi-
tal costs and operational efficiency. However, the increase of serum proteins which
have higher water-binding capacities than caseins leads to a negative effect on the
ripening of semi-hard and hard cheeses. Moreover the mineral content of the milk,
associated within the casein micelles, is also higher than in a traditional process in
which they are generally lost in the whey during coagulation. The higher content of
minerals leads to an increase in buffer properties, differences in acidification, lipoly-
sis, and proteolysis in cheese and to inherent properties of UF milk cheeses.
UF technology should be considered as a complementary process to cheese man-
ufacturing rather than an alternative process to traditional cheese-making. In order
to produce traditional cheeses, the MMV process actually requires numerous adap-
tations (Mistry and Maubois, 2004), and that is why it is often used in the develop-
ment of new types of cheeses, well-accepted by consumers.
UF of acidified milk is one of the process adaptations proposed to decrease the
mineral content of the retentate and lower the buffer capacities of the casein con-
centrate. Acid pH actually leads to a partial release of the minerals associated with
casein micelles. UF of acidified milk was developed for the production of fresh
cheeses, such as Fromage Frais. Prior to the development of UF process, these
products were manufactured by means of specially designed centrifugal separators,
sometimes combined with a special heat treatment of the feed. A breakthrough came
with the UF-based process illustrated in Figure 4.9.
Milk
Pasteurization
95°C/5 min
Fermentation
pH = 4.5
Thermization
55°C/3 min
Ultrafiltration
Cooling of the
retentate
UF Quarg
cream cheese
FIGURE 4.9 Manufacture of Quarg or cream cheese on a UF-based process. (Adapted from
Invensys—APV System. 2000. Membrane Filtration and Related Molecular Separation
Technologies, Silkeborg: APV Systems.)
In that process the milk is cultured to a final pH of 4.5–4.6 followed by UF. Due
to the extremely high viscosity caused by the low pH, the UF plant is based on a
plate-and-frame or tubular-type systems. The last loops of the plant are generally
equipped with a positive pump in order to handle the highly viscous concentrate.
The UF process makes it possible to manufacture products with exactly the required
flavor and consistency.
Manufacturing technologies including UF have also emerged for nearly 30 years.
They have become important for the production of dried milk protein concentrates.
Since there are no specific standards of identity for such concentrates, they cover a
wide range of compositional and functional characteristics and are manufactured
mainly using UF and diafiltration, for the reduction of the lactose and mineral
content.
4.1.3.4 Fractionation of Milk Proteins

The most promising technology for the selective separation of proteins is undoubtedly
membrane MF using a membrane with a pore size of 0.1 µm. Before the development
of this technology in the mid-1990s, two principal ways of manufacturing casein at
industrial scale were proposed. Both were based on the precipitation/aggregation
of casein and lead to the denaturation of the native casein micelles. In isoelectric
precipitation, destabilization of the casein micelles is accomplished at a pH around
Whole or skimmed milk

+ microfiltration (1.4 µm)
MF 0.1 µm
fractionation casein micelles/soluble proteins
Retentate Permeate
native casein micelles native whey proteins
“Ideal whey”
free of residual fat,
microorganisms
and GMP
Natural pH of milk
FIGURE 4.10 Fractionation of casein micelles from serum proteins using MF membrane
with a 0.1 µm mean pore diameter.
4.6: when milk is acidified, the net charge of the micelles decreases, the calcium
and phosphate are removed, and the micelles become less and less stable until the
caseins precipitate. Destabilization of casein is also caused by the proteolysis of the
micelle-stabilizing protein, namely κ-casein. The chymosin, the principal enzyme
present in the calf rennet, releases the glycomacropeptide (C-terminal segments of
glycosylated κ-casein), and renders the casein micelles susceptible to precipitate by
Ca2+ at the natural concentration in milk.
Contrary to these two ways of manufacturing casein, MF using a 0.1 µm mean
pore diameter makes it possible in one single operation, the separation of milk into
a retentate enriched specifically in native casein micelles (size ∼100–150 nm) and a
permeate containing native soluble proteins (size 2–10 nm) (Figure 4.10).
The resulting retentate has a high concentration of native casein micelles that can
be used for cheese-making in order to improve the rennet coagulability of casein and
the cheese-making process, as it is for UF process. The casein enrichment reduces
rennet coagulation time, accelerates curd firmness kinetics, and increases final curd
firmness compared to milk or caseinate. Consequently casein and fat retentions into
the cheese curd are significantly improved (less casein particles and fat in the drained
whey) resulting in a cheese yield increase. The fact that less serum proteins (com-
pared to UF) end up in the cheese manufacturing process offers also several advan-
tages: it reduces flavor and texture defects attributed to serum proteins and reduces
the detrimental effects of heat treatment on rennet milk coagulability. During heat
treatment, β-lactoglobulin (β-LG) actually forms complexes with the κ-casein sur-
rounding the casein micelles, resulting in a reduction of the rennet coagulability of
milk. This property was used to develop a new high-heat milk powder, mainly con-
sisting in the production of milk with low serum proteins content using MF and UF
(Quiblier et al., 1991). The high-heat milk obtained exhibits similar cheese-making
ability to that of raw milk.
The retentate can also be used to produce purified casein micelle concentrates
obtained by diafiltration against water. These purified concentrates, called native
phosphocaseinate, act as excellent starting materials for further fractioning indi-

vidual casein, which find applications as nutraceutical derivatives of milk proteins.
The permeate is sometimes called “ideal whey” because its composition is close
to that of sweet whey but free of rennet by-product glycomacropeptide, residual
fat, and microorganisms (phage, cellular debris, etc.) (Table 4.2). The permeate is
crystal clear (Figure 4.10) and its pH is similar to that of milk, and then higher than
all the pH of wheys that are more acidic (Table 4.2). It contains lactose, minerals,
and serum proteins in their native state, if the previous milk was not heat treated.
Due to its composition and because of the native state of its proteins, it is a useful
fluid to prepare WPCs and whey protein isolates (WPI, protein ratio up to 95%)
with very high functional and nutritional properties, in particular in comparison
with WPC obtained from cheese whey. These concentrates can advantageously be
used to further fractionate individual proteins. Despite these advantages, the micro-
filtrate is sometimes used in the cheese-making process by reincorporation in the
casein-enriched fraction after denaturation under a moderate concentration and a
heat treatment.
The first MF 0.1 µm of milk was implanted in the mid-1990s in France, and since
then this operation has enjoyed rapid industrial development. It is still expected to
significantly increase in the future because the fractionation and standardization of
milk proteins opens up new ways of manufacturing cheeses and caseins.
Today, this application is mainly conducted using a ceramic membrane either
with the UTP system or membranes with linear hydraulic resistance gradient, as it is
done for the removal of bacteria (Figure 4.11).
Separation is classically performed at 50–55°C, at high crossflow velocity (around
7 m/s), low transmembrane pressure (∼50 kPa), and with a VRR in the range of 2–4.
At VRR = 3 the transmission of serum proteins varies from 65% to 80% depending
on the milk heat treatment (pasteurization, thermization, or raw skimmed milk). The
higher the heat treatment, the more pronounced the association of serum proteins with
casein micelles, and then the lower the transmission of soluble proteins. Permeation
flux is ≈75–80 L/h/m2 for 10 h. The control of the membrane flux through control
of fouling is very important in this operation: the operating conditions should be
chosen according to the critical stability criterion in order to perform long runs with
very moderate fouling and high selectivity (Gésan-Guiziou et al., 1999). The overall
performance of the process is governed by the accumulation of casein micelles at the
membrane surface which leads to the formation of an irreversible deposit (a gel) in
critical hydrodynamic conditions (Gésan-Guiziou et al., 1999; Jimenez-Lopez et al.,
2008) (Figure 4.12).
To control the filtration performance, it is then necessary to understand how the
micelles accumulate at the membrane and how they interact with each other during
accumulation. Indeed, MF performances are very dependent on the balance of inter-
actions between and within the micelles (Jimenez-Lopez et al., 2011).
For some time now, due to the high running costs and investments imposed by
tubular ceramic equipment, the industry has begun to operate MF with spiral wound
polymer membranes. According to the manufacturers, about 25% of MF plants are
today assumed to be equipped with organic membranes and this proportion is likely
to increase for cheese applications in the future. Some data are becoming available
FIGURE 4.11 An MF plant for the fractionation of milk protein. (Courtesy of SPX Flow
Technology SAS, France.)
Permeation
flux (J)
120
100
Irreversible deposit
of casein micelle
80
60 Divergent runs
40
Reversible accumulation
20 of casein micelle
Steady runs
0
0 20 40 60 80 100 120 140
Wall shear stress, τw (Pa) Ceramic membrane 0.1 µm, UTP system,
VRR = 2, T = 50°C
FIGURE 4.12 Critical hydrodynamic conditions during MF 0.1 μm of skimmed milk.

(Adapted from Gésan-Guiziou, G., E. Boyaval, and G. Daufin. 1999. J. Membrane Sci.
158:211–222.)
on polymer membranes (Zulewska et al., 2009). Contrary to ceramic tubular mem-

branes, these membranes cannot be conducted with the UTP system, which leads
to significant heterogeneity of transport along the membrane. In this configuration
operating conditions and performance of the system are quite different from the
ceramic ones: filtration is generally performed at low temperature (<10°C) to reduce
the bacterial growth; crossflow velocity is low (∼0.5 m/s), and transmembrane pres-
sure is relatively high (1.0–1.5 × 105 Pa). The filtration of milk at low temperature
yields a higher concentration of free caseins in the MF, more particularly β-casein
that dissociates from the casein micelle at low temperature. Moreover in these con-
ditions, permeation flux is reported to be very low <10 L/h/m2. The protein trans-
mission ranges from 20% to 30% at VRR = 3, which requires diafiltration against
ultrafiltrate to decrease the whey protein level in the enriched casein fraction. The
MF-permeate (microfiltrate) containing the whey proteins is therefore concentrated
by an UF unit concentrating the whey proteins. The UF-permeate (ultrafiltrate) con-
taining the soluble low molecular weight substances of milk (lactose and ions) at the
original concentration is recirculated to the feed tank of the MF unit to wash out the
remaining whey proteins in a diafiltration mode. Using the ultrafiltrate instead of
water as a solvent for diafiltration allows one to avoid a change in the native aqueous
environment of the casein micelles.
4.1.3.5 Fractionation of Individual Caseins

Whole casein is highly functional, but this functionality is compounded from indi-
vidual components with contrasting character, due for instance to differences in the
number of phosphoserine residues or distinct hydrophilic and hydrophobic domains.
Therefore, there is a considerable interest in fractioning whole casein into individual
caseins. Potential uses include preparation of biologically active peptides and addi-
tives after specific hydrolysis of the individual caseins and bovine milk-based infant
formulas. Compared to caseinate and rennet casein, the native casein micelles reten-
tate obtained from skimmed milk 0.1 µm MF constitutes excellent raw material for
preparing individual caseins. Fractionation of casein is readily carried out in the
laboratory and very few methods of preparing casein fractions have received atten-
tion with a view to commercialization.
Most of them are related to the isolation of β-casein, the main casein of human
milk, which contains numerous peptide sequences with high physiological properties
(phosphopeptides, opioid activities, etc.). The essence of the techniques of β-casein
isolation relies on the preferential solubilization of this very hydrophobic protein at
low temperature. At ∼4°C, β-casein dissociates from the casein micelle and can be
recovered in the aqueous phase. The yield of β-casein is enhanced at low pH (4.2–4.6).
The isolation of the protein from the rest of the caseins (caseinate, renneted skimmed
milk, etc.) can be performed using separation techniques such as UF and MF or cen-
trifugation. Starting from rennetted casein, Le Magnen and Maugas (1991) reached
a purity of β-casein close to 90%. The co-product (retentate or sediment fractions) is
enriched in other caseins (αs1, αs2, and κ-caseins). Based on the same properties of
β-casein and development of skimmed milk MF 0.1 µm, a promising process to sepa-
rate this protein directly from milk has recently been proposed. The process operates
in two successive MF steps. Depending at which temperature they are obtained, the
permeate or retentate of the first MF step may be used to extract β-casein. A permeate
obtained in a first cold (≈ 4°C) MF of milk may be further filtered at ambient tempera-
ture to separate β-casein from milk serum proteins and prepare enriched fractions
containing β-casein (O’Mahony et al., 2007). The warming of the permeate results
in the specific aggregation of β-casein and the second MF retains the aggregated
β-casein while the native soluble proteins passed into the membrane. A retentate of
skimmed milk MF obtained at high temperature (≈ 50°C) may also be further filtered
at low temperature (≈ 4°C) to extract the β-casein (Van der Padt et al., 2012).
4.1.4 Membrane Separations Applied to Whey and Derivates

Because of its high water content and relatively high sugar and mineral content,
whey used to be considered a waste product from cheese production that was without
value and difficult to dispose of. Direct dumping in the sea or river, spraying it on
fields, or at best feeding it to pigs were the most common ways of disposal. In the
1980s, more than two thirds of whey production was still disposed of as waste with
a detrimental effect on the environment. Today, a significant amount of the whey
produced is being processed, mainly for the recovery of its protein content by UF.
The potential applications of membrane separations in whey processing are given
in Figure 4.13. Currently, four membrane technologies are in use for whey process-
ing: RO and NF for the concentration and partial demineralization (for NF) of whey;
UF (including diafiltration) for the concentration of proteins and MF for removal of
minerals and residual fat before further processing.
4.1.4.1 Concentration and Demineralization of Whey

4.1.4.1.1 Concentration
In the past, the concentration of whey was classically performed by RO. Today,
a large part of the RO membrane area carrying out the concentration on whey is
Whey
Option: pretreatment of whey

(heat-treatment, MF,…)
Protein concentration Concentration/ Concentration

by UF demineralization by NF by RO
Ultrafiltrate
Demineralization by NF
Concentration by RO Partially
Whey protein demineralized whey Concentrated
concentrates Lactose concentrates whey
FIGURE 4.13 Main applications of membrane technologies in whey processing.

replaced by NF membrane in order to simultaneously perform concentration and

partial demineralization (removal of 25%–50% of salts, mainly monovalent species)
of wheys.
RO was mainly applied for the concentration of wheys and various ultrafiltrates
on their production site. The concentration of ultrafiltrates, containing about 5% total
solids, (mainly lactose, salt, and other minor soluble components of the milk) using
RO leads to valuable uses (animal feed, recovery of lactose after crystallization,
fermentation of lactose into glucose and galactose as sweeteners for the confection-
ery industry, alcohol, lactic acid, etc.). The concentration was carried out in order
to reduce the volume of the product either before further transportation or prior to
vacuum evaporation and spray drying. This operations allow a large energy saving:
this membrane operation, known to mainly remove water, is flexible and requires
a lower energy consumption (9–20 kWh/m3 water removed) compared to vacuum
evaporation (≈ 90–100 kWh/m3). However, it is noticeable that an increase of dry
matter by RO from 10% and 20% prior to vacuum evaporation results in high cal-
cium phosphate fouling of evaporators.
Concentration of whey by RO is classically performed up to VRR of 4, resulting
in about 25%–27% dry matter. It is limited by high osmotic pressure, high retentate
viscosity, calcium phosphate precipitation, and lactose crystallization. The RO per-
meate can be reused for preparing cleaning solutions, but its composition is not simi-
lar to pure water. Urea can pass to some extent, and some salts and low-molar-mass
peptides may do so, leading to specific treatment of the reused water.
4.1.4.1.2 Demineralization
To make non-hygroscopic whey powder and make whey powder suitable for cer-
tain foods, whey is classically demineralized before evaporation (Gernigon et al.,
2011). The high salt content of whey, generally ranging from 8% to 10% minerals
on a dry weight basis, generates numerous processing difficulties especially when
concentrating, crystallizing lactose, and spray-drying whey (decrease in yield of
lactose crystallization, and high hygroscopicity of obtained powders). Moreover,
the high salt content leads to nutritional imbalance especially for the prepara-
tion of infant formulas and becomes a problem when using whey and whey pow-
ders as food. Partial demineralization is often needed in various situations when
manufacturing dairy ingredients, for example, various WPC products, in order to
adjust the mineral composition. For ice-cream applications, in order to reduce the
salty taste of ordinary whey powder, a 50%–70% overall reduction in minerals
is often enough. But in order to mimic the mineral composition of human milk,
a reduction of 90%–95% in minerals of whey (mainly Na+, K+, Cl−, and PO43−) is
generally required.
The demineralization of whey can be achieved with various processes (electro-
dialysis, ion exchange (resins), NF) according to the type of treated whey and the
required demineralization rate. For large demineralization installations (those treat-
ing more than 400 m3/day), and depending on the proportion of salts to be removed,
investment in combining technologies may be of interest (Largeteau, 2009; Gésan-
Guiziou, 2014). Today many modern demineralization plants are combinations of
classical ion exchange and/or electrodialysis with NF.
Regardless of the chosen processes, ions and not undissociated salts, are removed.
For a given overall proportion of salts removed, the rate of removal varies with the
kind of ions and with the technology used. NF for instance removes monovalent
ions (such as Cl−) and concentrates divalent nutrition value ions like calcium with
the proteins.
Electrodialysis can be used to demineralize whey either in continuous mode
or in batches. This separation process involves transport of the charged species
across one or more semi-permeable membranes under the influence of a direct cur-
rent. Using this technology, a demineralization reaching a reduction 60%–75% in
mineral content can be achieved in continuous process. A reduction of 90%–95%
in mineral is possible by recirculating the whey in electrodialysis cells until a given
ash level (indicated by the conductivity of whey) is reached. With the electrodialysis
technology, preconcentration of the whey to 20%–30% dry matter is desirable in
order to maximize the utilization of installed membrane area and reduce electric
power consumption.
By using NF membranes, it is possible to simultaneously retain proteins, lactose,
and multivalent nutrition value ions like calcium and remove monovalent co-ions
(ions with the same charge as the membrane). With this technology, the demin-
eralization efficiency is then almost restricted to the removal of monovalent ions.
Considering the case of sweet whey (Gernigon et al., 2011), at pH around the neu-
trality (pH 6.0–6.6), the whey proteins are negatively charged and the membrane is
also negatively charged because the proteins are adsorbed at the membrane surface
and give their charge to the membrane. Proteins and polyvalent anions are retained
by the membrane which leads to the presence of higher amounts of negative charges
in the retentate. Na+ and K+ (with charge opposite to the one of the membranes)
are partially transmitted. The increase in positive charges in the permeate results
in a high transmission of Cl− and OH− in order to maintain the electroneutrality in
the permeate fraction. Therefore, at pH around the neutrality, the demineralization
efficiency of whey is mainly restricted to the removal of Cl− and OH−, that is to say
to the removal of monovalent ions with charge similar to the one of the membrane
(called the co-ion). As the opposite, in the case of acid whey, the retention of proteins
(positively charged at acidic pH) and polyvalent cations result in a partial removal of
Cl− and then in an increased transmission of Na+, K+, and H+. At a volume reduction
factor of 4, the removal of mineral from whey reaches 40%–60% and corresponds
to 70%–80% for monovalent co-ions (Cl− and OH− for sweet whey and Na+, K+,
and H+ for acid whey) (Jeantet et al., 1996). Divalent ions are reduced in the range
of 3%–20%. By combining with diafiltration, the ash reduction can be driven from
35%–50% up to 60%–70%.
The benefits of NF are numerous compared to electrodialysis and ion exchange.
It is a simple process that has the advantage of simultaneously concentrating the liq-
uid, which is often desired, and demineralizing. Since whey in most instances has to
pass through a concentration stage prior to further processing, the NF option is very
attractive because the demineralization is obtained without further cost. Moreover,
the transmembrane pressure used in NF is lower than in RO and the operation is gen-
erally more cost-effective. NF offers low investment costs and simple installations,
which are easy to run. The amount of effluent is greatly reduced in comparison with
other demineralization processes. Electrodialysis and ion exchange actually lead to

high investment and running costs mainly due to membrane, spacers, and electrodes
replacement, as well as the wastewater treatment for electrodialysis and the high
consumption of regeneration chemicals for ion exchange. In addition, the effluents
generated by NF have a lower biological oxygen demand (BOD) compared to other
demineralization processes.
Because of these many benefits, NF has become, in 20 years, the industrial
method of choice for the partial desalting of whey and has become a fast-growing
technology in the dairy world for different application purposes.
4.1.4.2 Concentration of Serum Proteins

The development of UF membrane processes in the 1970s has offered new possibili-
ties to fully exploit the nutritional, biological, and functional properties of whey pro-
teins. Until the 1970s, the interesting properties of whey proteins could not be fully
exploited because of the damaging effect of heat/acid treatments used for their sepa-
rations from whey. It has actually been a long practice to fully obtain whey proteins,
in a denatured form, by heating acidified whey (temperature ≫90°C and pH ≪6)
according to the technology used for making whey cheeses, such as ricotta. Today,
the use of UF is extensively applied to whey to allow the development of a broad
array of WPC with a protein/total solids ratio ranging from 35% to 85% (expressed
in nitrogen N × 6.38 over dry matter). WPCs containing ∼35% protein for instance
are used in the manufacture of processed cheese, yogurt, and infant formulae, and
in various bakery applications. MF can be included as an option for the removal of
bacteria, casein fines, and residual fat, thus contributing to an improved quality of
the final product. Using MF as a pretreatment makes it possible to produce WPI with
90% protein in the total solids.
Numerous studies related to the manufacture of WPCs and to their properties
have been published. In summary, UF membranes used have classically a cut-off
ranging from 10 to 20 kg/mol in order to retain proteins and remove both the lac-
tose and ions. The obtained retentate can then be further processed by diafiltration
(for protein purification) followed by evaporation and spray drying. The protein
content of the final whey protein product will depend on the degree of concentra-
tion during UF: a VRR of 4.5–7.0 is required for 35% WPC, and it should reach
13–20 for 50%–60% WPC. Combined with a diafiltration, which removes min-
erals and lactose from the retentate, whey UF (VRR 30–35) can lead to WPC
purity of 75%–85%. The manufacture of high-quality WPCs required particular
care of the technological treatments applied to the milk used for making cheese.
Heat treatments have actually a cumulating effect on the thermosensibility of the
whey proteins. The presence of proteolytic enzymes issued from psychotrophic
or thermoduric bacteria also causes casein degradation and increases the nonpro-
tein nitrogen content of the whey. Regarding the whey, careful control of bacteria
growth is essential because the initial bacteria count can be concentrated by up to
30–50 times during UF.
Whey UF is mainly performed in multi-stage spiral wound systems with polyether-
sulfone membranes. Processes are currently operated at temperature either around
50°C or 10°C. Operating at “high” temperature (∼50°C) requires a pre-treatment in
order to avoid severe fouling during operation, mainly due to calcium phosphate in
these conditions. Flux is about twice as high as flux at 10°C, which is a major incen-
tive for operation at such high temperature. However, due to the rapid decrease in
membrane prices, a low-temperature process (10–12°C) is now favored to limit
bacteria development in filtration plants, respect of the microbiological quality of
the end product, and limiting the membrane fouling due to the precipitation of the
calcium phosphate.
The fouling of UF membrane treating whey has been widely studied in the 1980s
and 1990s and it has largely been demonstrated that during UF, membrane foul-
ing is mainly attributed to three different species: (i) presence of residual lipids
coming from the cheese manufacture and still present even after a previous cen-
trifugation of the whey to be treated; (ii) accumulation of proteins at the membrane
surface, more pronounced at pH closed to their isoelectric point (pH ∼ 5.0–5.5), and
(iii) precipitation of calcium phosphate enhanced under neutral pH (7.0–7.5) and
high temperature (55°C). During the past years several whey pretreatments, some
using membrane operations, have then been proposed (Gésan-Guiziou, 2014). Some
pretreatments increase the purity of the final concentrates, especially by reducing
the residual lipids content; and some others improve UF performance especially by
limiting calcium phosphate precipitation and protein accumulation (Maubois and
Ollivier, 1997). Like WPC by UF, WPI can be produced more efficiently today using
the MF (0.1 µm membrane) permeate of skimmed milk.
4.1.4.3 Fractionation of Individual Serum Proteins

Fractionation of whey protein mixture for the isolation of one or a group of proteins
is useful to exploit the particular properties of individual proteins, which are known
to exert a wide range of nutritional, functional, and biological activities (Korhonen
and Pihlanto, 2007). Some putative activities of serum proteins are digestive func-
tion (β-lactoglobulin), anticarcinogenic (α-lactalbumin), antimicrobial (lactoferrin
and lactoperoxidase), and passive immunity (immunoglobulins). Considerable pro-
gresses have been made over the last 20 years in technologies aimed at separation,
fractionation, and isolation in a purified form of many interesting proteins occurring
in both bovine colostrum and milk. Most of them however are based on gel filtration
and chromatographic techniques. Some industrial-scale methods have been devel-
oped using membrane technologies for isolation of some proteins but their large-
scale manufacture is still limited (Bonnaillie and Tomasula, 2008). Defatted WPI,
obtained either from pretreated whey (using MF) or microfiltrate of skimmed milk
MF, could be some excellent starting materials for the industrial production of indi-
vidual proteins.
Among the commercially interesting proteins, the two main proteins of the whey,
α-lactalbumin and β-lactoglobulin, can be produced in enriched fractions using
membrane or centrifugation processes: α-lactalbumin has a great potential market
mainly because of its high content in infant milk formula, and β-lactoglobulin is
largely used in gel and foam-type products and in the manufacture of protein hydro-
lysates for food ingredients. The process developed to fractionate α-lactalbumin and
β-lactoglobulin from whey is based on the property of α-lactalbumin to reversibly
aggregate under acidic conditions and moderate heat treatment. α-Lactalbumin is a
calcium metalloprotein that contains one mole of calcium per mole of protein. When
pH is lowered to 3.8 at ∼55°C (30 min), this protein loses its bounded calcium which
results in the reversible polymerization of the protein that precipitates together with
immunoglobulins and bovine serum albumin (Bramaud et al., 1997). The separation
of the resulting aggregates consisting of α-lactalbumin and whey proteins other than
β-lactoglobulin can then be carried out by MF or centrifugation. If highly purified
β-lactoglobulin (95% purity) can be obtained through this process using UF in com-
bination with diafiltration, there are some limitations, to our knowledge, related to
the purity of the industrially recovered α-lactalbumin after solubilization at neutral
pH: the purity of the protein reaches a maximum of 60%–70%, due to presence of
immunoglobulins, denatured β-lactoglobulin, and bovine serum albumin that co-
precipitated during the process. Starting from the permeate of milk MF performed
at temperature lower than 45°C, this principle can be used to produce high-purity
non-lactosylated β-lactoglobulin (Maubois et al., 2001).
Immunoglobulins can also be isolated from whey using an UF membrane with
a cut-off about 100 kg/mol. However, whey is a poor source of immunoglobu-
lins compared to colostrum (first secretion of mammals after parturition) or milk
produced by hyperimmunized cows. Cows’ colostrum contains substantially
higher concentrations of immunoglobulins than mature milk (20–200 g/L against
0.15–0.8 g/L) and then can be used as an appropriate starting fluid for a two-step
immunoglobulin extraction procedure. Therefore, much effort has been made to
extract these proteins from colostrum or colostral whey. By using several filtra-
tion techniques (RO, UF, and MF) and a cation-exchange resins as a molecular
sieve, Korhonen et al. (1998) concentrate immunoglobulins (Igs) from colostral
whey reach an Igs concentration up to 75% in the final freeze-dried fractions.
Piot et al. (2004) obtained enriched Igs fraction from MF and UF of cows’ colos-
trum. After an MF using a 0.1 µm pore membrane so as to obtain a permeate
(named “serocolostrum”) free of blood, somatic cells, fat globules, and casein
micelles, they concentrate the permeate fraction that contains 80% of the initial
immunoglobulins using UF (100 kg/mol). Commercial immunoglobulin products
are mostly used in veterinary medicine or in neonatal animal offspring for health
preservation through the stimulation of the immature immune system of young
animals (piglets, foals, calves, and lambs). Because ruminants are born without
blood antibodies, they are very susceptible to infection, and it is highly desirable
that they receive protection either by suckling colostrum for at least one week or
by ingesting an immunoglobulin concentrate.
4.1.4.4 Fractionation of Peptides

There is considerable commercial interest in producing bioactive peptides from milk
for applications in the food industry. Bioactive peptides have a positive impact on
body functions and conditions and may ultimately influence health (regulation of
weight; mood, memory, and stress control; immune defence, improvement of heart,
bone, dental digestive health, etc.) (Korhonen, 2009). The market of bioactive pep-
tides is increasing because the possibility of designing new dairy products with
health-promoting benefits looks promising and offers a new perspective for consum-
ers and producers. Over the past decades a number of methods have been developed
for their purification and to date, some casein-derived peptides have been manufac-
tured on an industrial scale.
The most common way to produce bioactive peptides is through enzymatic
hydrolysis of precursor proteins, using gastrointestinal enzymes, usually pepsin and
trypsin. After hydrolysis, the peptides are fractionated and enriched using different
methods such as precipitation with salts or solvents, NF, UF, or chromatography.
Application of UF reactor for continuous extraction of permeates enriched with bio-
active peptides has been described for the production of several peptides (Korhonen
and Pihlanto, 2006). For the preparation of phosphopeptides from casein, Brulé et al.
(1981) proposed for example the use of an UF membrane for processing perme-
ate after digestion of caseinate in solution with a proteolytic enzyme. The separa-
tion of the phosphopeptides present in the permeate was performed by UF of the
peptides solution after the addition of a bivalent cation salt (calcium chloride) so
as to cause aggregation of phosphopeptides. The nonphosphorylated peptides pass
the membrane and diafiltration against water, used to purify the phosphopeptides
in the retentate, resulting in a preparation which is rich (>90% w/w) in the desired
phosphopeptides.
The glycomacropeptide (C-terminal part of the κ-casein release in whey by the
action of chymosin) was shown to be separated from sodium caseinate using UF
membrane. This peptide has various uses (action on satiety, inhibition of Escherichia
coli cells adhesion to intestinal walls, etc.) and in particular it contains no phenyl-
alanine (Phe), which makes it suitable for use as a nutritional protein supplement for
patients suffering from phenylketonuria, who did not digest protein with phenylala-
nine due to their lack of the appropriate degrading enzyme.
The occurrence of many bioactive peptides in bovine milk is now well established
(Korhonen, 2009), but at present the industrial-scale production of such peptides is
limited by a lack of suitable separation technologies. Among them, membrane tech-
niques, such as NF or UF are used industrially to produce ingredients which contain
bioactive peptides based on casein or whey protein hydrolysates and seem to be the
best technology available for the enrichment of bioactive peptides.
4.1.5 Treatment of Effluents and Technical Fluids

In the food industry, the dairy sector generates a large volume of processing wastes. It
produces 0.2–11.0 L effluents/L of processed milk, with a mean value around 1.3 L/L
of milk. In spite of significant improvement over the last years, water consump-
tion still remains high especially for the cleaning of membrane plants: 1.25–5 m3 of
water for the cleaning of 100 m2 of membrane for each operation. Simultaneously
water cost steadily increases (1.2–5.7 €/m3 in France) and resources of appropriate
quality tend to become scarce. The generated effluents are rarely toxic but lead to
a relatively high polluting load: the BOD classically ranges from 0.2 to 2.5 g/L and
is mainly due to loss of raw material (0.5%–2.5% of milk). Although still a high
portion of dairy wastewater is still land spread, the treatment of the end-of-pipe
effluents has been mainly operated in biological treatment plants by the majority of
dairies. For a factory of a mean capacity of 106 L of milk a day, produced sludge is
usually used for land spreading (1–3 tons of dry matter) and purified water drained
to rivers (0.3 × 106 –3 × 106 L) (Daufin et al., 2001). Due to more and more severe
European regulations relating to landfill management, land spreading, and purified
water quality along with social pressure, the dairy industry has recently been pushed
to significantly reduce its production of sludge and to improve purified water qual-
ity. The dairy industry has then been attempting to find new processes to reduce its
effluents production and membrane technologies have offered new opportunities by
not only reducing the volume and the pollution load generated by the used water, but
also recycling a significant part of the milk water.
4.1.5.1 Recovery of Process Waters

Several dairy industry process waters resulting from starting, stopping, or rinsing
phases are separated and treated individually at source, mainly benefiting from the
potentialities of membrane technology. This type of effluent constitutes a major
source of milk protein and fat loss as well as pollution (Daufin et al., 2001). Most of
the earlier work on the process waters treatment has been done using NF and RO,
mainly in spiral wound configuration because of its availability and relatively low
cost (Jaffrin et al., 2010).
Washing waters of rennet casein precipitate and Emmental cheese were treated
respectively using NF and dead-end filtration; white waters, corresponding to waters
discharged after flushing phase, and pre-rinsing waters, corresponding to the first
step of cleaning-in-place, were treated using UF, NF, or RO (Daufin et al., 2001). The
treatments resulted in a significant improvement of water quality (suspended solids,
SS < 2 mg/L; chemical oxygen demand, COD < 35 mg/L; BOD5 < 3 mg/L) and took
into account the reuse of milk components as recycling back to the production unit
or animal feeding.
Permeates of milk and whey NF with COD content in the range 10–1000 mg/L
and evaporation condensates, usually called “cow’s water” in the dairy sector, can be
treated by RO with eventual UF or MF pretreatment (Horton, 1997). In both cases,
the RO permeate produced can be used as a source of water with “food quality,” for
rinsing and cleaning operations (Vourch et al., 2008).
4.1.5.2 Clarification of Brine

In recent years, efficient recycling and sanitation of cheese brine (170–230 g
NaCl/kg) has become a major concern to the dairy industry. In the cheese manu-
facture, the cheese brining is classically performed by submersion of the curd in a
salt solution in order first to slow down or stop the bacteria process of converting
lactose into lactic acid and second to develop the flavor and cheese properties. The
microbiological and chemical composition of used brine is critical for the produc-
tion of high-quality cheese. The brine may contain unwanted microorganisms able
to grow in 20% salt, that results from the possibility of the post-contamination of
cheese in the brine (Staphylococcus, Listeria). Since dumping of the cheese brine is
very costly and often prohibited due to the high salt content of the brine, cheese brine
has been classically treated for further reuse by heat treatment, Kieselguhr (diato-
maceous earth) dead-end filtration, UV radiation, or addition of preservatives. Heat
treatment and Kieselguhr filtration are so far the most successful technologies for
brine treatment but the first one changes the chemical composition by modification
FIGURE 4.14 MF plant for brine sanitation. (Courtesy of GEA, France.)
of the calcium phosphate equilibrium in solution, and the latter is recognized by The
World Health Organization as a cause of lung disease and requires ensuring safe
working conditions. Compared to traditional processes, the application of crossflow
filtration treatment and more particularly MF, results in superior cheese quality. The
recycling of cheese brine using an UF (50 kDa) or mainly MF (0.2–1.4 µm) step
reduces microbiological counts (decimal reduction around 2–3) without altering the
brine contrary to conventional pasteurization and avoids filter aids (Pedersen, 1992).
The composition and quality of cheese brine vary from one factory to another
and this makes it difficult to give a detailed description of the process. In the brine
treatment by MF, a prefiltration of the brine is necessarily done by dead-end filtra-
tion filter bag or cartridge with 100 µm pore size. The regeneration was primarily
based on ceramic membrane, but developments have recently been done with spiral
wound membranes (Figure 4.14). The operating temperature is normally the same as
that used for brining the cheese, that is to say around 13–20°C, which limits calcium
phosphate precipitation. The VRR is generally high, up to 200, resulting in a concen-
trate volume typically around 0.5% of the feed volume. Normally, the concentrate
volume is regulated to compensate the amount of surplus arising from the whey
release from the cheese.
4.1.5.3 Recycling of Cleaning Solutions

Used alkaline and acid cleaning in place (CIP) solutions, which are periodically
drained to waste on a frequency based on subjective criteria (color and odor), can
also be advantageously regenerated. Indeed, CIP solutions significantly contribute to
the level of water consumption and are responsible for 50%–95% of the overall vol-
ume of waste streams (Alvarez et al., 2007). Moreover, regardless of their frequency
of discharge, which varies according to the dairy equipment and plants to be cleaned
(1 day–1 year), these solutions are mainly responsible for the high pH value (9–11) of
the wastewaters reaching water treatment stations.
Desludging of caustic soda solutions is currently practiced using classical cen-
trifuge. However filtration processes, and more particularly MF, which retains sus-
pended solids and lets pass small molecules responsible for the low surface tension (γ)
property of the reused solutions, seems to be an appropriate regeneration operation
both for technical and economic reasons (Gésan-Guiziou et al., 2007). It has actually
previously been shown that during the cleaning-in-place with recycled solutions, sus-
pended solids and polluting load increased and a sharp decrease of the surface tension
(γ) of caustic soda (NaOH) solutions was observed: γ decreased from 74 mJ/m2 (sur-
face tension of fresh NaOH solution) down to 30 mJ/m2. The decrease of γ was shown
to result from the chemical reactions of the milk protein and fat with the cleaning
solutions (Alvarez et al., 2007). Because the suspended solids, which are detrimental
to the cleaning rate, were removed by MF membrane and the surface tension char-
acteristics maintained at low values (γ ≈ 30–35 mJ/m2), the MF-regenerated caustic
soda solutions are much more efficient than fresh caustic soda and become as fast as a
commercial alkaline detergent at a temperature of 50°C (Alvarez et al., 2007).
4.1.5.4 Treatment of End-of-Pipe Wastewaters

Several companies propose the use of a membrane aerobic bioreactor (MBR) for the
treatment of end-of-pipe industrial wastewaters, but very few are currently running.
Two designs of MBR exist: external loop with organic or ceramic UF membranes
and hollow fiber UF membranes immersed in the station. In both cases membrane
separation replaces the decantation practiced in classical waste treatment. Several
advantages were claimed by the manufacturers: a significant reduction of sludge
(×0.3–0.5 with a conversion rate in the range 0.1–0.4 kgdry sludge/kgCOD removed) and
an enhanced quality and stability of cleaned water. The water is announced to be
sanitized, at pH ranging from 6.5 to 7.5, containing no suspended solids, low COD
(<60 mg/L), and total Kjeldhal nitrogen <10 mg/L.
Research is currently in progress in these aerobic MBRs as well as anaerobic
MBRs, which theoretically should yield much lower sludge rates. The objectives are
to achieve high-active biomass concentration, minimum apparent growth of micro-
organisms, adaptation of microorganisms to the specific composition of food waste
streams, and optimization of the filtration performance at high cell density conditions.
4.1.6 Conclusions and Future Trends

Today, membrane-separation technologies offer the dairy technologist several kinds
of techniques for the extraction and purification of almost all the main proteins of
milk and for the treatment of wastewaters. Most of the industrial developments of
membrane technologies in the food industry originate from the dairy industry.
Membrane operations have made it possible for new and original products to be
created which were simply not possible before. The fractionation of casein micelles
from serum proteins using MF membrane is one of the best recent example of such
success, and would have been considered unlikely some years ago. The differences
in attributes between serum proteins obtained from milk (using milk MF) and those
isolated from cheese whey are becoming an important factor for dairy protein pro-
cessors considering, very recently, this new avenue for fractionating proteins and for
producing bioactive peptides. Apart from being a balanced source of valuable amino
acids, milk proteins contribute actually to the specific properties of various dairy
products, and possess interesting biological properties which make them potential
ingredients for health-promoting foods. A few commercial protein and peptides frac-
tions have been launched on the market and this trend is likely to continue alongside
with increasing knowledge about the functionalities of the products.
The advances in membrane design, the best understanding of the limiting phe-
nomena occurring during filtration operations, and the recent decrease of the pro-
cessing cost of polymer membrane, make this technology more and more attractive.
Then further integration of membrane operations is to be expected, provided they
are designed in such a way that at each processing step, membrane fouling is lim-
ited, membrane cleaning is optimized, and end-products, co-products, and wastes
are given even attention. Through the dairy industry, membrane processes have been
shown to provide the food industry with efficient tools for limiting the environmental
impact of the food sector. There is no doubt that in the near future any food process
will then include at least one membrane operation for its effluents treatment.
New applications are also likely to develop, like the recovery of phospholipids
derived from the fat globule membrane from buttermilk (the aqueous phase pro-
duced from churning butter), recovery of growth factors present in cows’ colostrum.
Moreover, new emerging technologies (such as rotating and vibrating filtration,
emulsification, supercritical carbon dioxide fractionation, etc.) have met some suc-
cess on a research level and could lead to more commercial applications in the com-
ing years (Jaffrin et al., 2010).
4.2 EGG-PROCESSING INDUSTRY

Today, worldwide egg production has reached 63 million tons of hen eggs, which
correspond to approximately one thousand billion eggs on a basis of 16.4 eggs per
kg (Nau et al., 2010). Approximately 30% of egg consumption is in the form of pro-
cessed egg products (Froning, 2008). The term “egg products” refers to eggs that are
removed from their shells for processing at facilities called “breaker plants.” They
include whole eggs, whites, yolks, and various blends.
Because of their high functionalities (foaming, coagulative, emulsification, bind-
ing, etc.), egg products are particularly appreciated as ingredients, either in the form
of fresh, dried or frozen egg solids, incorporated in a large number of food products
(bakery products, meringues, mayonnaise, cookies, etc.). Egg white for instance is
largely used in the baking, confectionary, and cake mix industries for its whipping
and foaming properties.
Since the 1960s, the hen egg processing industry has seen numerous technological
developments targeted at achieving high quality of processed egg products. Egg con-
tains about 75% water. Membrane processes do not involve a phase change. Membrane
separations also protect the egg proteins from thermal denaturation. With these bene-
fits, the introduction of membrane filtration for the concentration of eggs before drying
was a big step forward for the egg processing industry. In the recent years, innovative
researches have revealed the diversity of chemical structures, properties, and functions
of egg components especially in relation to biological and nutritional aspects. These
findings have led to the acceptance of processed eggs for many potential applications
in the food and pharmaceutical industries. The growing acceptance of processed eggs
has therefore led to improvements and innovations in processing methods.
Even though, membranes have been used for the extraction of egg components,
the majority of developments in this field have been focused on the use of chro-
matographic separation methods. As of today, in the hen egg processing industry,
membrane processes are mainly used for the concentration of some egg products and
more rarely for the extraction of proteins.
4.2.1 Characteristics of Hen Egg (White, Yolk, and Whole)

Hen eggs are composed of three main parts: the albumen also called the egg white,
the egg yolk, which is surrounded by the white, and the hard eggshell with the egg-
shell membrane, which in turn envelops the egg white (Table 4.3). Egg proteins are
essentially distributed between the egg white and the yolk, with a small proportion in
TABLE 4.3
Composition of Egg White and Yolk Protein
Molecular Weight
Protein Protein % of Egg White Isoelectric Point (kg/mol or kDa)
Ovalbumin 54 4.5 (5.1–5.3) 45 (42.4)
Ovalbumin Y (5.3–5.5) (53.4–54.3)
Ovotransferrin 12 6.1 (6.2–6.7) 76 (85–75)
Ovomucoid 11 4.1 28 (37.2–43.1)
Ovomucin 3.5 4.5–5.0 5500–8300
Lysozyme 3.4 10.7 14.3 (15)
Ovoglobulin (6.1–5.3)
G2 globulin 4.0 5.5 30–45
G3 globulin 4.0 4.8 Not determined
Ovoinhibitor 1.5 5.1 (6.2–6.4) 49 (69.5–63.6)
Ovoglycoprotein 1.0 3.9 (5.0–5.4) 24.4 (37.2–43.1)
Ovoflavoprotein 0.8 4 (5.0–5.2) 32 (37.4–40)
Ovomacroglobulin 0.5 4.5 769
Cystatin 0.05 5.1 (6.1) 12.7 (17)
Avidin 0.05 10 68.3
Source: Li-Chan, E. C. Y. and H. O. Kim. 2008. Structure and chemical composition of eggs. In Egg
Bioscience and Biotechnology, ed. Y. Mine, 1–95. New Jersey, US: Wiley, Interscience, Hoboken;
Data were compiled from Li-Chan, E. C. Y., W. D. Powrie, and S. Nakai. 1995. The chemistry of
eggs and egg products. In Egg Science and Technology, eds. W. J. Stadelman and O. J. Cotteril,
105–175, Binghamton, NY: Haworth Press, fourth edition, except for those in parentheses, which
are from Guérin-Dubiard, C et al. 2006. J Agric. Food Chem. 54(11):3901–3910.
the shell. Lipids are almost exclusively found in the egg yolk, and most of the miner-
als are found in the yolk and in the eggshell.
The egg white makes up about 66% of the liquid weight of the egg. It contains
about 88%–90% of water. Proteins are the major components of albumen solids
(about 10%–11% of the white weight) while carbohydrates (mostly free glucose,
2–4 g/kg) (≈ 0.8%–1.0%), minerals (≈ 0.5%), and lipids (≈ 0.03%) are minor com-
ponents. Except from lysozyme and avidin, egg white proteins are predominantly
globular proteins having an acidic isoelectric point and being negatively charged at
the natural pH of the egg white (pH = 9.0–9.3).
Egg yolk contains about 48%–51% of water and is mainly composed of proteins
and lipids. These constituents account for 16% and 31% of the yolk’s total weight,
respectively. The yolk lipid fraction contains about 65% of triglycerides, 28%–30%
phospholipids, and 4%–5% cholesterol. Yolk proteins consist of livetins and lipopro-
teins particles including low- and high-density lipoproteins. The yolk is also a major
source of vitamins and minerals (3.5% of dry yolk).
Whole egg, obtained by blending egg white with yolk, contains about 25% solids,
23% of proteins, and 10% of fat with traces of minerals and carbohydrate.
4.2.2 Concentration and Stabilization of Egg White and Whole Egg

The concentration of egg products is mainly applicable to the egg white and whole
egg. It is actually not crucial to concentrate egg yolk because it contains about 50%
solids. Egg products are concentrated for two primary reasons: first to increase the
concentration of egg components before spray drying and second for the stabiliza-
tion of egg white and whole egg.
4.2.2.1 Concentration Before Spray Drying or Storage in Liquid Form

Owing to its high water content, the egg white is quasi-systematically concentrated
before spray drying. The concentration of whole egg before spray drying is marginal.
Generally, a concentration factor of about two reduces the load on the dryer to around
50%. The concentration increases the dry matter of egg white from 10%–12% to
around 20%–24% (Figure 4.15). The concentration by a factor of two reduces the
energy costs of the dryer and increases the productivity of the spray dryer throughput
up to 230% of normal capacity. Additional related advantages of concentration are
smaller fermentation storage tanks, reduced tanker transportation costs, and reduc-
tion in freezing costs by 50% or more.
Egg products are rarely concentrated using conventional thermal evapora-
tion because the high heat and shear can damage the sensitive egg white proteins.
Nowadays, membrane filtration is being increasingly used for the concentration of
egg products either to obtain products to be marketed in a concentrated form or to
achieve required concentration before dehydration (spray drying). The advantage of
membrane-based separation is that it does not involve heat and therefore protects the
important functional properties of egg white powder such as whip height and cake
height for angel food cakes and gel strength for surimi and sausage applications. In
addition, the concentrated egg products, which are liquid at intermediate moisture
contents, can be kept anywhere from 6 months to 1 year at ambient temperature.
Shell eggs
Egg breaking
Egg yolk Egg white Whole egg

10%–12% dry matter
Concentration by UF Concentration by UF
Concentration by RO
Up to 33% Up to 20%–24%
Spray drying
Spray drying Addition of Spray drying
salt/sugar
Egg white Egg white Stabilized egg Whole egg Whole egg
concentrates powder white products powder concentrates
Partially demineralized Partially demineralized

and desugared egg and desugared egg
white powder white concentrates
FIGURE 4.15 Applications of membrane filtration for the concentration and purification of
egg white and whole egg.
Membrane processes, especially RO and UF have been investigated and commer-

cially applied to the concentration of egg, especially egg white (Bergquist, 1995). RO
can be used to concentrate all egg components (Figure 4.15) and generally leads to a
permeate containing mainly water free of organic matter. The RO permeate can be
used as process water for intermediate cleaning operations. UF process involves mem-
branes which are more open as compared to RO. UF is also used for the concentration
of proteins and low molecular weight cut-off (MWCO) is generally used in order to
limit the loss of nitrogen matter. Like RO, UF membranes also permeate water but in
addition, UF membranes also permeate glucose and minerals such as sodium and potas-
sium up to about 50%, then resulting in enriched egg proteins. In some applications,
the presence of glucose is actually undesirable since it causes a detrimental effect on
storage stability and quality of the product, by forming off-flavors and brown pigments
caused by Maillard reaction during heat processing. Glucose reduces the stability of
manufactured egg products and is usually removed through a bacterial fermentation
or an enzymatic hydrolysis process (prohibited in France) using glucose oxidase and
catalase. By using UF membranes, the glucose content is automatically reduced, which
contributes to reduced problem during storage and improved quality product. A higher
removal of glucose (higher transmission in the permeate), while retaining the egg white
proteins, can be achieved by carrying out UF in conjunction with diafiltration. In gen-
eral, removal of sugar from egg whites improves their foaming capacity.
When comparing RO and UF processes for egg white concentration, UF was
found to lead to higher permeate flux, lower energy consumption (due to lower applied
transmembrane pressure), and superior functional properties of the concentrate due
to the removal of free glucose and salts. Neither of the concentration methods (RO
or UF) significantly affected foaming properties of the final products. UF was also
observed to improve the gel strength of egg white, which was likely related to the
increase in protein concentration.
4.2.2.2 Stabilization
Another purpose of the concentration of liquid egg white and whole egg is to achieve
stabilization of the product. The stabilization of eggs is achieved by first concentrat-
ing the egg product by UF and then adding salt and/or sugar so as to decrease the
water activity (aw) of the product under the thresholds of microorganism develop-
ment (aw = 0.85) (Bonduelle, 1978; Liot, 1980). This process enables the processing
of concentrated egg white up to 33% dry matter content with a maximum sugar con-
tent of 50% or salt content of 9% (0.80 < aw < 0.85) (Figure 4.15). Such egg products
can be stored several months at ambient temperature, without special attention. The
functionalities of the stabilized egg products can be maintained for months since
concentration by membranes does not involve any thermal treatment. Lastly, the
concentrated and sugar stabilized products also possess high foaming properties,
particularly required in cake processing.
Despite several improvements in the process of UF, its application for the concen-
tration of whole eggs is still not common. The primary reason is the low flux obtained
during UF of whole eggs. A vacuum plate evaporator with low residence time is pre-
ferred for the concentration of whole eggs. Using a vacuum plate evaporator, it is pos-
sible to obtain a concentrate up to 70%–74% of dry matter with 50% of sugar.
4.2.2.3 Types of Filtration Systems

Similar to other industries, initially the egg industry also adopted the plate-and-
frame type of membrane filtration systems. However, today most egg white treat-
ment plants use spiral wound systems and sometimes tubular ceramic membranes.
The spiral wound systems are cheaper than most other filtration type systems as
they incorporate high membrane areas in less space. The tubular ceramic systems
are easier to clean as they can withstand extremes of pH and temperature and can
reach superior dry matter. For the concentration of egg white, it is recommended
that the product is prefiltered before membrane filtration to remove the residual yolk
and shells. In order to avoid microbial issues and potential heat and shear damage
of the proteins, the following controls of the operating conditions are required: (i)
the temperature should be lower than 45°C, often between 35°C and 40°C; (ii) the
transmembrane pressure, ΔP for UF should be lower than 600 kPa, and for RO ΔP is
around 2–4 MPa; and (iii) the crossflow velocity is lower than 4 m/s.
VRR of about 2.0 is achieved using either RO or UF. VRR is limited at 2.0 due
to the high viscosity of eggs beyond this point. A VRR of 2.0 leads to the final total
solids ranging between 20% and 24%. The plant is normally designed to operate in
the continuous mode: the feed material is introduced into the plant on a continuous
basis while the concentrate and permeate is continuously withdrawn from the plant.
Permeate flux of about 5–15 L/h/m2 at 450 kPa is achieved for VRR of 2.0 using UF.
The UF system for egg white concentration is generally designed to run in produc-
tion mode for 20 h and CIP for 3–4 h. UF can also be to concentrate up to 3.0 VRR
thereby reaching as much as 32% total solids. RO leads to permeate flux around
5–10 L/h/m2 at ΔP of 3–4 MPa.
Whole eggs are difficult to process using membranes, especially due to their high
fat content (11%). The total solid of whole eggs is about 25%. Ceramic UF membranes
are sometimes used for the concentration of whole eggs to about 42% total solids.
4.2.3 Extraction of Egg-White Proteins

Due to the high nutritional, functional, and biological properties of egg-white pro-
teins, there is a need to develop efficient, simple, and cost-effective methodologies for
the isolation and purification of egg proteins, and substitutes (peptides, etc.). Many
studies are currently in progress for the extraction of albumen proteins. Several
methods for the isolation and fractionation of proteins have already been proposed,
but very few have been applied or adopted at industrial scale (Nau et al., 2010). Only
a few of the protein isolation or fractionation techniques are based on the utilization
of membrane separations.
Lysozyme is the only hen egg protein which is commercially used. Lysozyme
can be used as a preservative and finds practical applications in the food and phar-
maceutical industries (Lesnierowski and Kijowski, 2007). For example, lysozyme is
used in cheese to prevent contamination without inhibiting the starter and secondary
cultures required for the ripening of cheese. Lysozyme possesses antibacterial prop-
erties, particularly against Gram-negative bacteria, among them a number of food
pathogens such as Listeria monocytogenes. Lysozyme is known as a hydrolysate that
cuts the β-1–4 linkage of the glycosidic bond between polysaccharide copolymers,
which represent the structural units of many bacterial cell walls.
Lysozyme from hen egg white is a small protein with a molecular weight of
14.2 kg/mol. It has a strong basic character (isoelectric point of 10–11) unlike other
egg proteins. Both the physical and chemical properties of lysozyme have been
exploited to isolate or fractionate this protein. The small size of the protein has been
used to propose membrane techniques, especially UF or MF to separate the lysozyme
from the egg white. However, the ability of this enzyme to electrostatically bind with
other negatively charged egg white proteins greatly reduced the transmission of the
protein through the membrane. Ceramic MF membranes have been found to achieve
high recovery rates of lysozyme from 50% to 80% with a final purity greater than
80% (Lepienne et al., 1986). Although some of these membrane processes have been
tested on a large scale (Peri and Feriscini, 1972; Lepienne et al., 1986; Kijowski
et al., 1998), none of them have been adopted at the industrial level. Today the com-
mercial procedures of lysozyme isolation are (i) the selective precipitation of the
lysozyme and (ii) the extraction of lysozyme using ion exchange chromatography
(Gésan-Guiziou, 2010b). Both these processes exploit the highly basic characteristic
(very high isoelectric point) of lysozyme.
4.2.4 Conclusions and Future Trends

The egg-processing industry has made tremendous progress since the 1950s. The
introduction of membranes to the egg processing industry has been one of such
improvement methods. Membrane filtration in the egg processing industry is primar-

ily used for the concentration and stabilization of egg white and whole egg. The egg
processing industry has also recently learned to fractionate its products. The develop-
ment in the separation methods to produce enriched fractions (ovotransferrin, avidin
for instance) of egg proteins are likely to happen soon. This will lead to increasing
the potential utilization of egg in food and pharmaceutical applications. For exam-
ple, the enzymatic hydrolysis of egg white to produce various peptides with specific
activities (bacteriostatic, antioxidant, etc.) has been promising (Chay Pak Ting et al.,
2010). Thus processed egg products have a strong potential to influence the future of
the food and pharmaceutical markets with special emphasis on the health benefits of
eggs. Therefore, for this purpose, there is a growing need to develop new technolo-
gies for the production of specific bioactive peptides. Membrane-based separation
techniques, which have traditionally been used to separate molecules of different
sizes and low-molecular-weight components from proteins, could offer huge separa-
tion benefits for the egg processing industry with lower costs and reduced load of
industrial wastewaters compared to chromatographic techniques.
Finally, since membrane-based separation processes are environmentally friendly,
they can therefore be developed in the coming years to treat the wastewater produced
by the egg-processing industry (Fuchs et al., 2003; Yordanov, 2010). The load of the
effluents issued from egg-breaking machines for instance is particularly high with
a biological demand in oxygen at 5 days (BDO5) ranging from 1 to 22 g/L. The
membrane technologies offer good opportunity to decrease the load of effluents sent
to the purification station (Yordanov, 2010). Treatment of the process wastewater
is nothing new to the dairy industry and it is therefore extremely possible to do the
same in the egg processing industry.
4.3 OTHER SECTORS

4.3.1 Seafood Processing Industry
Membrane applications in the seafood sector emerged in the early 1980s. But due
to the high development of the fish meal industry (for instance, +600% increase
of surimi-based products since 1994), the considerable wasting of biotechnological
material contained in marine resources, and the increase of environmental restric-
tions, such techniques are expected to grow in the coming years for better utilization
of by-products from fisheries. World fisheries in 2004 were about 140 billion tons
and only 75% were used as food, leaving about 35 million tons for non-food uses, a
significant part even being discarded (7.3 million tons in 2004) (FAO, 2004, 2006).
Membrane separations are actually useful techniques to extract, concentrate, frac-
tionate, or even purify valuable marine molecules from seafood effluents, wastes, or
by-products (Almas, 1985; Jaouen and Quémeneur, 1992; Bérot et al., 1998; Afonso
and Borquez, 2002). These effluents contain a high organic load, present high turbid-
ity, strong greenish yellow color, and a stinky odor. They do not comply with restric-
tive regulations and should not be discharged anymore directly into the sea without
an effective treatment in order to prevent negative environmental impacts. At the
same time, the wastewater from fish processing contain a large amount of potentially
valuable components (proteins and enzymes) that can be recovered by concentration

and purification under mild conditions by membrane operations.
Reducing pollution, recovering proteins, and reclaiming reusable water from sea-
food wastewater by membrane filtration has been reported by many authors (Afonso
and Borquez, 2002).
4.3.1.1 Recovery of Proteins from Surimi Production

Surimi is a Japanese term for washed and dewatered fish mince widely used as a raw
ingredient in manufacturing products such as crab meat incorporated into a variety
of Asian foods. It is a concentrate of the myofibrillar proteins of fishes.
During surimi processing, the harvested fish are mechanically headed, gutted,
skinned, and comminuted into fish mince. This mechanical separation is followed
by successive washings with chilled water (5–10°C) to remove most of the fat and
water-soluble substances (sarcoplasmic proteins, vitamins, pigments, and enzymes)
responsible for odor and color of the fish mince. In addition to the soluble compo-
nents, a considerable amount of myofibrillar proteins is also washed out from the
fish mince. After dewatering of the minced fish muscle, the fish mince is mixed
with cryoprotectants and deeply frozen. As a result of washing, large volumes of
wastewater are generated in the downstream dewatering operations: about 27 m3 per
ton of surimi (Afonso and Borquez, 2002). The effluents also contain high concen-
trations of organic materials: about 30%–50% of the fish solids are lost to the wash
water and the final wastewater contains about 2–6 g of lost proteins/L (Watanabe
et al., 1982). It can be noticed that the wastewater from the first washing/rinsing
by fresh water in surimi production contains the highest concentrations of soluble
components, although it constitutes only 1%–2% of the total processing water. The
chromatographic analysis of the mixture of proteins contained in washing waters
showed three main fractions: one around 70 kg/mol, another one around 20 kg/mol,
and a peptides/amino-acids fraction with a mass <1 kg/mol.
In that context membrane technologies, and mainly UF, offer four main advan-
tages: (1) recovery of soluble proteins for fish protein, value-added flavorings or
bioactive compounds, (2) recovery of large particle-sized suspended solids such as
myofibrillar proteins, (3) reclaiming reusable water, and (4) reduction of the pollut-
ing load of the discharged effluent.
Currently, most emphases have been focused on recovering soluble species after
performing centrifugation to remove suspended matter and fat, and reclaiming water
from the waste streams. UF is technically and economically attractive to reach these
goals (Afonso et al., 2004). The purification of the 20 kg/mol protein fraction is
usually performed in two steps: a previous removal of 70 kg/mol proteins by coagu-
lation, pH variation or centrifugation; and a removal of the peptides/amino-acids
fraction by UF and diafiltration. The small molecules can actually pass through
membranes with 10–20 kg/mol cut-off. In order to preserve functionalities of pro-
teins, UF is generally performed at a temperature around 15°C.
Table 4.4 gives an overview of the major studies performed on the UF of waste-
water produced by the washing of surimi. Watanabe et al. (1986) for instance inves-
tigated the recovery of soluble proteins using self-rejection dynamic membrane,
which was an artificially induced protein layer formed on the surface of ceramic
132
TABLE 4.4
Main Studies Performed on UF of Wastewaters Produced by the Washing of Surimi
Wastewaters
Concentration
References Fish (g/L) Module Membrane Remarks
Tsuchiya and Jack mackerel 10 – 20–30 kg/mol Treated volume: 30 L
Takahashi (1983) Sardine Duration: 5–6 h
Miyata (1984) Mackerel 2–9 Tubular, IHI Co Cellulose acetate 4.9 bar; 10°C
Sardine 4.5 × 11.1 mm J = 10 L/h/m2 at a VRR = 10
Ninomiya et al. Jack mackerel 1–20 Tubular 20 kg/mol Five to seven groups of proteins with mass in the
(1985) Sardine IHI Co range 4–150 kg/mol were identified
Mackerel 90% yield of recovery for protein with mass higher
Cod than 10 kg/mol
Pollock
Watanabe et al. – 1.24 22 tubes “Dynamic membrane” Treated volume = 60 L
(1986) Diameter = 5 mm; (artificially induced protein 8.2 bar; 1.4 m/s; T = 15°C
L = 500 mm layer formed on the surface of Duration: 18 h
porous ceramic microfilter) ∼100% yield of recovery for protein with mass
0.05 µm higher than 10 kg/mol
Jaouen and Pout Sardine 6 Millipore DDS, 30 commercial mineral and Polysulfone and sulfonated polysulfone showed a
Quémeneur Tech-Sep organic membranes strong affinity for fish proteins, while no adsorption
(1986) 10 kg/mol < cut-off < 100 kg/mol was detected for membranes of regenerated
Jaouen, et al. cellulose (hydrophilic material);
(1989) The effluent pollution (COD, BOD) was reduced by
75%; protein rejection was 100%, and permeate
was clear
(Continued)
TABLE 4.4 (Continued)
Main Studies Performed on UF of Wastewaters Produced by the Washing of Surimi
Wastewaters
Concentration
References Fish (g/L) Module Membrane Remarks
Dumay et al. Flat sheet, Orelis Four membrane materials The regenerated cellulose material led to the best
(2008) (polyether sulfone, results, followed by the polyacrylonitrile and
polyacrilonitrile, poly- polyvinylidene fluoride materials. Poor results were
vinylidene fluoride and obtained with polyether sulfone membrane.
regenerated cellulose) High recovery rate of the lipids and proteins the
5 Cut-off (from 3 to 100 kg/mol) COD was reduced by 75% (with the 10 kg/mol
membrane)
Khatprathuma – 2.7 Plate and frame Regenerate cellulose 30 and A VRR = 40 was reached
et al. (2010) 100 kg/mol protein retention was about 98% for both membranes
The permeate flux at the same TMP of the 30 kDa
Dairy Industry and Animal Products Processing Applications
membrane was higher than that of the 100 kDa

membrane
84% of COD was reduced
133
microfilters. Jaouen and Quémeneur (1986, 1992) studied surimi wastewater treat-
ment, using different types of UF membranes, namely, cellulose, polysulfone, and
zirconium oxide (10 kDa < cut-off < 100 kDa). They analyzed the contribution of
proteins adsorption upon membrane fouling and membrane performance (perme-
ation flux decline and regeneration after cleaning) against the operating conditions
(transmembrane pressure and crossflow velocity).
Nevertheless, today, recovering the suspended solids (myofibrillar proteins) is of
more commercial interest for surimi processors. Lin et al. (1994) demonstrated that
solids recovered from surimi wastewater by MF had highly functional properties and
composition comparable to the proteins in regular surimi. They could be directly
added to surimi to increase yield without affecting quality, while solids recovered by
UF (30 kg/mol) had a dark color and an unpleasant odor.
Huang and Morrisey (1998) investigated the membrane fouling during MF (poly-
sulfone membrane; 0.2 μm) of surimi wash water with the goal of recovering sus-
pended myofibrillar proteins.
4.3.1.2 Treatment of Other Effluents

Several types of effluents are currently produced and treated in the seafood industry:
pumping water, filleting rinse water, washing, cooking, and pressing waters, brines,
wastewaters generated during the fish meal production, etc. The treatment of these
effluents are one of the most likely potential uses for membrane techniques.
The first investigations on the use of filtration techniques for the treatment of
fish processing effluents were performed in Sweden (Ericksson, 1974). Experiments
were conducted in order to recover proteins from herring juice, filleting rinse water
and pressing water. The combination of UF and precipitation of proteins at their iso-
electric point was efficiently used to recover proteins from the wastewater generated
by the production of “Lutfish,” a popular Scandinavian dish which consists of stock-
fish soaked in lye. 85% of the proteins can be recovered at a VRR of 5 by UF and
the recovery yield can be increased with isoelectric precipitation of proteins by HCl.
RO can be used to concentrate proteins released in the process water from the
filleting industry and reused water at the same time. In the filleting industry the
consumption of fresh water is actually high (10–30 tons/ton of raw fish) and a high
proportion of proteins (5%–15%) can be lost in the rinsing water, especially after the
first rinse where the fish meat is directly put into contact with water.
Notable valuable substances can be recovered from the pumpwater used to unload
ships into the factories. Pumps are frequently used for that purpose and water is used
as a carrier medium to enable the fish mass to be pumped. During transport, the loss
of proteins and fat into the water leads to its high polluting load: the flow rates of the
polluted water are generally high (1–10 m3 per ton of unloaded fish) with an organic
load of several tens of gCOD/L (Afonso and Borquez, 2002). RO and UF may succeed
in the clarification of the contaminated seawater and in the recovery of solids that
can be used as animal feed (Afonso and Borquez, 2002).
Several studies have reported the application of membrane technologies for the
treatment of spent brines with the aims of both regenerating brines and recovering
useful products, mainly proteins. During salting of herring for instance, approx-
imately 200 L of brine is formed per ton of fish, containing proteins and aroma
components. Processes such as coagulation/flocculation and dissolved air flotation

are not the most suitable methods because of huge amounts of sludge generated.
In the 1980s, UF with organic membranes was used. Welsh and Zall (1984) used an
UF-activated carbon system to recover contact refrigeration brines used in fishing
(tuna) vessels. Spent brine was first filtered with a 30 kg/mol Amicon membrane
and then passed through a column of activated carbon. The final concentrate had
nutritional value suitable for animal feed, and the permeate could be reused after
being treated by activated carbon. Paulson et al. (1984) indicated that a fish process-
ing company in Minnesota used UF for the treatment of brine. The system, equipped
with a 20 kg/mol polysulfone membrane, recover proteins and oils that are being
reused in the process. More recently, inorganic membranes have been used because
of their chemical, mechanical, and thermal stability. Kuca and Szaniawska (2009)
used a Tami ceramic membrane with a 150 kg/mol cut off for the treatment of salted
wastewater from the fish industry containing 12.3% of NaCl and a COD in the range
of 4–15 g/L. The obtained results were satisfactory: low rejection of NaCl (6.5%) and
high rejection of proteins (81%).
Membrane techniques have also been used for the recovery of fish meal and
fish oil. In the processing of meal and oil, effluents are generally highly concen-
trated and anaerobic treatment is inefficient due to the high salt content, in the range
50–130 g/L. RO and UF proved to be an adequate alternative with stable permeation
fluxes (around 15 L/h/m2 with PCI membrane, with a pressure of 15 bar) and a COD
reduction reaching 95% (Bérot et al., 1998).
Several authors investigated the treatment of effluent discharged from the pro-
cessing of shellfish and/or crustaceans. In the United States, the concentration of
small added value molecules contained in the effluent from blue crab cooking is
performed with UF prior to drum drying or evaporation. The final concentrate can
be added to the crabmeal processed.
The concentration of process water coming from the steam cooker of shrimps was
investigated with UF. The permeate containing aroma compounds could be applied
in the brine of the shrimps after peeling. UF was shown to be efficient to recover
soluble components from oyster shucking wastewater and made it possible to prepare
oyster flavoring ingredients from the recovered waste.
4.3.1.3 Fractionation and Concentration of Protein Hydrolysates

Solid by-products such as filleting wastes or heads are usually converted to fish meal
or oil for feed with a low added-value, but better upgrading can be found. The enzy-
matic hydrolysis of protein-rich fish wastes is for instance a mean of transforming
the fishery by-products into products of high value having functional or biological
properties. Fish protein hydrolysates (FPH) are produced industrially with the help
of enzymes and are one of the most promising products for the future. In recent
years, a great number of peptides of biological interest have been produced in mild
controlled conditions by enzymatic hydrolysis. Fish protein hydrolysis can produce
peptides with excellent nutritional properties and/or interesting biological activities
such as antioxidant, antiradical, anticancer, antihypertensive, opiate-like, antiviral,
or secretagogue activities (Guérard, 2007). They can be sold for nutritional, dietetic,
or cosmetic purposes.
Obtaining high bioactivities from a given substrate is mainly controlled by the

enzyme specificity and hydrolysis conditions. The relation between the structure of
peptides and their activities is not known in detail but depends on various charac-
teristics of the peptides (amino-acid sequence, molecular mass, charge, etc.). In par-
ticular, the peptide mass has a great impact on the final properties of the concentrate
so that a membrane fractionation operation can be used as a second control step to
increase the specific activity of the final concentrate.
Therefore, UF and NF can be used to refine hydrolysates and also to fractionate
them in order to obtain a peptide population enriched in selected properties before
further concentration by evaporation and drying (Jeon et al., 1999; Wang et al., 2002;
Vandanjon et al., 2007).
Peptides can be separated from hydrolyzed and non-hydrolyzed proteins or
proteolytic enzymes with UF membranes with cut-off ranging from 20 to 100 kg/
mol. The peptides in the permeate can then be fractionated with UF membranes of
intermediate cut-off of approximately 4–8 kg/mol (Vandanjon et al., 2007). Peptide
solutions can also be concentrated with NF membranes with low cut-off, approxi-
mately 200–300 kg/mol which retains almost all the peptides except the smallest
ones (Vandanjon et al., 2007). UF and NF can also be used in a diafiltration mode
for desalination and partial deodorization with NF membranes.
Several works have then been carried out on marine hydrolysates. But in the
majority of the reported studies, the hydrolysates were not processed in “industrial”
conditions: the hydrolysates were diluted (about 1 w/v% or less) and studies were
performed either at total recycling or at a low VRR which is not appropriate on the
industrial scale due to low productivity, large membrane surface area required, and
low economic acceptability. Further experimental works are then required to con-
trol and adapt the operating conditions of the fractionation process. The coupling of
membrane operations to other technologies could also be proposed to improve the
selective fractionation of bioactive peptides.
4.3.2 Animal Products Industry: Blood and Gelatin

4.3.2.1 Blood
Increasing efforts have been made in the last years in order to collect animal blood
from slaughterhouses and ensure its valorization. Blood is actually one of the most
problematic by-products obtained while processing animals for meat: it is produced
in great amounts: around 3%–5% of animals live weight and about 6%–8% of the
carcasses is blood; the percentage of collected blood is low: during sticking, only
50%–60% of the blood is collected, while the remainder stays in the animal body
such as muscles, organs, etc.; and its pollutant load is particularly high (∼500 g
O2/L) (Linden and Lorient, 1994; Ockerman and Hansen, 2000). Moreover, blood
contains about 15%–18% protein, similar to that found in lean meat (Table 4.5),
having very high biological and nutritive values. Due to the important economic
value of proteins, the possibility of recovering the proteins contained in the blood
from slaughterhouses appears to be an interesting option to consider. For this reason,
blood is used as a valuable additive in the food sector as well as in the pharmaceuti-
cal and pet food industries (Mandal et al., 1999). All the protein concentrates and
TABLE 4.5
Composition of Blood in g/100 g
Blood Plasma (60% v:v) RBC (40% v:v)
Water 80–85 90–92 70–78
Proteins 15–18 6–8 25–29
Lipids 0.15 0.5–1.0 0.2
Glucids 0.10 0.08–0.12 –
Minerals 1 0.8–0.9 Traces
Source: Linden, G. and D. Lorient. 1994. Biochimie agro-industrielle: Valorisation

alimentaire de la production agricole. Paris: Masson.
isolates obtained from animal blood have excellent functional properties and nutri-
tive value, which make them suitable for use in meat and bakery products. They can
for instance replace the use of chicken egg to some extent in food products without
affecting acceptability.
Blood consists of a blood plasma fraction (∼60%) and a corpuscles or red blood
cells (RBC) fraction (∼40%). The protein contents of plasma and RBC are 6%–8%
and 25%–29%, respectively (Table 4.5). Blood plasma is the most valuable part of
the blood: it basically includes all the blood proteins consisting of albumin, immu-
noglobulin, lipoprotein, transferrin, and fibrinogen except hemoglobin, the major
protein of the cellular fraction. 75% of plasma proteins have a molecular weight
higher than 30,000 g/mol.
Figure 4.16 represents a complete scheme for blood processing including mem-
brane operations. The technical description of the process involves several steps. For
food use, blood should obviously be collected in a hygienic manner.
When the blood is collected from slaughtered animals, it can be directly concen-
trated by UF and spray dried as regular whole blood to prepare blood meal used for
animal feed and fertilizer (Fernando, 1981) (Figure 4.16). For further fractionation,
and in order to prevent the blood from clotting, an anticoagulant is generally added.
Calcium-binding substances such as citrates or sodium tripolyphosphate are suitable
for this purpose. Then, to carry out the separation and purification of blood proteins
the separation of plasma from the heavier cellular fraction is performed. This can
easily be carried out by means of a centrifuge (classically a cream separator). Porter
and Michaels (1971) advanced the idea of using UF for the separation of blood cells
from plasma, but 40 years later centrifugation is preferred.
The plasma proteins can then be either directly frozen or concentrated by UF
from 7% to 26% protein prior to drying (Figure 4.16). In the latter case, and in
order to protect the membrane system against fouling, the plasma is sometimes pre-
filtered. For applications in human foodstuffs such as ice creams, cakes, breads,
etc., a further removal of organic compounds (such as citrate) and salts from blood
plasma is necessary. Several techniques have been developed for these purposes.
Among them, ion exchange and UF associated with diafiltration are commonly
used in industry and lead to higher quality plasma protein than that obtained by
Whole raw blood
Concentration (UF) Drying

Cooling
Blood meal
Separation
(centrifugation)
5–10,000 g
Blood cell fraction Blood plasma
Coagulation Hemolysis Concentration/ Freezing

purification
(UF + diafiltration
Drying Hydrolysis
or ion exchange)
Frozen plasma
Blood cell Inactivation Spray drying
powder
Concentration/
purification
Plasma powder
(UF + diafiltration)
Concentration (RO)
Spray drying
Dried hydrolysates
FIGURE 4.16 Schematic representation of blood processing including membrane operations.
conventional vacuum evaporation (Del Hoyo et al., 2008). It has recently been shown
that membranes (UF ≈ 10 kg/mol + diafiltration) are more suitable for treating high
volumes of plasma, resulting in a good removal of the major ions in the permeate,
with low protein loss and no variations in pH (Del Hoyo et al., 2007). But if very
high demineralizing is required, ion exchange is more appropriate (Del Hoyo et al.,
2007). The concentrated plasma is further spray dried to a powder with a moisture
content of 5%.
The blood cell fraction can also be processed using a membrane technique
(Figure 4.16). Animal blood cell fraction can be spray dried or can be fractionated in
order to valorize its protein fractions. One significant problem with the cell fraction
is the dark color due to hemoglobin, which affects its acceptability in most foods.
For the preparation of hemoglobin isolates, decolorization is then one of the most
important steps of the process. Several procedures were proposed to reduce the color
of the protein extract: oxidation using hydrogen peroxide; separation of the heme
group from the hemoglobin, which leads to a reduction of the stability of the protein;
and finally digestion of the hemoglobin with proteolysis enzymes and the use of
membranes to recover the breakdown products. In the latter method (Figure 4.16),
the cells are lysed with water (hemolysis), the solution is centrifuged to further sepa-
rate hemoglobin from the cell membranes, and then the hemoglobin is hydrolyzed
using enzymes (pepsin) in a membrane bioreactor (membrane of 20 kg/mol cut off).
Finally the iron pigment is removed from the hemoglobin by UF. The hydrolyzed
proteins may be further concentrated by RO prior to spray drying.
Plasma and blood cells have been subjected to UF processes. Both spiral wound
and plate and frame systems equipped with membrane of 10–20 kg/mol cut-off are
used to concentrate plasma from 7 up to 26% of proteins. With the plate and frame
system, it is possible to reach 30% total solids in the concentrate while the spiral
wound system can only provide up to 20% total solids. The permeation flux is low,
from 10 to 15 L/h/m2 when filtration is carried out at transmembrane pressures rang-
ing from 1 to 2 × 105 Pa. The processing temperature usually ranges from 15 up to
43°C. At a temperature higher than 43°C plasma proteins coagulate. The perme-
ate, containing 1.5%–2.0% total solids, may be further processed by means of RO.
Gel concentrations were approximately 45% for plasma protein and 35% for RBC
(Cheryan, 1986). In general, the flux of RBC is higher than that of the plasma/serum
phase because of the colloidal nature of the former fraction. Regardless of the fluid
treated (plasma, RBC, and whole blood) the process is concentration polarization
controlled and thus high crossflow and low transmembrane pressure regimes are
required.
Membrane processes can also be used for the treatment of wastewater from meat
processing plants. Slaughtering wastewater normally comes from regular floor wash-
ing that will carry with it blood, bits of carcasses, and that includes animal waste
as well.
The load of wastewaters largely depends on the number of animals handled each
day but more important is how these activities are being controlled and carried out.
This is especially true for those slaughter process whereby large animals such as
goats, cattle, and pigs generate huge amounts of blood which can create strong a
wastewater stream if those are not properly collected and recovered.
In several European countries animal by-products processing has led to the estab-
lishment of a strong consortium of rendering plants imposing high fees for meat
processing. In many countries outside the EU, the management of such effluents
is not regulated and blood is disposed of directly into the environment. But due to
the tightened rules by governmental bodies, the direct discharge of the effluent to
the sewer and to the municipal treatment plant has been made more and more diffi-
cult. Furthermore, the substantial volume of blood produced leads to significant road
transport which also negatively impacts on the environment.
On-site treatment has been developed and in that context, membrane filtration
wastewater treatment systems have been developed. The intrinsic characteristics of
the membrane bioreactor, MBR, technology such as the ability to treat high strength,
greatly fluctuating wastewater, resilience in the face of shock loads and toxic chemi-
cals, and production of superior quality effluent justify consideration of the process
in food processing facilities (Cicek, 2003). Analyzing and studying the characteris-
tics of the wastewater suggest that most of the compounds are highly biodegradable
(indicated by the ratio of BOD:COD about 2:1) with a relatively moderate amount
of suspended solid materials present (about 1000 ppm). A high percentage of BOD
in the water is actually contributed by the blood washed away. Just like many other
food industry effluents, slaughterhouse waste effluents are then mainly composed
of proteins and fat. They are highly biodegradable: the BOD at 5 days of blood is
167 g/L. Due to their high fat and protein content slaughterhouse wastewaters are
very suitable for anaerobic treatment. It makes more sense energetically to degrade
the high BOD anaerobically and to yield some biogas and energy rather than to
oxidize it with high power input in an activated sludge system (Saddoud and Sayadi,
2007). According to the literature the combination anaerobic treatment and aerobic
polishing seems therefore most suitable. Biogas yields also tend to be very high. A
very typical treatment regime would be screening, balancing, anaerobic treatment
(thermophilic), and aerobic polishing to reduce BOD and COD for discharge compli-
ance. Pilot-scale testing and optimization of the process would obviously be required
on a case by case basis. The treated water resulting from the plant can be reused by
slaughterhouses which thereby directly reduces water consumption.
4.3.2.2 Gelatin
MF and UF are industrially used to prepare concentrates of gelatin, mainly manufac-
tured from the by-products of the meat and leather industries (cattle hides, pig skins,
and bones). Porcine and bovine gelatins are the most widely used today; but recently,
due to the health-related issues that bovine gelatin has a potential risk of spreading
bovine spongiform encephalopathy and because of religious constraints, alternative
sources have been proposed. Fish by-products for instance have been considered
because they eliminate some of the religious obstacles surrounding gelatin consump-
tion (Herpandi and Adzitey, 2011).
Gelatin is in high demand from an enormous range of industries: it is widely used
in the food industry, in the pharmaceutical industry, in the production of photographic
films (Rainville, 1997), and less frequently in cosmetics manufacturing. In the food
sector gelatin is probably best known as a gelling agent in cooking: common exam-
ples of foods that contain gelatin are gelatin desserts, trifles, marshmallows, gummy
bears, etc. Gelatin may be used as a stabilizer, thickener, or texturer in food as jams,
yoghurt, and margarine; it is also used in fat-reduced foods to simulate the mouthfeel
of fat and to create volume without adding calories. In the pharmaceutical industry
gelatin is generally used in capsules, tablets suppositories, and vitamin encapsulation.
Gelatin is a proteinaceous material derived by partial hydrolysis of collagen
extracted from animal skin and bones. It contains polypeptides in the molecular
weight range from 15,000 to above 400,000 kg/mol. Between 5 and 8 kg of raw mate-
rial is usually needed for extracting 1 kg of gelatin. All gelatin production processes
have several operations in common, and the manufacturing processes consist of four
main stages (Figure 4.17): (i) pretreatment; (ii) extraction step; (iii) clarification (with
MF)/purification treatments; (iv) concentration (with UF) and drying steps.
• The pretreatment of the raw material consists in the removal of some of

the impurities such as fat and salts which may have negative effects of final
properties of the product and in the reduction of the cross-linkages between
collagen components. In order to extract the collagen, the raw materials
are pretreated at high temperature either with acid (Type A, Figure 4.17) or
with alkali (Type B, Figure 4.17) (Ward and Courts, 1977). These processes
may take up to 10–48 h for Type A and up to several weeks for Type B, and
result in great differences on the properties of the final gelatin products,
Raw materials
Type A gelatin Type B gelatin
Cattle hides Bones Pig skins Bones
Degreasing
Pretreatment
Demineralization
Acidification Liming
Extraction
Hot water or dilute acid

extraction
Purification
Clarification (MF)
Ion exchange
Concentration (UF)
Concentration/
drying
Sterilization/cooling
Drying
Gelatin
FIGURE 4.17 Simplified representation of the gelatin process.
mainly due to differences in their isoelectric points. Enzymatic treatments

used for preparing raw material for the main extraction are still relatively
new even if the advantages are numerous: shorter duration, increase yield of
recovery, higher purity, better physical properties of the final gelatin prod-
uct, in contrast to alkali treatments. The extract typically contains 2%–5%
protein in the form of polypeptides and approximately 0.6% ash.
• After preparation of the raw material, collagen is converted into gelatin by
extraction with either hot water or dilute acid solutions. Alkali treatments
are known to degrade proteins. This extraction step is a multi-stage process,
and the extraction temperature is usually increased in later extraction steps
to minimize the thermal degradation of the extracted gelatin.
• After extraction, gelatin extract is clarified. The clarification step is tra-
ditionally done by means of Kieselguhr earth filters and cellulose sheet
filters of 20 µm but MF is an alternative that is more and more used in
order to remove the very high molecular weight molecules of the extract
(dirt, coagulated proteins, residual fats, and other particulate materials) and
then improve the purity and the functional properties of the final gelatin on
a continuous basis. Production of low ash gelatin, for example, for photo-
graphic purposes, may furthermore require ion exchange.
• After clarification, the gelatin solution has traditionally been concentrated
by means of vacuum evaporators to 25%–40% dry matter. However, evapo-
ration leads to some product degradation and loss of functional properties.
UF is then more and more used to concentrate the solution at lower tem-
perature (40–55°C). Spiral wound-type membrane is classically used for
this operation, and depending somewhat on the product quality, it is pos-
sible to concentrate the product to 20% of proteins prior to the flash steril-
ization at 140°C. Jönsson and Trägardh (1990) reported an industrial plant
equipped with 7 stages of spiral wound membranes concentrating 23.6 m3/h
of gelatin from 2.5% to 20% of dry matter. With an UF membrane of 5 kg/
mol membrane cut-off the permeation flux could reach 50–80 L/h/m2 at
ΔP = 3·105 Pa and 50°C with solutions of 2%–3% of proteins. The perme-
ation flux decreased to 3–4 L/h/m2 when concentration increased up to
18%. The sterilized solution if then rapidly cooled, extruded in gel forms
under septic conditions and dried (spray or roller dryer) to form granules,
powder, or thin sheets. The final products classically contain 85%–90% of
proteins and less than 0.3% of minerals.
REFERENCES
Afonso, M. D. and R. Borquez. 2002. Review of the treatment of seafood processing wastewa-
ters and recovery of proteins therein by membrane separation processes—Prospects of
the ultrafiltration of wastewaters from the fish meal industry. Desalination 142:29–45.
Afonso, M. D., J. Ferrer, and R. Borquez. 2004. An economic assessment of proteins recovery
from fish meal effluents by ultrafiltration. Trends Food Sci. Technol. 15:506–512.
Almas, K. A. 1985. Applications of crossflow membrane technology in the fishing industry.
Desalination 53:167–180.
Alvarez, N., G. Gésan-Guiziou, and G. Daufin. 2007. The role of surface tension of reused
NaOH on the cleaning efficiency in dairy plants. Int Dairy J. 17:404–411.
Bergquist, D. H. 1995. Egg dehydration. In Egg Science and Technology, eds. W. J. Stadelman
and O. J. Cotterill, 335–369. Binghamton, NY: Haworth Press, fourth edition.
Bérot, S., F. Nau, J. L. Thapon, F. Quémeneur, P. Jaouen, and L. Vandanjon. 1998. Protéines
végétales et animales. In Les séparations par membrane dans les procédés de
l’industrie alimentaire, (Animal and vegetal proteins. In Membrane Operations in
Food Processing.) eds. G. Daufin, F. René, and P. Aimar, 374–417. Paris: Lavoisier
Tec&Doc.
Berton, A., B. Rouvellac, B. Robert, F. Rousseau, C. Lopez, and I. Crenon. 2012. Effect
of the size and interface composition of milk fat globules on their in vitro digestion
by the human pancreatic lipase: Native versus homogenized milk fat globules. Food
Hydrocolloids 29(1):123–134.
Bonduelle, M. 1978. Une nouvelle technique dans la conservation des ovoproduits (A new
technology for eggproducts stabilization.). Ind. Agric. Alim. 95:1043–1048.
Bonnaillie, L. and P. M. Tomasula. 2008. Whey protein fractionation. In Whey Processing,
Functionality and Health Benefits, eds. C. I. Onwulata and P. J. Huth, 15–39. Singapore:
Wiley Blackwell.
Bramaud, C., P. Aimar, and G. Daufin. 1997. Whey protein fractionation: Isoelectric precipi-
tation of α-lactalbumin under gentle heat treatment. Biotechnol. Bioeng. 56(4):391–397.
Brulé, G., L. Roger, J. Fauquant, and M. Piot. 1981. Phosphopeptides from casein-based mate-
rial. US Patent 4358465.
Chay Pak Ting, B. P., Y. Pouliot, S. F. Gauthier, and Y. Mine. 2010. Fractionation of egg
proteins and peptides for nutraceutical applications. In Separation, Extraction and
Concentration Processes in the Food, Beverage and Nutraceutical Industries, ed. S. S.
H. Rizvi, 595–618. Oxford: Woodhead Publishing Limited.
Cheryan, M. 1986. Ultrafiltration Handbook. Lancaster: Technomic Publishing Company Co, Inc.
Cicek, N. 2003. A review of membrane bioreactors and their potential application in the treat-
ment of agricultural wastewater. Can. Biosyst. Eng. 45:6.37–6.49.
Dalgleish, D. G. 2011. On the structural models of bovine casein micelles—review and pos-
sible improvements. Soft Matter 7(6):2265–2272.
Daufin, G., J. P. Escudier, H. Carrere, S. Bérot, L. Fillaudeau, and M. Decloux. 2001. Recent
and emerging applications of membrane processes in the food and dairy industry. Trans
IChemE 79(Part C):89–102.
Del Hoyo, P., F. Moure, M. Rendueles, and M. Diaz. 2007. Demineralization of animal blood
plasma by ion exchange and ultrafiltration. Meat Sci. 76:402–410.
Del Hoyo, P., M. Rendueles, and M. Diaz. 2008. Effect of processing on functional properties
of animal blood plasma. Meat Sci. 78:522–528.
Dumay, J., S. Radier, G., Barnathan, J. P. Berge, and P. Jaouen 2008. Recovery of valuable
soluble compounds from washing waters generated during small fatty pelagic surimi
processing by membrane processes. Env. Technol. 29(4):451–461.
Ericksson, G. 1974. Applied research for reverse osmosis and ultrafiltration. Process Biochem.
9:18–19.
FAO. 2004. Discards in the world’s marine fisheries: An update. FAO Report.
FAO. 2006. The state of the world fisheries and aquaculture. Annual FAO Report.
Fauquant, J., B. Robert, and C. Lopez. 2009. Procédé pour réduire la teneur bactérienne
d’un milieu alimentaire et/ou biologique d’intérêt, contenant des gouttelettes lipidiques.
(Process to remove microorganisms from food and biological fluids containing fat
droplets.) French Patent FR 2953686-A1.
Fernando, T. 1981. Concentration of animal blood by ultrafiltration. Biotechnol. Bioeng.
23:19–27.
Froning, G. W. 2008. Egg products industry and future perspectives. In Egg Bioscience and
Biotechnology, ed. Y. Mine, Hoboken, New Jersey, US: Wiley Interscience.
Fuchs, W., H. Binder, G. Mavrias, and R. Braun. 2003. Anaerobic treatment of wastewater
with high organic content using a stirred tank reactor coupled with a membrane filtra-
tion unit. Water Res. 37:902–908.
Gernigon, G., P. Schuck, and R. Jeantet. 2011. Demineralization. In: Encyclopedia of Dairy
Science, eds. J. W. Fuquay, P. F. Fox, and P. L. H. McSweeney, vol. 4, 738–743. London:
Elsevier, second edition.
Gésan-Guiziou, G. 2010a. Removal of bacteria, spores and somatic cells by centrifugation
and microfiltration techniques. In Improving the Safety and Quality of Milk—Volume
1: Milk Production and Processing, ed. M. W. Griffiths, 349–372. Oxford: Woodhead
Publishing Ltd.
Gésan-Guiziou, G. 2010b. Separation technologies in dairy and egg processing Part II. Separation
technologies in the processing of particular foods and nutraceuticals. In Separation,
Extraction and Concentration Processes in the Food, Beverage and Nutraceutical
Industries, ed. S. S. H. Rizvi, 341–380. Oxford: Woodhead Publishing Limited.
Gésan-Guiziou G. 2014. Integrated membrane operations in whey processing. In Integrated
Membrane Operations in the Food Production, eds. A. Cassano and E. Drioli, Chap.
6, 133–146. Berlin: De Gruyter.
Gésan-Guiziou, G., N. Alvarez, D. Jacob, and G. Daufin. 2007. Cleaning-in-place coupled

with membrane regeneration for re-using caustic soda solutions. Sep. Purif. Technol.
54:329–339.
Gésan-Guiziou, G., E. Boyaval, and G. Daufin. 1999. Critical stability conditions in crossflow
microfiltration of skimmed milk: Transition to irreversible deposition. J. Membrane
Sci. 158:211–222.
Goudédranche, H., J. Fauquant, and J. L. Maubois. 2000. Fractionation of globular milk fat
by membrane microfiltration. Lait 80:93–98.
Guérard, F. 2007. Enzymatic extraction methods for by-product recovery. In Maximizing
the Value of Marine By-Products. Part 2 By Products Recovery and Processing, ed.
F. Shahidi, 107–143. Cambridge: Woodhead, CRC Press.
Guérin-Dubiard, C., M. Pasco, D. Molle, C. Desert, T. Croguennec, and F. Nau. 2006.
Proteomic analysis of hen egg white. J Agric. Food Chem. 54(11):3901–3910.
Herpandi, N. H. and F. Adzitey. 2011. Fish bone and scale as a potential source of Halal gela-
tin. J. Fish. Aquatic Sci. 6(4):379–389.
Horton, B. S. 1997. Water, chemical and brine recycle or reuse—Applying membrane pro-
cesses. Aust. J. Dairy Technol. 52(1):68–70.
Huang, L. and M. T. Morrisey. 1998. Fouling of membranes during microfiltration of surimi
wash water: Roles of pore blocking and surface cake formation. J. Membrane Sci.
144:113–123.
Invensys—APV System. 2000. Membrane Filtration and Related Molecular Separation
Technologies, Silkeborg: APV Systems.
Jaffrin, M. Y., V. S. Espina, and M. Frappart. 2010. Milk and dairy effluents processing
of crossflow dynamic filtrations. In Membrane Technology—Vol 3: Membranes for
Food Applications, eds. K. V. Peinemann, S. Pereira Nunes, and L. Giorno, 45–74.
Weinheim: Wiley-VCH.
Jaouen, P. 1989. Etude des techniques de séparation par membrane dans le domaine des
pêches et des cultures marines. (Membrane filtration in fishing and seafood processing
sector.) PhD dissertation, Univ. Nantes, France.
Jaouen, P., M. Bothorel, and F. Quémeneur. 1989. Recovery of soluble proteins by membrane sep-
aration processes: Performance and membrane cleaning, Sixth International Symposium
on Synthetic Membranes in Science and Technology, Tubingen, Germany, 4–8 Sept.
Jaouen, P. and F. Quémeneur. 1986. Membrane filtration for waste-water protein recovery.
In Food Engineering and Process Applications, vol. 2, Unit Operations, eds. M. Le
Maguer and P. Jelen, 213–248. London: Elsevier.
Jaouen, P. and F. Quémeneur. 1992. Membrane filtration for waste-water protein recovery.
In Fish Processing Technology, ed. G. M., 212–248. London: Blackie Academic and
Professional.
Jeantet, R., P. Schuck, M. H. Famelart, and J. L. Maubois. 1996. Nanofiltration benefit for
production of spray-dried demineralized whey powder. Lait 76:283–301.
Jelen, P. 2011. Standardization of fat and protein content. In Encyclopedia of Dairy Sciences,
eds. J. W. Fuquay, P. F. Fox, and P. L. H. McSweeney, 4, 545–549. London: Academic
Press Elsevier.
Jeon, Y. J., H. G. Byun, and S. K. Kim. 1999. Improvement of functional properties of cad frame
protein hydrolysates using ultrafiltration membranes. Process Biochem. 25:471–478.
Jimenez-Lopez, A. J. E., N. Leconte, O. Dehainault, C. Geneste, L. Fromont, and G. Gésan-
Guiziou. 2008. Role of milk constituents on critical conditions and deposit structure in
skim milk microfiltration (0.1 µm). Sep. Purif. Technol. 61:33–43.
Jimenez-Lopez, A. J. E., N. Leconte, F. Garnier-Lambrouin, A. Bouchoux, F. Rousseau, and
G. Gésan-Guiziou. 2011. Ionic strength dependence of skimmed milk microfiltration:
Relations between filtration performance, deposit layer characteristics and colloidal
properties of casein micelles. J. Membrane Sci. 369:404–413.
JO. 2007. Official Journal of the French Republic. Décret no. 2007-628 relatif aux fromages
et spécialités fromagères, (Decree no. 2007-628 related to cheeses and cheese speciali-
ties.) JO 29 April 2007, Text no. 14.
Jönsson, A. S. and H. Trägardh. 1990. Ultrafiltration applications. Desalination
77(1–3):135–179.
Khatprathuma, A., P. Siriwongpaisaan, and W. Youravong. 2010. Concentration of protein
in fish mince wash water discharged from Surimi processing plant by ultrafiltration.
Desalination Water Treat. 21(1–3):1–7.
Kijowski, J., G. Lesnierowski, and A. Fabisk-Kijowska. 1998. Methods of lysozyme separa-
tion, enzyme molecular form and functional quality of the residual egg white. In The
2nd Int Symp Egg Nutrition Newly Emerging Ovotechnologies, Banff, Alberta, 54.
Korhonen, H. 2009. Milk-derived bioactive peptides: From science to applications. J. Funct.
Foods I:177–187.
Korhonen, H. and Pihlanto, A. 2006. Bioactive peptides: Production and functionality. Int
Dairy J, 16, 945–960.
Korhonen, H. and A. Pihlanto. 2007. Technological options for the production of health-
promoting proteins and peptides derived from milk and colostrums. Curr. Pharm. Des
13:829–843.
Korhonen, H., E. L. Syväoja, E. Vasara, T. Kosunen, and P. Marnila. 1998. Pharmaceutical
composition, comprising complement proteins, for the treatment of Helicobacter infec-
tions and a method for the preparation of the composition. PCT Patent Application
WO98/00150.
Kuca, M. and D. Szaniawska. 2009. Application of microfiltration and ceramic membranes for
treatment of salted aqueous effluents from fish processing. Desalination 241:227–235.
Largeteau, D. (EURODIA). 2009. Electrodialysis in food processing. Aarhus Seminar,
Aarhus, Danemark.
Le Magnen, C. and J. J. Maugas. (EURIAL). 1991. Method and device for obtaining beta
casein. Patent PCT/FR 91/00506.
Lepienne, A., J. L. Maubois, M. Thireau, and M. Piot. 1986. Procédé pour l’obtention de lyso-
zyme par microfiltration à partir d’une matière à base de blanc d’œuf. (Microfiltration
for the recovery of lysozym from egg white.) French Patent 25697222.
Lesnierowski, G. and J. Kijowski. 2007. Lysozyme. In Bioactive Egg Compounds, eds. R.
Huopalahti, R. Lopez-Fandino, M. Anton, and R. Schade, 33–42. Berlin: Springer.
Li-Chan, E. C. Y. and H. O. Kim. 2008. Structure and chemical composition of eggs. In Egg
Bioscience and Biotechnology, ed. Y. Mine, 1–95. New Jersey, US: Wiley, Interscience,
Hoboken.
Li-Chan, E. C. Y., W. D. Powrie, and S. Nakai. 1995. The chemistry of eggs and egg prod-
ucts. In Egg Science and Technology, eds. W. J. Stadelman and O. J. Cotteril, 105–175,
Binghamton, NY: Haworth Press, Fourth edition.
Lin, T. M., J. W. Park, and M. T. Morrissey. 1994. Recovered protein and reconditioned water
from surimi processing waste. J. Food Sci. 60:4–9.
Linden, G. and D. Lorient. 1994. Biochimie agro-industrielle: Valorisation alimentaire de
la production agricole. (Industrial biochemistry: Food valorisation of the agricultural
production.) Paris: Masson.
Lindquist, A. 1998. A method for the production of sterile skimmed milk. PCT Patent WO
57549.
Liot, R. 1980. Produit hautement concentré de blanc d’œuf ou d’œuf entier salé et son procédé
de préparation. (Process for the concentration of egg white and salty whole egg.) French
Patent 80 22309.
Lipnizki, F. 2010. Cross-flow membrane applications in the food industry. In Membrane
Technology: Vol 3: Membranes for Food Applications, eds. K. V. Peinemann, S. Pereira
Nunes, and L. Giorno, 1–24. Weinheim: Wiley-VCH.
Lopez, C., V. Briard-Bion, O. Ménard, E. Beaucher, F. Rousseau, J. Fauquant, N. Leconte,

and B. Robert. 2011. Fat globules selected from whole milk according to their size:
Different compositions and structure of the biomembrane, revealing sphingomyelin-
rich domains. Food Chemistry 125:355–368.
Malmberg, R. and S. Holm. 1988. Producing low-bacteria milk by microfiltration. North Eur.
Dairy J. 54:30–32.
Mandal, P. K., V. K. Rao, B. N. Kowale, and U. K. Pal. 1999. Utilization of slaughter house
blood in human food. J. Food Sci. Technol. 36(2):91–105.
Marshall, K. R. 1982. Industrial fractionation of milk proteins: Serum proteins. In
Developments in Dairy Chemistry-1, ed. P. F. Fox, New York: Applied Science
Publishers.
Maubois, J. L. 1981. Perspectives d’utilisation des techniques à membranes dans les indus-
tries agro-alimentaires. Académie d’Agriculture de France, (Future trends in mem-
brane filtrations in the food industry. Agricultural Academy of France.) Procès-verbal
26 nov. 1980, 1451–1461.
Maubois, J. L., Fauquant, J., Famelart, M. H., and Caussin, F. 2001. Milk microfiltrate, a con-
venient starting material for fractionation of whey proteins and derivates, in Proceeding
of the 3rd International Whey Conference, Munich, September 12–14, Behr’s Verlag,
Hamburg.
Maubois, J. L. and G. Ollivier. 1997. Extraction of milk proteins. In Foods Proteins and Their
Applications, eds. S. Damodaran and A. Paraf. 579–595. New York: Marcel Dekker
Inc.
Michalski, M. C., B. Camier, J. Y. Gassi, V. Briard-Bion, N. Leconte, M. H. Famelart, and
C. Lopez. 2007. Functionality of smaller versus control native milk fat globules in
Emmental cheeses manufactured with adapted technologies. Food Res. Int. 40:191–202.
Michalski, M. C., N. Leconte, V. Briard-Bion, J. Fauquant, J. L. Maubois, and H.
Goudédranche. 2006. Microfiltration of raw whole milk to select fractions with dif-
ferent fat globule size distributions: Process optimization and analysis. J. Dairy Sci.
89(10):3778–3790.
Mistry, V. V. and J. L. Maubois. 2004. Application of membrane separation technology to cheese
production. In Cheese Chemistry, Physics and Microbiology. Vol 1 General Aspects, eds.
P. F. Fox, P. L. H. McSweeney, T. M. Cogan, and T. P. Guinee, London: Elsevier.
Miyata, Y. 1984. Concentration of protein from the wash water of red meat fish by ultrafiltra-
tion membrane. Bull. Jap. Soc. Sci. Fish. 50(4):659–663.
Nau, F., C. Guérin-Dubiard, F. Baron, and J. L. Thapon. 2010. Science et technologie de l’œuf
et des ovoproduits Vol 2: De l’œuf aux ovoproduits, (Science and Technology of Eggs
and Eggproducts Vol 2: From Egg to Eggproducts.) Paris: Tec&Doc Lavoisier.
Ninomiya, K., T. Ookawa, T. Tsuchiya, and J. J. Matsunoto. 1985. Recovery of water soluble
proteins in waste water of fish processing plants of ultrafiltration. Bull. Jap. Soc. Sci.
Fish. 51:1133–1138.
Ockerman, H. W. and C. L. Hansen. 2000. Animal by-Product Processing and Utilization,
Florida, USA: CRC Press.
O’Mahony, J. A., K. E. Smith, and J. A. Lucey. 2007. Purification of beta casein from milk.
Patent US 2007/0104847.
Paulson, D. J., R. L. Wilson, and D. D. Spatz. 1984. Cross-flow membrane technology and its
applications. Food Technol. 38(12): 77–111.
Pedersen, P. J. 1992. Microfiltration for the reduction of bacteria in milk and brine. In New
Applications of Membrane Processes, ed. International Dairy Federation, Brussels,
33–50, Special issue 9201.
Peri, C. and C. Feriscini. 1972. Concentration and fractionation of egg white by ultrafiltration.
Sci. Technol. Alimenti. 2:120–122.
Piot, M., J. Fauquant, M. N. Madec, and J. L. Maubois. 2004. Preparation of “serocolostrum”

by membrane microfiltration. Lait 84:333–342.
Porter, M. C. and A. S. Michaels. 1971. Membrane ultrafiltration. Chem. Tech. April(Part
2):248.
Quiblier, J. P., C. Ferron-Baumy, G. Garric, and J. L. Maubois. 1991. Procédé de traitement
des laits permettant au moins de conserver leur aptitude fromagère. (Milk treatment for
maintaining its cheese ability.) Patent FR 2 681 218 A1.
Rainville, R. F. 1997. Plate and frame filtration in photographic gelatin manufacturing—
Some practical considerations. Imaging Sci. J. 45(3–4):128–135.
Saddoud, A. and S. Sayadi. 2007. Application of acidogenic fixed-bed reactor prior to anaer-
obic membrane bioreactor for sustainable slaughterhouse wastewater treatment. J.
Hazard. Mater. 149:700–706.
Sandblöm, R. M. (Alfa-Laval). 1974. Filtering process. Swedish Patent 7,416,257.
Skrzypek, M. and M. Burger. 2010. Isoflux® ceramic membranes—Practical experiences in
dairy industry. Desalination 250:1095–1100.
Tamine, A. Y., R. K. Robinson. 2007. Yoghurt: Science and Technology. Abington, England:
CRC Press.
te Giffel, M. C., A. J. Van Asselt, and P. de Jong. 2006. Shelf extension. Dairy Ind. Int.
71(3):44–49.
Tregret, L., Y. Berlier, D. Dhaler, and P. Dupuy. 2008. Support for tangential flow filtration
and preparation method for same. Patent WO 2008/132357.
Trouvé, E., J. L. Maubois, M. Piot, M. N. Madec, J. Fauquant, A. Rouault, J. Tabard, and
G. Brinkman. 1991. Rétention de différentes espèces microbiennes lors de l’épuration
du lait par microfiltration en flux tangentiel. (Retention of various microorganisms
using microfiltration.) Lait 71:1–13.
Tsuchiya, T. and J. Takahashi. 1983. Investigating the food applications of soluble proteins.
J. Fish. Sausage Gyoniku Soseji 215:3–19.
Vandanjon, L., R. Johannsson, M. Derouiniot, P. Bourseau, and P. Jaouen. 2007. Concentration
and purification of blue whiting peptide hydrolysates by membrane processes. J. Food
Eng. 83(4):581–589.
Van der Padt, A., G. Klarenbeek, A. P. J. Sweere, A. D. Siemensma, and J. A. Nieuwenhuijse.
2012. Method of making a milk protein composition. Patent WO 2012/148269.
Vourch, M., B. Balannec, B. Chaufer, and G. Dorange. 2008. Treatment of dairy industry
wastewater by reverse osmosis for water reuse. Desalination 219:190–202.
Wang, T., T. Q. Zeng, and Y. Ye. 2002. Application of ultrafiltration in separation of scallop
skirt enzymatic hydrolysates. J. Fish. Sci. China 9(3):255–259.
Ward, A. G. and A. Courts. 1977. The Science and Technology of Gelatin. New York:
Academic Press.
Watanabe, A., T. Ohtani, H. Horikita, H. Ohya, and S. Kimura. 1986. Recovery of soluble
protein from fish jelly processing with self-rejection dynamic membrane. Food Eng.
Proc. Appl. 2:225–236.
Watanabe, H., R. Takai, A. Sekigawa, and H. Hasegawa. 1982. An estimation of the amount
of protein lost in the effluent from frozen surimi manufacture. Bull. Jap. Soc. Sci. Fish.
48:869–871.
Welsh, F. W. and R. R. Zall. 1984. An ultrafiltration activated carbon treatment system for
renovating fishery refrigeration brines. Can. Int. Food Sci. Technol. 17(2):92–96.
Yordanov, D. 2010. Preliminary study of the efficiency of ultrafiltration treatment of poultry
slaughterhouse wastewater. Bulg. J. Agric. Sci. 16(6):700–704.
Zulewska, J., M. Newbold, and D. M. Barbano. 2009. Efficiency of serum protein removal
from skim milk with ceramic and polymeric membranes at 50°C. J. Dairy Sci.
92:1361–1377.
5 Wine Production
Using Membranes
Erika Bekassy-Molnar
CONTENTS
5.1 Introduction: Wine History............................................................................ 150
5.2 Chemical Components of Wine..................................................................... 150
5.3 Medical Effects of Wine................................................................................ 157
5.4 Main Steps of Traditional Wine Making....................................................... 159
5.5 Membranes in Wine Making......................................................................... 162
5.5.1 Wine Clarification, Sterilization, and Stabilization: Fouling............ 164
5.5.2 Low-Alcohol Wine Production.......................................................... 169
5.5.2.1 Traditional Methods and a Modern Method for Ethanol
Reduction of Wines............................................................. 170
5.5.2.2 Membrane Methods for Ethanol Reduction in Wines........ 170
5.5.2.3 Dealcoholization by Reverse Osmosis and Nanofiltration......171
5.5.2.4 Dealcoholization by Pervaporation..................................... 174
5.5.2.5 Dealcoholization by Osmotic Distillation.......................... 176
5.5.2.6 Dealcoholization by Liquid Emulsion Membrane.............. 179
5.5.2.7 Dealcoholization by Combined Method: Reverse
Osmosis + Osmotic Distillation.......................................... 180
5.5.2.8 Pervaporation for Aroma Recovery.................................... 180
5.5.3 Concentration of Wine, Increase of Valuable Components’ Content.....181
5.5.3.1 Concentration with Nanofiltration...................................... 181
5.5.3.2 Increase of Wine Ingredients Content by RO and Other
Methods.............................................................................. 184
5.5.4 Special Wine Products, By-Products: Wastewater in Wineries........ 186
5.5.4.1 Special Wine Products........................................................ 186
5.5.4.2 By-Products in Wineries..................................................... 188
5.5.4.3 Wastewater in Wineries...................................................... 189
References............................................................................................................... 189
Wine is a fermented alcoholic drink produced from grape juice. The juice itself is a
tasty drink, full of wholesome nutritional components. During the fermentation of
grape juice, these nutritional components are preserved, and new valuable compo-
nents are formed.
Wine production requires different operational methods and machinery; among
them, membrane separations have gained significance in the last 20 years. This
chapter summarizes the recent applications of membranes in wine preparation.
149
5.1 INTRODUCTION: WINE HISTORY

Grape is principally utilized for wine making. There are other fruit wines, prepared
from fruits other than grape. These drinks are mostly homemade and their production
volume is negligible compared to grape wine. Therefore, the word “wine”—without
any attribute—means grape wine in the literature and in everyday talk (Figure 5.1).
Grape cultivation and wine making has been a traditional activity for thousands
of years. Wine production originated in Western Asia and the Black Sea region,
and then spread through Eastern Europe to all parts the world. Wine is loved by
both ancient and modern nations; wine consumption is an important part of fes-
tive meetings and religious ceremonies. The ancient Greeks formulated that wine is
nourishment, medicine, and poison at the same time, depending on the volume of
consumption. Its moderate consumption is beneficial to health, but its consumption
beyond measure is poisonous because of its ethanol content.
The worldwide production of wine is about 270 million hL/year. Of this, 50% is
red wine, 25% is white wine, and the remaining 25% is shared between rosé wine,
sparkling wine, and cognac. The most important wine producer is Europe (about
75%), followed by America (18%), and the rest 7% is produced in Africa, Asia, and
Oceania. In Europe, the main wine-producing countries are Italy and France, and
wine consumption is the highest in these two countries. In the past few years, new
successful countries have appeared in the wine market—Argentina, Chile, Australia,
and South Africa.
5.2 CHEMICAL COMPONENTS OF WINE

Wine is composed of 10%–15% alcohol, besides water, sugars, organic acids, proteins,
antioxidant agents, and vitamins. Tables 5.1 and 5.2 show the average concentration
FIGURE 5.1 Grape and wine.

Wine Production Using Membranes 151
TABLE 5.1
Main Chemical Substances in Wine
Alcohols Methyl alcohol 20–350 mg/L
Ethyl alcohol 7%–17% v/v
High-ranking alcohols 150–500 mg/L
Glycerol 6–10 g/L
Sorbitol <100 mg/L
2,3-Butylene-glycol 0.42–1.46 g/L
Meso-inositol 300 mg/L
Sugars Glucose 0.1–0.5 g/L
Fructose 1–2 g/L
Pentoses 0.3–2 g/L
Organic acids l-Tartaric acid 1–5 g/L
l-Malic acid 0–8 g/L
Citric acid <1 g/L
Amber acid 0.5–1.5 g/L
Lactic acid 1–5 g/L
Acetic acid 0.8–1 g/L
Nitrogen-containing substances Amino acids 15–540 mg/L
Biogenic amines 1.65–13.06 mg/L
Proteins 44–750 mg/L
Pectins, polysaccharides Pectin 0.1–0.2 g/L
Gums 0.1–3 g/L
Phenolic substances Anthocyanins 150–450 mg/L
Source: Adapted from Eperjesi, I., M. Kallay, I. Magyar: Boraszat (Oenology),

Mezogazda Kiado, Budapest, 1998 (in Hungarian).
TABLE 5.2
Vitamins, Anions, and Cations in Wines
Vitamins (Average in Red Wines) Anions Cations
B1 (thiamine) <10 μg/L Cl− 20–200 mg/L K+ 100–1800 mg/L
B2 (riboflavin) 177 μg/L SO42− 50–100 mg/L Na+ 10–200 mg/L
B6 (pyridoxine) 0.35 mg/L PO43− 200–540 mg/L Ca2+ 50–160 mg/L
B12 (cobalamin) 0.06 μg/L SiO32− 0–52 mg/L Mg2+ 60–140 mg/L
H (biotin) 2.1 μg/L Br− 0.1–0.8 mg/L Fe 5–15 mg/L
PP (nicotinamide) 1.36 mg/L F− ∼1 mg/L Cu 0.1–2 mg/L
Pantothenic acid 0.98 mg/L I− Some mg/L Al3+ <50 mg/L
Folic acid 2 μg/L BO34− 10–80 mg/L Mn2+ 1–2 mg/L
Meso-inositol 0.33 g/L NO3− Traces Pb2+ 0.1–0.4 mg/L
Choline 35 mg/L Zn2+ 0.1–5 mg/L
As3+ ∼0.01 mg/L
Source: Adapted from Eperjesi, I., M. Kallay, I. Magyar: Boraszat (Oenology), Mezogazda Kiado,
Budapest, 1998 (in Hungarian).
of the main components, vitamins, and minerals in the wines (Eperjesi et al., 1998;
Kallay, 2012).
Phenolic compounds are among the most important quality parameters of wine
since they contribute to organoleptic characteristics such as color, astringency, and
bitterness. Besides, phenolic compounds possess antioxidant activity, which have a
beneficial effect on humans. Antioxidants are important substances that possess the
ability to protect the body from damages caused by free radical-induced oxidative
stress.
Phenolic compounds of wine can be divided into two main classes:
• Nonflavonoids
• Stilbenes (e.g., resveratrol)
• Hydroxybenzoates
• Hydroxycinnamates
• Flavonoids
• Flavonols (e.g., quercetin, myricetin)
• Flavan-3-ols (e.g., (+)-catechin, (−)-epicatechin)
• Procianidins and their polymers
• Anthocyanins (pigments)
Many recent articles deal with the measurement and comparison of various valu-
able components, mostly phenolic compounds, of wines from different regions and
different varieties.
Paixao et al. (2007) analyzed commercial Portuguese wines and established that
red wines have a higher total phenolic content than rosé and white wines (Table 5.3).
The total phenolic content and the antioxidant capacity were highly correlated with
antiradical activity.
Ribeiro de Lima et al. (1999) measured the stilbene concentration in Portuguese
wines. The average stilbene concentration was 11.2 mg/L in white wines and
30.5 mg/L in red wines. The average trans- and cis-resveratrol level in white wines
TABLE 5.3
Average Total Phenolic Content (TPC) and Average
Total Antioxidant Capacity (TAC) of Portuguese Wines
Total Phenolic Total Antioxidant Capacity,
Wine Content, TPC (mg/L)a TAC (mg/L)a
Red 1800 900
Rosé 660 500
White 380 440
Source: Adapted from Paixao, N. et al.: Food Chemistry, Vol. 105, 204–
214, 2007.
a Values expressed as mg gallic acid equivalent (GAE).
was 0.2–2 mg/L for both compounds, while it was 2–20 mg/L in red wines for both
compounds. Taking into account the average consumption of red + white wines,
which is 160 mL/day/individual, the stilbene intake in the Portuguese population
can be estimated to be 3.0 mg/day/individual, which is a good value, higher than it
was supposed before.
Gerogiannaki-Christopoulou et al. (2006) investigated trans-resveratrol in major
Greek varieties: 13 red and 18 white wines were examined. The average value of
trans-resveratrol in Greek red and white wines appeared to be lower than those
reported for wines from other countries. This fact can be explained by a number
of factors that affect the resveratrol content, such as climate, geographical area of
cultivation, growing conditions, wine-making techniques, and storage conditions.
Minussi et al. (2003) dealt with polyphenol compounds and the total antioxidant
potential of commercial wines from Brazil, Portugal, Chile, and Italy and estab-
lished the following:
• The total polyphenol content is 1.9 g/L in red wines (3.7 g/L in Italian

wines) and 0.3 g/L in white wines (0.6 g/L in Italian wines).
• A strong correlation was measured between the antioxidant potential
(expressed in gallic acid) of gallic acid and (−)-epicatechin, (+)-catechin,
and total phenol content.
Abril et al. (2005) measured trans- and cis-resveratrol in 98 Spanish wines. Rosé
wines contain lower resveratrol than red wines, and young wines contain more res-
veratrol than older wines (Table 5.4). A high correlation between trans-resveratrol
and total resveratrol was found.
Similar resveratrol concentrations in red and rosé wines were determined in
wines from California, Australia, Italy, Portugal, France, and Greece. The res-
veratrol content is influenced by geographical location, wine variety, and wine
making.
In the article of Lopez-Vélez et al. (2003), the antioxidant activity of some pheno-
lic compounds of five Spanish red wines was compared. The measured proportions
of the total antioxidant activity expressed in gallic acid equivalent were as follows:
gallic acid:trans-resveratrol:quercetin:rutin = 4.3:4.0:4.7:3.8
TABLE 5.4
Resveratrols in 98 Commercial Spanish Wines
Resveratrol Red Wine Rosé Wine
trans-Resveratrol (mg/L) 0.32–4.44 0.12–2.80
cis-Resveratrol (mg/L) 0.20–5.84 0.02–3.17
Source: Adapted from Abril, M. et al.: Food Chemistry, Vol.

92, 729–736, 2005.
Cliff et al. (2007) examined 173 commercial red wines from 7 vintages and 13
vineyard locations in British Columbia, Canada. They studied the anthocyanin con-
tent and the phenolic composition, and color measurements and sensory analysis
were performed. The average value of anthocyanins was 0.1 g/L (in malvidin-3-glu-
coside) and that of total phenolics was 1.06 g/L (in gallic acid). Younger wines had
higher concentrations of anthocyanins than older wines.
Sicilian red wines were analyzed by Careri et al. (2003). The study focused on the
simultaneous determination of trans-resveratrol and quercetin in grape skin, pom-
ace, and then the red wine prepared from the same grape variety. The concentration
of trans-resveratrol and quercetin in the wine ranged from 0.56 to 2.86 mg/L and
from 0.89 to 8.84 mg/L, respectively. The main new result was that not only was
grape skin a good source of the investigated two ingredients, but also that the wine
pomace, a by-product of wine, also contains a very high level of quercetin and a
remarkable level of trans-resveratrol.
Japanese researchers Mori et al. (2007) determined the mechanism of inhibition
of anthocyanin accumulation in red grape berries. The high ambient temperature
(maximum 35°C) decreased the anthocyanin content to less than half of that in the
control berries (maximum 25°C). Temperature is an important factor that affects
anthocyanin biosynthesis in plants.
Gambuti et al. (2004) measured the concentration of trans-resveratrol, quercetin,
(+)-catechin, and (−)-epicatechin in 13 red and 18 white Italian wines and realized
that there is a positive correlation between maceration time and the above concentra-
tions. During 6 days of maceration, the concentration of the valuable components
increased, but after the 12th week, a decrease in concentration was observed.
The same observation was published by Lachman et al. (2007) on the basis of
maceration of Bohemian red and white wines. Besides, in the red wines, 10 times
higher antioxidant status was detected than in white wines.
Kelebek et al. (2006) followed the concentration of anthocyanins in Turkish
wines during the maceration time. They observed that the total anthocyanin reached
its maximum value within 6 days maceration time, while the phenolic compounds
increased with skin contact time till the 10th day of maceration.
In a subsequent article, Kelebek et al. (2007) stated that enzyme-treated wine,
using commercial pectolytic enzymes, had a higher concentration of phenolic com-
pounds and the taste of the wine was better.
Gurbuz et al. (2007) studied trans-resveratrol, catechin, and epicatechin in grape
juices and wines produced from red and white grapes in various regions of Turkey.
Grape contains a large amount of various phenolic compounds in the skins, pulp, and
seeds. In wines, the investigated phenolics had about 10 times higher concentration
than in the must because significant changes occur during the wine-making process.
Comparing the white and red wines, it was interesting to realize that the average
epicatechin level was higher in white wines than in red wines. The average catechin
level was similar in both types of wines, while the resveratrol level was higher in red
wines, as also reported by other authors.
Chinese researchers Fang et al. (2008) analyzed Chinese wines and arrived at
similar results that flavonoids are greatly affected by grape variety, maturation tech-
nology, and aging in barrels.
The influence of wine vigor on grape anthocyanins and pigmented polymers was
investigated by Cortell et al. (2007), analyzing grapes and wines from Oregon, USA.
They found a strong positive relationship between pigmented polymer concentration,
proanthocyanidin concentration, and color density in the wines prepared from the
investigated grapes. The berry size alone did not explain differences in the antho-
cyanin concentration of the wine. Color density was higher in wines from low-vigor
fruit.
Pour Nikfardjam et al. (2006a) measured polyphenols, anthocyanins, and trans-
resveratrol in 67 Hungarian red wines. They separately measured 14 polyphenols
(among them trans-resveratrol, quercetin, catechin, epicatechin, rutin) and 4 antho-
cyanins (delphinidin-3-glucoside, petunidin-3-glucoside, peonidin-3-glucoside, and
maldivin-3-glucoside). Vintage year had a significant influence on the polyphenolic
composition of the wines from the Villany region, while on the basis of wine vari-
eties and origin, no distinction could be made. Higher values of polyphenols and
anthocyanins were detected in younger wines.
Tables 5.5 and 5.6 show the mean values of the polyphenol, anthocyanin, and
trans-resveratrol content of 67 red wines; the mentioned components have a positive
effect on human health. After the mean value, the standard deviation is mentioned.
Another publication of Pour Nikfardjam et al. (2006b) compared 18 quality white
wines from the Tokaj region of Hungary and 15 quality white wines from Germany.
Among them were wines from botrytized grapes. The resveratrol, total polyphenol,
and antioxidant capacity were compared. The botrytized wines had a considerable
TABLE 5.5
Polyphenol Contents (mg/L) of Various Red Wines from the Hungarian
Villany Region
Wine Trans-Resveratrol Quercetin Catechin Epicatechin Rutin
Cabernet franc 0.8 3.7 62.1 92.0 9.5
Cabernet sauvignon 2.8 5.6 81.8 102.8 13.1
Cuvee 1.9 3.5 73.8 110.0 20.2
Kadarka 0.9 8.7 77.0 81.9 12.1
Kekfrankos 2.8 11.3 71.5 126.0 13.6
Merlot 3.9 11.2 89.1 126.0 16.9
Oporto 1.2 9.8 98.6 75.6 19.4
Pinot noir 3.2 7.5 103.0 64.6 9.7
Portugieser 1.4 5.8 77.2 87.6 14.7
Royal cuvee 1.9 5.8 75.9 98.2 13.6
Rubin cuvee 3.1 12.2 79.8 95.9 13.3
Shiraz 1.1 13.4 68.2 99.7 15.5
Zweigelt 2.7 6.0 73.4 111.0 6.8
Total (mean of N = 67) 2.3 7.4 79.4 103.0 14.2
Std. dev. 2.2 6.7 37.7 60.4 11.0
Source: Adapted from Pour Nikfardjam, M.S. et al.: Food Chemistry, Vol. 98, 453–462, 2006a.
TABLE 5.6
Anthocyanin Contents (mg/L) of Various Red Wines from the Hungarian
Villany Region (Calculated as Malvidin-3-Glucoside)
Delphinidin- Petunidin- Peonidin- Malvidin-
Wine 3-Glucoside 3-Glucoside 3-Glucoside 3-Glucoside
Cabernet franc 63.4 73.0 39.3 656
Cabernet Sauvignon 92.8 74.2 43.5 565
Cuvee 69.3 56.9 32.1 394
Kadarka 48.4 46.2 41.0 415
Kekfrankos 64.4 72.4 82.3 797
Merlot 53.7 49.6 38.2 276
Oporto 63.3 103.0 64.3 1411
Pinot noir 43.0 39.9 48.1 316
Portugieser 56.8 57.5 43.7 560
Royal cuvee 15.2 14.0 11.7 138
Rubin cuvee 45.3 45.6 34.3 352
Shiraz 152 220 128 1810
Zweigelt 71.5 88.0 61.7 754
Total (mean of N = 67) 60.7 62.7 45.0 545
Std. dev. 53.0 60.4 42.0 581
Source: Adapted from Pour Nikfardjam, M.S. et al.: Food Chemistry, Vol. 98, 453–462, 2006a.
amount of resveratrol and derivatives, so the white “Tokaji aszu” wines are excel-
lent sources of polyphenols with antioxidant capacity. As resveratrol is located in
the berry skin, the longer contact of the botrytized grapes in the base wine results
in a better extraction of polyphenols. The resveratrol content of Tokaji wine had an
average of 2.5 mg/L resveratrol and 4.2 mmol/L antioxidant activity. The German
botrytized wines had lower average concentration of the earlier-mentioned valuable
components due to the different production techniques (resveratrol 0.9 mg/L and
antioxidant capacity 1.4 mmol/L).
According to Jimenez et al. (2007), the trans-resveratrol content in wine can be
increased by an anoxic pretreatment of harvested grapes with dry nitrogen at low
temperature.
Danish researchers Stervbo et al. (2007) prepared a comprehensive investigation
with different red wines from Australia, Brazil, Czech Republic, France, Greece,
Hungary, Italy, Japan, Spain, Switzerland, and the United States. Five hundred and
eleven samples were evaluated from 18 regions and the concentrations of two iso-
mers of resveratrol, trans- and cis-resveratrol, were compared. No specific region or
variety was found to be outstanding in relation to the level of resveratrols. However,
given the large variation between regions and varieties, the red wines contain an
average value of 1.9 ± 1.7 mg/L trans-resveratrol, changing from the nondetectable
levels to very high values: 14.3 mg/L in Merlot, Hungary, 8.0 mg/L in Pinot Noir,
Spain, and 10.5 mg/L in Pinot Noir, Czech Republic. The levels of trans-resveratrol
glucosides varied significantly between regions, while cis-resveratrol glucosides

showed a smaller deviation from the mean value.
Many new efforts have been made to increase the phenol and tannin content in
wines. For example, new enzymes are used (Kelebek et al., 2007) and anoxic treat-
ment is applied (Jimenez et al., 2007). With the new wine-making patent of Norrie
(2009), much higher resveratrol content could be reached than the average resvera-
trol content in the red and white wines.
The methods for the chemical analysis of the valuable and other components of
wines can be found in many publications, mostly in the Journal of Food Chemistry.
The analysis is under development today and many efforts are being made to stan-
dardize the best methods.
Taking into account the different analysis methods for the determination of the
different valuable components of fruit juices, beverages, and wines, a panel of 11
institutions prepared a collaborative study with the organization of Lee et al. (2005).
The total monomer anthocyanin content was measured by the pH differential method
with excellent agreement between laboratories. The method was adopted as a first
action official method of AOAC International.
5.3 MEDICAL EFFECTS OF WINE

In the last 10 years, many medical articles appeared on the positive effect of wine—
mostly red wine—on human health.
Norrie (2009) wrote that wine has been used as medicine for the past 5000
years, and nowadays, it is not only the experience that recommends wine con-
sumption, but the biological explanation of the effect of wine has begun to be more
evident.
A study followed 1400 males for the past 40 years. All wine drinkers, in modera-
tion, lived an average of 5 years longer than abstainers.
The healthy components of wine are the various antioxidants, such as polyphe-
nols, quercetin, epicatechin, and resveratrol. Resveratrol is not only an antioxidant
but also stimulates the gene that allows organisms to live longer.
Recently, efforts have been made to increase the resveratrol content by modi-
fied wine making. Using methodologies from new patents, there was an increase in
resveratrol content by 50% instead of the average 1–2 mg/L (white) and 3–6 mg/L
(red wine).
The term “French paradox” was first coined by Serge Renaud (Yoo et al., 2010).
It has been suggested that the resveratrol present in wine reduces the mortality from
coronary diseases, even in some French population with a high fat intake.
With extensive research, it has been found that resveratrol in wine (and grape,
berries, peanuts, etc.) has cardiovascular-protective benefits, anti-inflammatory
effects, antiaging effects, and strong antitumor activities, and prevents tumor inva-
sion and metastasis and moderates the immune system to kill tumor cells (Xuan
Yang et al., 2014).
Minussi et al. (2003) listed wine components from the point of view of human
health and divided the polyphenolic compounds into two main classes:
• Nonflavonoids: stilbenes (e.g., resveratrol), hydroxybenzoates (e.g., gallic

acid), hydroxycinnamates
• Flavonoids: flavonols (e.g., quercetin and rutin), flavan-3-ols, anthocyanins
After investigating red and white wines from Brazil, Portugal, Chile, and Italy,
it was established that flavonoids act as antioxidants and prevent the aging process,
cell destruction, and irreversible malfunctions. They protect against arteriosclerosis,
coronary artery disease, and tumor growth.
According to Balestrieri et al. (2008), resveratrol is the most promising polyphe-
nol. They performed in vitro experiments, which established that the resveratrol con-
tent of red wine has a beneficial effect on ischemic tissues and injured blood vessels.
Hackman et al. (2008) studied flavonols or flavan-3-ols, which can be obtained from
red wine, cocoa, green tea, red grapes, berries, and apples. In vitro and in vivo experi-
ments proved that flavonols are potent antioxidants, scavenging free radicals. They
obtained good results against cardiovascular diseases. Murias et al. (2008) established
that resveratrol in the diet can act as a chemotherapeutic agent to inhibit mammary
carcinogenesis in humans. In vivo experiments of Serafini et al. (1998) established the
positive effect of red wine components on the human body. The strong antioxidant
activity of alcohol-free red wine is proportional to its higher phenolic compound con-
centration. Vingtdeux et al. (2008) found that red wine is rich in antioxidant polyphe-
nols with potential neuroprotective activities. In vivo data clearly demonstrated that
moderate consumption of red wine has a beneficial effect against Alzheimer’s disease.
Regitz et al. (2016) found that resveratrol caused 40% decrease in paralysis. Marel
et al. (2008) and Juan et al. (2008) realized the chemopreventive aspect of trans-
resveratrol against colon carcinoma, without cytotoxicity. Mi Oh et al. (2015) inves-
tigated the antiviral effect of red wine, especially the resveratrol content in red wine.
A protective effect was observed against foodborne norovirus, which can cause acute
gastroenteritis and significant mortality worldwide. Mokni et al. (2007) studied the
hemodynamic parameters (heart rate, developed pressure, maximal positive values)
in isolated heart from control or resveratrol-treated rats. Chronic treatment with res-
veratrol exerted strong cardioprotective effects by inhibiting ischemia–reperfusion
injury. The clinical research by Anstey and Cherbuin (2010) verified that light to
moderate consumption of wine reduces the risk of different diseases and the cog-
nitive decline of elderly people, due to the antioxidants in wine. Resveratrol has a
multitarget effect against diabetes, and it reduces diabetic complications (Bagul and
Banerjee 2015).
Saiko et al. (2008) prepared a review on the basis of 190 research articles about
the medical effect of resveratrol and its analogs on human organ. Resveratrol in
the dried roots of the Japanese ko-jo-kon was traditionally used in Asian medicine
against suppurative dermatitis, gonorrhea, and favus. Resveratrol was first isolated in
1940, and has been found in about 70 plants, including grapes, berries, and peanuts.
Recent in vitro, ex vivo, and in vivo experiments proved many positive effects of
resveratrol on humans (Artero et al., 2015), including the following:
• Prevents tumor development (leukemia, colon, breast, prostate cells)

• Has a defensive effect against incident type 2 diabetes
• Protects the organism against the effect of diverse environmental toxins

• Has a beneficial effect on cardiovascular diseases
• Has a neuroprotective effect (Alzheimer’s, Huntington’s, Parkinson’s dis-
eases), protects the brain from damage caused by metabolic toxins, disease,
or age
Resveratrol targets whole pathways and sets intracellular events rather than an
enzyme. Owing to their pharmacological safety, resveratrol and its analogs may be
used in combination with other chemotherapeutic agents in order to enhance their
efficacy, thus minimizing chemotherapy-induced toxicity.
In their review article, Biagi and Bertelli (2015) state that French paradox is
ascribed to resveratrol in wine, although the resveratrol content in wine is low. An
intake of concentrated resveratrol in the form of pills has a very low effect or some-
times the effect is undetectable. In conclusion, the authors propose to consume a
glass of wine with our meals and enjoy the benefits of the French paradox. The
authors underline that the influence of resveratrol calls for additional experiments.
5.4 MAIN STEPS OF TRADITIONAL WINE MAKING

Properly ripe grape is harvested by hand or by machine. Manual harvesting is more
time consuming but gives better quality. It has the advantage to pick only the ripe
clusters and not to pick those that are not ripe or have any defect.
Destemming is the process of separating stems from the grape berries. The next
step is the crushing, breaking the berries. In bigger wineries, mechanical crusher-
destemmer is used (Figure 5.2). The crushed grape is introduced to the fermenter and
FIGURE 5.2 Machinery for harvest, crusher-destemmer, press, and fermenters.

White grape
Destemming + Pressing + (Filtration) Marc

containing skin
Crushed grape
Fermentation without skin
Crude white wine
Cold sterilization + (Sweetening)
Filtration Membrane
filtration
White wine for

finalization
Barrels for curing + (Bottling)
White wine
FIGURE 5.3 Simplified flow sheet of white wine production.
yeast is added into it, which converts the sugars of the grape to ethanol and carbon
dioxide. The fermentation is a long process—it takes 1–2 weeks. White wine and red
wine need different fermentation processes (Robinson, 2003).
White wine is made by fermenting the juice of white grape. The skins are removed
and play no further role (Figure 5.3).
Red wines are prepared from the must of red or black grapes, which are fermented
together with the grape skin (Figure 5.4). The skin is separated after fermentation,
and then the once-fermented wine is submitted to a second (bacterial) fermentation
to decrease the acidity.
Rosé wines are made from red grapes. The juice is allowed to stay in contact with
the skin of the grape only for a short period of time, until the juice picks up a pinkish
color. The skin is then removed and the fermentation is continued.
At the end of the fermentation, the new wine is pumped to reservoirs.
Chemical additives and/or sedimentation/filtration/membrane filtration can
Red grape
Destemming + Pressing Marc
Crushed grape + skin
Fermentation with skin
Crude red/rosé wine
Filtration
Membrane
filtration
Red/rosé wine for

finalization
Barrels for curing + (Bottling)
Red/rosé wine
FIGURE 5.4 Simplified flow sheet of red/rosé wine production.
eliminate its turbidity. In case of red wine, a cap of grape skins is formed on the
top of the fermented wine. This cup is removed before the sedimentation/filtra-
tion. Traditional filters have been replaced by membrane filtration in the last few
decades. Membrane filtration removes bacteria as well—this is cold sterilization
of wine.
There are many other tasks to be followed by the wine maker to produce high-
quality wine: choose proper machinery, find optimal yeasts, find optimal tempera-
tures of operations, fining the wine, reach optimal proportion in the mixture of cuvee
wines, barrel and bottle the wine, advertise and sell the product, etc. It is not the
main aim of this chapter to review all the details of wine production and special
drinks (ice wine, sparkling wine, botrytized wine, fruit wine, honey wine, brandy,
etc.), utilization of side products, wastewater treatment, etc.
A typical popular light wine contains 12%–13% v/v ethanol. A recent problem of
wine producers is that the alcohol content in wines in many cases is 15%–17% v/v
and does not meet the European standard, which is now 12%–13% v/v.
One of the reasons is climate change. As the average temperature increases or

as the number of sunny days increases, the grape ripens sooner and better, its sugar
content becomes higher, and consequently the alcohol content in the wine increases
(sometimes 15%–17% v/v).
The other reason is the producers’ force of habit. The ripe grape is more tasty
and succulent, but has higher sugar content, and after fermentation, higher alcohol
content.
For medical purposes, there is a need to prepare wine with very low alcohol con-
tent (0.5%–3% v/v ethanol). There are different traditional and modern methods to
decrease the alcohol content, which will be detailed in Section 5.5.2.
This chapter focuses on the possibility of using membrane separations, which are
not yet widespread in traditional wine making, but successfully and economically
applied to follow the new regulations of wine quality and to solve the present prob-
lems of wine production.
5.5 MEMBRANES IN WINE MAKING

In the wine-making industry, membranes were used in the 1970s. The first poten-
tial scope for wine production was grape juice correction, using a reverse osmosis
membrane, by Alfa Laval Nakskov in 1974. This method reduced the water concen-
tration of the must by 5%–20%, increased sugar content, enriched the tannins and
other organoleptic components in the must, and consequently improved wine quality
(Lipnizki et al., 2006).
Nowadays, different membrane methods are applied in enology for different
purposes.
Microfiltration (MF) can be considered the most traditional method for wine
sterilization and clarification. The MF membrane removes bacteria, viruses, small
solid particles, and haze; produces clear, sterile wine; and substitutes the fining
processes.
In the last two decades, new membranes, new membrane methods, and new appli-
cations have become widespread for producing low-alcohol-content wine, concen-
trated wine, and biological wine (without SO2, filter aids, and coagulants), and for the
utilization of by-products and wastes.
Massot et al. (2008) gave a good review of the supposed future application of
membrane and other coupled techniques in wine making.
Wine clarification by MF with 0.2 μm cut-off mineral or organic membrane has
been accepted in wineries long ago. Today, MF for must and wine with 0.1–1.2 μm
cut-off is largely used.
Must concentration by reverse osmosis (RO) is a practical tool after an efficient
clarification using double-spacer modules. The permeate contains—beside water—
alcohol, acetic acid (∼60% of the initial concentration), ethyl acetate (∼40% of the
initial concentration), and lactic acid (∼15% of the initial concentration). The reten-
tion depends on the selected membrane.
New applications of nanofiltration (NF) in enology are foreseen. Coupling NF
with other techniques (such as with RO and ultrafiltration [UF]) is promising in the
following fields:
• They decrease the alcohol content of overalcoholized Mediterranean,

Californian, and South American wines, from ∼17% v/v ethanol to 9%–13%
v/v. This decrease can be brought about by sugar reduction in the must
using UF + NF or RO + membrane contactor (Memstar, Australia).
• The production of quality wine with reduced alcohol content by mem-
branes has been proposed by different companies: Bucher Vaslin, Michael
Paetzold, IMECA, Inter Rhone.
• The problem of malic acid or volatile acidity reduction can be solved by
coupling RO + ion exchange or by NF + selective adsorption.
• When two RO is coupled, the first membrane poorly retains the free acids,
salts, esters, and other small molecules. Therefore, this first permeate can
be neutralized by KOH and the salt will remain in the second RO. The other
components passing through the second membrane are reinjected into the
initial wine.
• By coupling two RO stages the acetic acid content of the wine can be
decreased, as well. After the first RO, the acetic acid content is 40%–50%.
After the neutralization, the rejection of potassium acetate is >90%.
• Tartaric acid stabilization of wines is done by cold treatment, but this is
nowadays replaced by electrodialysis.
• Reduction of bad taste by a combined membrane and adsorption technique
has been proposed.
Table 5.7 summarizes the objectives and the proposed membrane configurations
of the authors.
TABLE 5.7
Proposed Membrane Processes
Objective Processes
Concentration of must Reverse osmosis
Reduction of the sugar content in must Ultrafiltration + nanofiltration
Ultrafiltration + evaporation
Partial alcohol removal Reverse osmosis 1 + reverse osmosis 2
Reverse osmosis + distillation
Reverse osmosis + membrane contactor
Reduction of volatile acidity Reverse osmosis + anionic resins
Reverse osmosis + reverse osmosis
Reverse osmosis + adsorption
Tartaric stabilization Electrodialysis
Nanofiltration + microfiltration
Bad taste reduction Nanofiltration + resins adsorption
Nanofiltration + PVPP
Reduction of malic acid Nanofiltration + nanofiltration
pH control Electrodialysis
Source: Adapted from Massot, A. et al.: Desalination, Vol. 231, 283–289, 2008.
Nowadays, there are some newer solutions for partial alcohol removal by using
membrane methods. These methods are detailed in Section 5.5.2.
Numerous other membrane applications could be proposed, for instance, bringing
some corrections to must or wine, reduction of malic acid content, pH control, etc.
5.5.1 Wine Clarification, Sterilization, and Stabilization: Fouling

In wine production, a traditional application of membrane filtration is the use of
MF membranes after fermentation for the removal of bacteria, viruses, small solid
particles, and haze, and for the production of clear, sterile wine. MF can simplify
the traditional fining process; combine clarification, stabilization, and sterilization in
one operation; and consequently eliminate the use of fining substances. Stabilization
means the removal of potassium bitartrate, which produces sediment in the wine.
A schematic diagram of the MF equipment is shown in Figure 5.5. MF membranes
with a pore size of 0.2–0.45 μm for white wines and 0.2 μm for red wines have been
proposed (Lipnizki et al., 2006). Many studies have proved that MF does not signifi-
cantly modify the sensory quality of wines. A major limiting factor is the flux decline
in the function of time because of membrane fouling. Fouling can be reduced by the
application of optimal transmembrane pressure and cross-flow velocity. Fouling of
MF membranes is considered as the principal drawback in the beverage industry.
Cross-flow MF can be used satisfactorily in other clarification and stabilization
steps; on the one hand is the clarification of must, removal of wine lees, and partially
fermented lees, and on the other is the microbiological and chemical stabilization of
wine.
In enology, the other membrane type for sterilization and stabilization can be
the UF membrane, but MF is more recommended than UF because the latter can
reduce some colloidal and phenolic fractions of wine, and therefore decrease its sen-
sorial characteristics; besides, the UF gives a lower filtration yield. In earlier years,
2
7
9
PI
8
1
6
5
TI PI
3 4
FIGURE 5.5 Schematic diagram of microfiltration equipment. (1) Feed tank, (2) cooling
system, (3) pump, (4) bypass valve, (5) valve to set pressure, (6) MF membrane, (7) permeate
(filtered wine), (8) valve to set recycle flow rate, and (9) rotameter.
diatomaceous earth was applied as a filter aid. In the study of Palacios et al. (2002),
the behavior of MF was compared with that of traditional sand filter, plate-and-frame
filter, and cartridge filter. Diatomaceous earth was applied as a filter aid. The filtered
wines were cherry wines with 15.4% and 17.5% v/v ethanol and brandy with 40.3%
v/v ethanol. As a final result, it was established that MF confers higher physico-
chemical stability in wine than conventional filtrations.
Vernhet et al. (2003) investigated the cases of fouling of MF membranes. Red
wines were applied. Crude red wine is a multicomponent system including dissolved
constituents, colloids, and large particles. There are solutes (salts, organic acids,
polyphenols), macromolecules, colloidal particles, microorganisms (yeast, lactic
bacteria), and large solid particles (tartrate crystals) in it.
Wine components have an impact on the fouling of an MF membrane. Fouling
depends on the wine processed and also on the membrane and the process conditions.
The consequences of fouled membranes are a reduction in permeation rates, affecting
the economic viability of the process, and a risk to the product’s organoleptic quality.
The results of the analysis of the investigated wine are presented in Table 5.8.
In this study, an MF membrane was applied for separation. The MF membrane
was hydrophilic, with an average pore size of 0.1 μm, while the maximal pore size
was 0.2 μm.
The particles of the wine components were separated into two parts: the large
particles (colloidal-size aggregates, residual particles, lactic bacteria) had >2 μm
hydraulic diameter, and could be removed from the crude red wine by centrifuga-
tion. The smaller particles, the fines, had <2 μm hydraulic diameter and gave the
composition of the red wine after centrifugation.
TABLE 5.8
Main Components of Crude and Centrifuged Wines
Crude Wine Centrifuged Wine
Ethanol (% v/v) 12.8 12.8
pH 3.7 3.7
Neutral sugars (mg/L)
Rhamnose 36 ± 5 34 ± 4
Arabinose 159 ± 14 152 ± 4
Xylose 7 ± 1 7 ± 1
Mannose 95 ± 1 92 ± 10
Galactose 117 ± 2 111 ± 4
Total 414 ± 23 396 ± 23
Total polyphenol 47 47
indexa
Total tannins (mg/L) 780 837
Source: Adapted from Vernhet, A., D. Cartalade, M. Moutounet: Journal

of Membrane Science, Vol. 211, 357–370, 2003.
a Absorbancy at 280 nm and under 1 cm optical path.
On the basis of experimental results, the authors proposed the following mecha-
nism to account for membrane fouling during the MF of crude red wine:
• Fine particles (<2 μm), dissolved constituents, and colloids penetrate into

the membrane by molecular adsorption and/or colloids deposition within
the membrane pores, and cause internal fouling and consequently a sharp
flux decline in the first few minutes/seconds of filtration.
• Larger particles (>2 μm) are retained by the membrane and cause a revers-
ible external deposit on the membrane surface. This cake layer can be easily
removed by back pulse, infrasonic pulse, or by stopped pressure drop and
rinsed membrane.
• No deposition was observed on the membrane surface at the critical flux
(when the pressure difference was ≤0.15 bar); above 0.15 bar, particle depo-
sition was realized.
Ulbricht et al. (2009) investigated the influence of the membrane polymer mate-
rial on the adsorption of polyphenols and polysaccharides during model red wine
MF. The applied polymers were polypropylene (PP) and polyethersulfone (PES),
the membranes were capillary type with 0.2 μm cut-off pore size, and the apparatus
had industrial size. The model solution for wine was prepared by using commercial
red grape extract from grapes after fermentation. It was established that individual
polyphenols and polysaccharides were only marginally adsorbed by PP but strongly
adsorbed by PES membranes. The polar interactions were much stronger with PES
than with PP. The low adsorption tendency of wine ingredients resulted in higher
fluxes and longer service life.
Field et al. (1995) modeled the MF fluxes and introduced the concept of critical
and sustainable fluxes and many researchers, among them Bacchin et al. (2006),
applied and refined the expressions based on numerous measurements.
Fouling in wine MF using row white wines was investigated by Manninger
et al. (1998). A continuous fouling caused a strong decrease in the permeate flux
(Figure 5.6).
Because of the fouling, a systematic membrane cleaning is advised. The cleaning
of the microfilter can be done by physical methods and by chemical washing.
According to Salazar et al. (2007), the 20–70 kDa-molecular-weight proteins gen-
erate membrane fouling and this causes a flux decline.
To remove the gel layer from the surface of the membrane, and the fouling from
the fouled membrane in order to increase the permeate flux during the filtration,
systematic back pulse, infrasonic pulsing, or combined methods are proposed in the
enology.
Systematic back pulse was applied by Boissier et al. (2008), who performed
experiments with synthetic and actual red wine. MF was used to investigate the
impact of red wine particles—that is, Saccharomyces cerevisiae, lactic acid bacte-
ria, colloidal aggregates, and fines—on the membrane fouling and particle deposi-
tion. Scanning electron microscopy (SEM) observation was used to compare fouling
at different compositions and different hydrodynamic conditions. Systematic back
pulse was applied with rather high transmembrane pressure values (between 100
300
Racked + clarified + filtered
250 Racked + clarified
Racked
200
Flux (L/(m2h))
150
100
50
0
0 100 200 300 400 500 600
Permeate volume (cm3)
FIGURE 5.6 Microfiltration with 500 nm pore size ceramic membrane, 400 L/h recycle
flow rate. Influence of pretreatment on permeate flux of white wine. (From Manninger, K.
et al.: Acta Alimentaria, Vol. 27, 377–387, 1998.)
and 200 kPa). The removal efficiency strongly depended on the fouling rate between
two back pulses. The yeast deposit can be removed easily, while the deposit formed
by bacteria can be more difficult to eliminate, when a high transmembrane pressure
is applied. In spite of intensive back pulsing, the main permeate flux remained low.
Infrasonic pulsing was applied by Czekaj et al. (2001) to remove foulant cake.
They examined the MF of fermented beverages such as beer and wine, and the foul-
ing was compared with that of model turbidity suspensions, based on gelatin and
tannic acid. Different plastic membranes were used with 0.2 μm pore size.
Fouling was investigated using a separate protein solution or a separate polyphe-
nol solution. When both fouling materials were applied together, the fouling was
much stronger. Fouling in wine was mainly caused by light scattering complexes
formed by polyphenols and proteins. Internal fouling dominated first; it was fol-
lowed by external fouling, and both caused a strong decrease in the permeate flux.
Infrasonic high-frequency pulses of the permeate were sent back in the direction
of the membrane. The pressure of the pulses was lower than the transmembrane
pressure. Model solution and fermented wine were filtered; the infrasonic pulsing
removed the fouling and increased the permeate flux 2.5–4 times.
Mannapperuma (2003) reported a combined method, which was developed at the
Californian E&J Gallo Winery. Combined MF + NF membrane system was applied
for the removal of potassium bitartrate and for wine stabilization. The system is
shown in Figure 5.7. The molecular weight of potassium bitartrate is 188; therefore,
it can be concentrated by RO or NF; then the tartrate crystals can be removed from
the retentate by MF. In this case, NF was applied to separate the wine and the tartrate
crystals appeared in the retentate, which were removed by MF. The microfiltered
permeate was mixed with the NF permeate in a ratio of 84:16. This reconstituted
NF
Wine 100 L Permeate 80 L
MF
Permeate 19 L Wine 99 L
Concentrate 1 L
FIGURE 5.7 Combined MF + NF system for wine stabilization. Gallo winery, California.
(From Mannapperuma, J.D.: Membrane application in grape juice and wine processing, 2003.
Internet document, www.energy.ca.gov/reports2003-03-21_400-02-020F.PDF. Accessed
20/01/04.)
wine was stable and clarified. This method of stabilization is cheaper than that
gained by refrigeration and is more simple than using electrodialysis.
van der Bruggen and Vandecasteele (2001) performed experiments with aqueous
solutions of organic components using NF membranes and established similar high
flux decline in the function of concentration, than in the case of MF. However, in
the case of NF, the pore size cannot explain the flux decline; there is an influence of
polarity and polarizability, as well.
Salazar et al. (2007) proposed a hybrid process to reduce the unstable proteins of
Pinot Noir wine and to improve the permeate flux. The process contains an adsorp-
tion column, packed with zirconium oxide and ceramic package, coupled with an
MF tubular ceramic membrane of zirconium oxide with a 0.2 μm pore size.
Three different pretreatment agents were applied to the wine to decrease the pro-
tein and polyphenol content: bentonite, activated carbon, and the mixture of both.
MF experiments were carried out with row wine and pretreated wines. The perme-
ate fluxes of MF showed a slow decrease in the function of time. The permeate
flux of row wine was the lowest, the zirconium oxide adsorption increased the flux
by 15%–20%, while the pretreatment with bentonite + activated carbon caused the
highest increase in permeate flux due to the strong reduction in proteins and poly-
phenols. The 20–70 kDa-molecular-weight proteins generate membrane fouling and
this causes the flux decline.
Buffon et al. (2014) have found that a 0.22 μm pore size MF membrane in cross-
flow filtration mode have a stabilizing effect on the sensory profile of California
white wine blend and California red wine blend, but the color changed significantly.
The ethanol content of the red and white wines is very similar, while the anion
content is different. In the white wine the higher tartaric acid concentration causes
instability.
El Rayess et al. (2011) published a good review about cross-flow MF applied to
enology.
Goncalves et al. (2003) applied electrodialysis (ED) for tartaric stabilization of

wines. The ED process was mild; the operation voltage was 1.0 V/cell, and after the
treatment, no undesirable precipitation occurred.
For chemical cleaning of membranes, the producers proposed using the solu-
tion of different detergents, alcohols, bases, etc., combined by rinsing water
treatment.
5.5.2 Low-Alcohol Wine Production

Wine is one of the most widely consumed alcoholic drinks, but recent years have
witnessed an increased demand for reduced alcohol beverages because of health
and social concerns. Moderate consumption of wine may help to protect against
coronary, Parkinson’s, Alzheimer’s, and Huntington’s diseases and many forms of
cancer. At the same time, an excessive amount of wine consumption can have nega-
tive effect on human health because its alcohol content is poisonous for the cells of
the human body.
There is a considerable worldwide interest, for health reasons, in developing
methods for selective removal of alcohol from certain beverages like wine, without
adversely affecting their taste, odor, or mouth feel. Increasing number of consumers
from both domestic and foreign markets prefer lighter wines characterized by mod-
erate alcohol content (12%–13% v/v), intensive color, and primary bouquet (Palliotti
et al., 2014).
Nowadays, the main efforts devoted to decrease ethanol content are
• To produce lighter wines. In some cases, a reduction of alcohol from wine

is necessary: to keep the valuable components in the wine, while decrease
its alcoholic content till 12%–13%.
• For health reasons, two new wine products are introduced in the market,
both with significant reduction of alcohol content:
• “Low-alcohol” wine with ≤3% v/v ethanol
• “Alcohol-free” wine with ≤0.5% v/v ethanol
The low-alcoholic content (≤3% v/v) and the alcohol-free (≤0.5% v/v) wines can
be consumed by sick or elderly people as well.
The major defect in many modern wines is the excessive ethanol. In the very
sunny geographical area (Mediterranean, California, Australia, South America,
etc.) in the last 10–20 years, the alcohol content in wines increased to 15%–17%
v/v because of the intensive sunshine and higher ripening rate of grapes (Palliotti
et al., 2014). The law allows only 12%–13% v/v ethanol in wines. It needs a decrease
in ethanol concentration with about 2%–4% v/v. The European Union regulation
recently permits a maximum of 2% v/v dealcoholization level.
To produce low-alcohol and alcohol-free wines is a difficult task; many research-
ers deal with suitable solutions. The main difficulty is that there are flavor and aroma
components, which are soluble only in ethanol and not in water; therefore, the etha-
nol removal reduces these components, and decreases the accustomed mouth feel of
wine (Fedrizzi et al., 2014).
5.5.2.1 Traditional Methods and a Modern Method

for Ethanol Reduction of Wines
• The simplest method for achieving lower alcohol is to pick the grapes ear-
lier. With this method, less sugar, but less flavor, color, and body of the wine
could be reached.
• Early arrest of fermentation reduces convertible sugar.
• Application of low-alcohol-producing yeast (Gonzalez et al., 2013; Quiros
et al., 2014).
• One approach is to add water to the grape must or wine. While this has
been practiced for centuries, it diminishes wine quality by reducing the
overall concentration of the wine.
• Adsorption of wine alcohol on zeolites is applied as well.
• Using a low-temperature distillation technique such as the spinning cone,
volatile components of the wine, including alcohol, are removed in the dis-
tillate, and then the volatile flavors are separated from this and returned to
the wine being treated. This system is complex and capital intensive. There
is also some possibility of flavor loss, but most importantly, the alcohol is
removed, so the overall volume loss from the wine is significant.
In the study of Gomez-Plaza et al. (1999), distillation was applied to decrease the
alcohol content in white wines. Some volatile components like linalool, α-terpineol,
and benzyl alcohol practically disappeared from the dealcoholized wine. Some
esthers maintained their initial concentration, others escaped quickly. The dealco-
holized wine was an organoleptically unacceptable product with low level of volatile
compounds. A better product was obtained by the addition of condensed volatile
fraction, or by the addition of new wine.
• Supercritical fluid extraction with CO2 is a modern, mild but expensive

method for dealcoholization. Two steps were proposed by Ruiz-Rodriguez
et al. (2012). First step: extraction and recovery of aroma compounds from the
original wine. Second step: extraction for the dealcoholization of the aroma-
free product, receiving ≤1% v/v ethanol content in the raffinate. The novel bev-
erage was the reconstituted rosé wine, which had similar antioxidant activity
and polyphenol content, similar aroma profile to that of the original rosé wine.
5.5.2.2 Membrane Methods for Ethanol Reduction in Wines

• Membrane filtrations, like RO, NF, or their combination, contrary to the
traditional separation methods, can reduce ethanol content in a much milder
way because their production temperature can be ambient or lower, so the
organoleptic features might have less or negligible change.
• Pervaporation is a mass transfer membrane operation, which is a competi-
tive method for alcohol removal from wine. Its advantage is the low temper-
ature, which protects the wine components against thermal degradation. Its
disadvantage is the higher prize of membranes and higher operation costs.
• Osmotic distillation process is capable of water and ethanol removal
from wine at ambient or lower temperature. In this membrane contactor
technique, a porous hydrophobic membrane separates two aqueous solu-

tions, the feed wine and an osmotic agent. The osmotic agent—mainly salt
solution—draws the water and ethanol through the porous membrane in
the form of vapor. The performance depends on the vapor pressure differ-
ences between feed and stripping streams. Low ethanol concentration can
be achieved this way in the feed wine.
• Separation by liquid emulsion membrane can significantly decrease the
alcohol concentration. A thin liquid film separates the feed and the internal
aqueous phases, and controls the mass transfer. The transport of alcohol
present in the feed takes place across the membrane due to its ability to
partition into the membrane phase and its diffusion through the membrane.
The driving force is the concentration gradient.
5.5.2.3 Dealcoholization by Reverse Osmosis and Nanofiltration

The decrease of alcohol concentration in wines and other beverages can be fulfilled
by RO and NF (Figure 5.8). RO and NF are the most promising processes for the
reduction of the alcoholic degree of wine because they operate at low temperature
and their energy consumption is not high. The most important parameters that have
the largest effect on investment and operating costs are recovery rate and membrane.
Many researchers try to lower the costs and make the process economically feasible.
Taking into account the decrease of investment costs and power consumption, the
dealcoholization price of wine and beverages is continuously decreasing.
Labanda et al. (2009) investigated the permeation of several characteristic aroma
components of white model wine. Glycerol, tartaric acid, albumin, pectin, tannic
acid, and sodium metabisulfite was dissolved in the mixture of water and 120 mL/L
absolute ethanol. Three membranes were tested and the NaCl retention of them was
99.0% (M1), 97.2% (M2), and 98.0% (M3). The transmembrane pressure differ-
ence was 29, 10, and 17 bar, respectively. The membranes were conditioned with
10
PI
11
11
9
1
5
8 7
6
TI PI
4
3 5
FIGURE 5.8 Flow sheet of high-pressure RO/NF system. (1) Feed tank, (2) cooling system,
(3) high-pressure pump, (4) bypass valve, (5) valve to set RO or NF, (6) RO membrane, (7) NF
membrane, (8) recycle valve, (9) pressure valve, (10) rotameter, and (11) permeate.
5
4.5
4
3.5
Flux (kg/(m2h))
3
2.5
2
1.5
1 Membrane M1
Membrane M2
0.5 Membrane M3
0
0 5 10 15 20 25 30 35 40
Δp · 10–5 (Pa)
FIGURE 5.9 Solvent flux as a function of transmembrane pressure for three RO membranes
tested. M1: Osmonics-SE, M2: Toray-UB70, M3: Osmonics-DK. (From Labanda, J. et al.:
LWT—Food Science and Technology, Vol. 41, 1390–1395, 2009.)
ethanol solvent before the experiments. The filtration temperature was kept constant:
15 ± 0.1°C.
The solvent flux increased proportionally with transmembrane pressure (Figure 5.9).
The permeate flux of model wine was very low with respect to the pure water flux;
the permeability of membranes decreased by around 90% with respect to the water
permeability. The highest permeability was measured on the 97.2% NaCl rejection
membrane. While solvent permeability decreased, global rejection increased as the
NaCl retention of membrane was increased.
The retentate concentrations were greater than the permeate concentrations for all
membranes. The solute rejection was high at all the three membranes (Figure 5.10).
As a general result, it was observed that the decrease of alcohol content in model
wine was about 33%, while the removed solutes were less than 15%. The organoleptic
quality of the final wine was not determined. A mathematical model was presented
for the retention of solutes, and a good agreement with measured data was reached.
In the publication of Pilipovik and Riverol (2005), different homemade bever-
ages were separated by a spiral wound RO membrane under high pressure. The feed
beverages had 5.5%–7.1% of ethanol. Low-molecular-weight compounds such as
water, methanol, and ethanol passed through the membrane, while other compounds
(carbohydrates, apparent extracts) were retained. The system worked at high pres-
sure (35–50 bar) and very low temperature (0°C); therefore, the thermal degradation
could be neglected.
The lowest alcohol percentage obtained in all cases was 0.5%. Different scenarios
were tried, but the reduction under 0.5% was impossible. A reduction in the apparent
extract and the carbohydrates content were observed when the system was working
under 45 bar. The quality of the product was not constant, and, depending on the
operation conditions, different results were obtained.
1.2
Concentration (mg/L) 1
0.8
0.6
Retentate Permeate
0.4
0.2
0
0 100 200 300 400 500
Permeate volume (mL)
FIGURE 5.10 Evaluation of cis-3-hexenol concentration in retentate and permeate during

the concentration process for membrane M1 (Osmonics-SE). (From Labanda, J. et al.: LWT—
Food Science and Technology, Vol. 41, 1390–1395, 2009.)
A new strategy of the authors was dilution of the feed solution; this is diafiltration.
The dilution compensated the water loss, reduced the salt content, kept the carbohy-
drate concentration constant without remarkable alteration of the flavor and quality
of the product. This method avoids the major problem in dealcoholization: to keep
the quality of the final product in a reasonable range.
As a conclusion the authors established that high pressure is needed for the RO
concentration of the diluted feed, and the low alcohol content is acceptable. However,
the authors recommend using flavoring additives for restoring the flavor.
In the article of Gil et al. (2013), industrial RO (Society Michael Paetzold) was
applied for partial dealcoholization of Cabernet Sauvignon wine (14.8% v/v) and
Grenache-Carignan blend coupage (16.2% v/v). The impact of dealcoholization with
−1% v/v or −2% v/v was investigated in red wine composition and sensory charac-
teristics. Standard wine analysis, phenolic compounds, color parameters, polysac-
charide, and sensory analysis were performed. The results indicated that the partial
dealcoholization by RO does not appreciably alter the chemical composition and the
color of the wine, except the ethanol content. The authors think the RO is an impor-
tant tool to decrease the ethanol content, which increases because of the climatic
changes. For removing 1% ethanol, the calculated price was 0.15 EUR/L.
Catarino and Mendes (2011) used different RO and NF membranes in diafiltration
mode for red wine dealcoholization. RO membrane (CA 995PE, Alpha Laval), and
four NF membranes (NF99 HF, NF99, NF97 from Alpha Laval and YMHLSP1905
from Osmonics) were applied to remove ethanol from a 12% v/v red wine.
Before the dealcoholization step, pervaporation membranes (POMS/PEI from
GKSS) were used to recover aroma compounds. After the dealcoholization, the
aroma compounds were added to the wine. This combined process was effective for
alcohol removal and preserving the original characteristics of the wine.
Experimental results obtained by Bogianchini et al. (2011) testified that after RO
filtration, the <2 v/v % ethanol content wine maintain phenolic compounds and anti-
oxidant activity. Besides, this dealcoholized wine with active compounds was more
stable after 70 months of storage than dealcoholized wines obtained by other methods.
5.5.2.4 Dealcoholization by Pervaporation

The alcohol content of Tokaji Hárslevelű white wine was reduced by pervaporation in
laboratory scale using Pervap Sulzer 1060 organofil membrane of 131 cm2 active area.
Takacs et al. (2007) performed the experiments in batch mode, at 1.9 L input of wine.
The pressure at the feed side was atmospheric. Constant liquid recycle rate was applied
because the change in recycle had no influence on the pervaporation performance. The
increase of temperature from 40°C till 70°C strongly increased the permeate flux.
Figure 5.11 shows the scheme of the laboratory-scale equipment. The liquid
(mostly ethanol and volatile components dissolved in ethanol) from the wine passed
through the pervaporation membrane in vapor phase. The back side of the membrane
was swept by inert gas (air) using a dry vacuum pump.
The measured permeate fluxes are shown in Figure 5.12. The total flux, the flux
of ethanol, and other components increased by an increase in the temperature, while
the separation factor decreased. At low temperature (40°C), 38.5% v/v ethanol was
reached in the permeate.
PI TI
TI 11
2
1 6
3 13
12
9
4
10 8
FIGURE 5.11 Laboratory-scale pervaporation equipment. (1) Pervaporation membrane, (2)

liquid mixture inlet, (3) permeate vapor, (4) vacuum pump, (5) condenser, (6) liquid tank,
(7) insulated permeate collector, (8) pump, (9) thermostat, (10) outlet valve, (11) flow control
valve, and (12) pressure control valve. (From Takacs, L., G. Vatai, K. Korany: Journal Food
Engineering, Vol. 78, 118–125, 2007.)
1.4
1.2
1.0
Flux (kg/(m2h))
0.8
0.6
0.4
0.2
0.0
35 40 45 50 55 60 65 70 75
Temperature (°C)
Permeate Ethanol Others
FIGURE 5.12 Relationship between permeate flux and temperature on Sulzer Pervap 1060
membrane. (From Takacs, L., G. Vatai, K. Korany: Journal Food Engineering, Vol. 78, 118–
125, 2007.)
The change of permeate flux and separation factor was strongly influenced by the
process temperature (Figure 5.13).
The decrease of the ethanol content has a disadvantage: 70% of the aroma com-
pounds were concentrated in the permeate, dissolved in the permeated ethanol. This
fact caused a change of the aroma of the product low-alcoholic-content wine.
5
Separation factor, α (–)
4
2
Permeate flux (kg/(m2h))
1
0
35 40 45 50 55 60 65 70 75
Temperature (°C)
Model solution’s total permeate flux Wine sample’s total permeate flux
Model solution's separation factor Wine sample’s separation factor
FIGURE 5.13 Change of permeate flux and separation factor of the wine sample and identi-
cal concentration model solution as a function of temperature. (From Takacs, L., G. Vatai,
K. Korany: Journal Food Engineering, Vol. 78, 118–125, 2007.)
An economic analysis shows a great investment cost demand because of the rela-
tively high price of nonporous pervaporation membrane and high heating and cool-
ing costs. With an increase in the temperature, the price can be decreased, but the
quality of the product decreases, at the same time. Therefore, an optimum tempera-
ture can be chosen as a compromise.
The by-product, the permeate with high alcohol and aroma content, can be uti-
lized as wine distillate or industrial spirit. This fact strongly decreases the costs of
pervaporation preparing low-alcoholic-content wine.
5.5.2.5 Dealcoholization by Osmotic Distillation

The osmotic distillation (OD) is an alternative method for wine dealcoholization. OD
is an isothermal process, which can be operated at low temperature and atmospheric
pressure. The process takes place in a porous hydrophobic membrane contactor,
which separates two aqueous solutions, as shown in Figure 5.14. On the feed side
of the membrane, the wine is recycled, while on the permeate (stripping) side, an
osmotic solution of salt, glycerol, etc. (Varavuth et al., 2009) (sometimes clean water)
(Lisanti et al., 2013) is circulated.
The water and the ethanol pass through the membrane from the wine side to the
osmotic/stripping solution side, in the form of vapor. Figure 5.15 illustrates the con-
centration profile and ethanol pressure change in OD.
In the experiments of Varavuth et al. (2009), 0.2 μm hydrophilic poly(vinylidene
fluoride) (PVDF) hollow-fiber membrane was applied. The liquids to dealcohol-
ize were red wine and model wine (ethanol–water solution). Besides, water with
50 mg/L ethyl acetate and water with 400 mg/L iso-amyl alcohol were prepared to
study the aroma loss during OD.
Three stripping solutions were used: pure water, 50% w/w glycerol, and 40% w/w
CaCl2 solutions. The influence of stripping velocity, feed velocity, and temperature
were investigated.
PI
TI
TI PI
5 4
4 5
PI TI
1
TI
TI
2 PI
7 3
TI
6
7
9
8 8
FIGURE 5.14 Flow sheet of osmotic distillation (OD). (1) Membrane, (2) feed (fruit juice),
(3) osmotic agent (saturated CaCl2 solution), (4) heat exchanger, (5) thermostat, (6) digital
balance, (7) rotameter, (8) peristaltic pump, and (9) PC.
Macroporous hydrophobic
membrane
Feed solution Stripping solution
Cf,b Cf,m
Cs,m
Cs,b
Pef,b Pef,m
Pes,m
Pes,b
Ethanol vapor flux
FIGURE 5.15 Concentration profile (c) and partial pressure (p) of ethanol in dealcohol-
ization process by OD membrane. (From Varavuth, S., R. Jiraratananon, S. Atchariyawut:
Separation and Purification Technology, Vol. 66, 313–321, 2009.)
When 13% v/v ethanol solution was used, with an increase in velocity of the
different stripping solutions, ethanol fluxes were enhanced due to the increase of
Reynolds numbers of ethanol phase (laminar flow). In the removal of ethanol, there
is a simultaneous transfer of water vapor as well. The water flux increased with the
stripping solution velocity due to the increase of Reynolds numbers of water. The
ethanol flux increased with increasing feed side velocity due to the increase in the
mass transfer coefficient (Figure 5.16).
The change in feed velocity influenced more on flux than the stripping velocity.
When wine was circulated at the feed side (laminar flow), lower ethanol flux was
observed, than in case of ethanol–water solution, because the complex nature of
wine can result in fouling on the membrane.
By increasing the temperature of the OD process from 30°C to 40°C, the ethanol
and water fluxes strongly increased because the mass transfer coefficients for both
feed and stripping solutions improved.
During the OD process at 30–40°C temperature, a very high aroma loss was
observed in the function of time: 70% in ethyl acetate and 44% in iso-amyl alcohol
was lost within 360 min. In order to minimize the aroma loss in the OD process, it
is necessary to reduce the system temperature. The low system temperature will also
guarantee the product quality.
Comparing the influence of the nature of the stripping solution, it was observed
that the water was more appropriate to be used for dealcoholization in the OD pro-
cess than the other stripping solutions. The use of water as the stripper provided the
better solution in terms of ethanol flux, removal of ethanol performance, and water
flux than others. Ethanol removal measured with OD membrane is shown in Figure
5.17. The ethanol removal performance in the long-term test of OD showed that the
1.20
13.50
Ethanol concentration in retentate

1.00
13.00
0.80
Flux (kg/(m2h))
v (% v/v)
12.50
0.60
0.40 12.00
0.20 11.50
0.00 11.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Feed velocity (m/s)
EtOH flux of EtOH solution [EtOH conc.] of EtOH solution

EtOH flux of wine [EtOH conc.] of wine
FIGURE 5.16 Effect of feed velocity on ethanol and water flux, and retentate concentration
of ethanol solution and wine (stripping solution: water; system temperature: 30°C; stripping
velocity: 0.4 m/s). (From Varavuth, S., R. Jiraratananon, S. Atchariyawut: Separation and
Purification Technology, Vol. 66, 313–321, 2009.)
14
Wine Ethanol solution
Ethanol concentration retentate (% v/v)
12
10
8.71
8
8.10
4
0 60 120 180 240 300 360 420
Time (min)
FIGURE 5.17 Dealcoholization of ethanol solution and wine in OD process (stripping solu-
tion: water; system temperature: 35°C; feed velocity: 0.5 m/s; stripping solution velocity:
0.4 m/s). (From Varavuth, S., R. Jiraratananon, S. Atchariyawut: Separation and Purification
Technology, Vol. 66, 313–321, 2009.)
ethanol content in the ethanol solution and wine can be reduced with 38% and 34%
of the initial concentration.
Diban et al. (2008) dealt with the application of OD for partial dealcoholization
of wine (by 2% v/v reduction). Hollow-fiber hydrophobe PP membrane was applied
at room temperature. On the feed side, synthetic wine solution was circulated (shell
side), and on the tube side, degassed water was circulated that allows the ethanol
transfer, but avoids the water transfer. The synthetic wine contained water, etha-
nol, and aroma compounds in a concentration, as their actual appearance in wines,
confirmed by wine experts. The results were checked by Merlot grape wines, too.
Once-through mode of feed and stripping phase was applied. As a result, about 2%
v/v decrease in ethanol content was reached in each experiment, although the ethanol
concentration of the original model wines and Merlot wines were different (10%–
13% v/v). The aroma losses increased, in some cases, the aroma disappeared from
the wine, when long residence time was applied.
In the subsequent article of Diban et al. (2013)—using the earlier-mentioned OD
apparatus and method—they could find a good equilibrium of dealcoholization rate
and aroma loss. At 2% v/v removal of alcohol, <20% aroma compound loss was
measured, in contrast with earlier publications (30% and 50%).
Similar results were achieved by Lisanti et al. (2013). Dealcoholization of red
wines by 2% v/v ethanol—the actual European Union limit—using clean water
in the shell side of a 20 m2 membrane contactor minimally affected the sensory
properties of the red wine. However, the highest considered dealcoholization level
(by 5% v/v) caused great modifications of the sensory profiles and very great losses
(up to 100%) of volatile compounds.
Liguori et al. (2013a) used the OD technique for the total dealcoholization of
red wine up to 0.19% v/v ethanol content. Subsequent cycles were applied and
analyzed. Two important results were established: (1) During the OD process, the
main chemical and physical properties of the red wine (total phenols, flavonols,
tartaric esters, organic acids) did not show significant differences compared to the
control wine. (2) Volatile fraction, color intensity, and tonality of wine decreased
substantially together with the dealcoholization level. Therefore, flavor enrich-
ment is needed.
Liguori et al. (2013b) modeled the OD by dimensionless numbers (Re, Sc, Sh).
Fedrizzi et al. (2014) used pilot- and industrial-size membrane contactor for the
dealcoholization of several red and white wines, and measured significant changes
in aroma and flavor composition.
5.5.2.6 Dealcoholization by Liquid Emulsion Membrane

Chanukya and Rastogi (2013) applied hexane or heptane as liquid emulsion mem-
brane phases, and surfactant and distilled water as the inner aqueous phase. About
50% of the alcohol was removed from the wine using one-step extraction and >92%
of the alcohol was removed using multistep extraction. The efficiency of the deal-
coholization process is dependent on surfactant concentration, treatment ratio of
emulsion to feed, volume ratio of internal phase to membrane phase, stirring speed,
stirring time, and rate of membrane swelling.
5.5.2.7 Dealcoholization by Combined Method:

Reverse Osmosis + Osmotic Distillation
The Australian Wine Research Institute over the past 20 years has shown a steady
increase in the mean alcohol level of wines from 12.4% v/v in 1984 to 14.2% v/v in
2002. One reason is that winemakers want to avoid unpleasant green fruit charac-
ters by leaving their grapes longer as they strive for more mature flavors, tannins,
and softer acidity. The resultant higher sugar and hence high alcohol levels have
been an unwelcome but necessary consequence of this greater ripeness. (The other
reason of alcohol increase is the earlier-mentioned climate change in the last few
decades.)
A new technology, Memstar AA, was developed for reducing excess wine alcohol
without affecting any other components. The new technique is based on a combina-
tion of two membrane processes, RO and OD (Wollan, 2004).
Wine to be treated is separated by RO into retentate and permeate streams. The
retentate of RO preserves flavones, tannin, and color, while the water and partly the
alcohol passes through the membrane into the permeate. The alcohol-rich permeate
is degassed and heated. This alcohol-rich liquid then passes through an evapora-
tive membrane contactor, on the other side of which is a counterflow of strip water.
Alcohol passes through the membrane from the permeate into the strip water. The
permeation rate depends on the alcohol concentration gradient across the membrane
and on the temperature.
The dealcoholized permeate is then recombined with the wine from which it
was extracted, thus lowering the alcohol of the blend. The extraction of volatiles is
reduced because of their limited passage from the wine into the permeate stream.
The process is carried out in closed oxygen-free environment.
Garcia-Martin et al. (2010) introduced a two-step NF method to decrease the
sugar concentration in the must and consequently to obtain wine with a slight alcohol
reduction. To work with must instead of wine preserved the organoleptic properties
resulting during fermentation.
5.5.2.8 Pervaporation for Aroma Recovery
Aroma compounds are organic compounds that are extremely volatile.
Consequently, during the industrial production of drinks, like wine, there are
losses or chemical modifications of the aroma components; the product quality
and acceptance decreases. Xiuzhi Tian et al. (2005) experimentally proved that
pervaporation is a good tool for aroma recovery. Different membranes were com-
pared, and the influence of temperature on permeate rate and separation factor
was determined. The removed aroma can be added to the drink to recover the
good taste.
Lipnizki et al. (2002) applied hydrophobic pervaporation membrane for recov-
ery of natural aroma compounds from apple juice. The method is proper for other
liquid foods with multicomponent aroma content as well. The recovery and con-
centration of aroma components is cost-effective compared to the traditional heat-
treatment processes. Based on the results of simulation, a mathematical model was
developed to design the pervaporation unit and calculate the investment and opera-
tion costs.
5.5.3 Concentration of Wine, Increase of

Valuable Components’ Content
As it was detailed in Sections 5.2 and 5.3, wine contain many compounds (poly-
phenols, resveratrol, anthocyanins, minerals, etc.), which have beneficial effects on
human health. In contrast, excessive wine consumption is poisonous for the cells of
the human body, because of the 10%–14% v/v alcohol content.
The “concentration” of wine with membranes is a mild method to increase the
concentration of valuable components. This “wine concentrate” contains valuable
components in about twice higher measure, while the 10%–12% v/v ethanol pre-
serves the solution without any additives. The “wine concentrate” can be applied as
a nutrition complement in its concentrated form, or in diluted form. The dilution with
water produces a low-alcohol-concentration wine (4%–6% v/v) and can be consumed
by elderly or sick people.
The production of “concentrated wine” can be done by NF, RO, or other methods.
5.5.3.1 Concentration with Nanofiltration

The NF membrane permeates the water and the ethanol; therefore, the ethanol con-
tent in the permeate and in the retentate is practically equal. So a significant alcohol
removal can be reached besides the concentration of the wine. The permeate flux of
an NF membrane is higher; the needed pressure and the energy consumption of NF
is lower than that of an RO membrane. The disadvantage of NF is a certain loss of
valuable components, which appear in the permeate; however, this loss can be uti-
lized in preparing brandy from the wine permeate.
Banvolgyi et al. (2006) applied a very simple method for wine concentration:
red wine (Egri Cuvee, Hungary) was filtered by NF, and the retentate was the main
product, the concentrated wine. The permeate contained volatile and valuable com-
ponents in a low extent; it could be utilized as a row material in the alcohol industry
(“brandy”). The taste of this “brandy” was like that of the brandy, prepared from the
same red wine.
The applied membrane was XN45 Trisep membrane with 78.1% salt rejection and
0.046 m2 active filtrate surface and with different recycle flow rates in the module
(Re = 6400–9600). The transmembrane pressure was 20 bar and the temperature
range was 30–50°C. The ethanol, sugar, acid, free sulfurous acid, total extract, and
volatile acid were analyzed.
Table 5.9 shows the concentrations of the original wine, retentate, and permeate
at 20 bar and 30°C.
The alcohol content in the retentate was 9.7%, while sugar, extract, etc. practi-
cally remained in the retentate. Remarkable losses were measured in sulfurous
acid, which is a positive effect, and in volatile acid, which was found partly in the
permeate.
The final product is the retentate—the concentrated wine—with about two times
higher concentration of valuable components than that of the original wine. The
alcohol concentration of the retentate makes possible the preservation of the concen-
trated wine without additives. If water was added to the retentate, the product was
similar to the original wine but with a decreased alcohol content.
TABLE 5.9
Concentrations of the Original Red Wine (Egri Cuvee), Retentate, and
Permeate at 30°C, 20 bar, 400 L/h and the Calculated Retentions on NF
Membrane
Concentrations Red Wine Retentate Permeate Retention (R) (%)
Alcohol (% v/v) 12.81 9.7 10.75 9.70
Sugar (g/L) 2.8 10.4 0.1 99.04
Total acid (g/L) 4 9.3 1.1 88.17
Free sulfurous acid (mg/L) 6 2 1 50.00
Total sulfurous acid (mg/L) 52 74 2 97.30
Total extract (g/L) 25.29 71.59 4.92 93.13
Sugarless extract (g/L) 23.49 62.19 4.92 92.09
Volatile acid (g/L) 0.58 0.68 0.37 45.59
Source: Adapted from Banvolgyi, S. et al.: Desalination, Vol. 198, 8–15, 2006.
In a later work of Banvolgyi et al. (in press), the above-mentioned experiments

were continued with the same apparatus and membrane at a lowered temperature
range (20–40°C). The main aim of the experiments was to describe the influence
of the operation parameters on the anthocyanins, on the cis- and trans-resveratrol
content of the retentate and permeate. The total monomeric anthocyanin content was
determined by the pH differential method. The resveratrols were analyzed by HPLC.
The main valuable components of the original red wine (Egri Bikaver, Hungary)
are listed in Table 5.10.
TABLE 5.10
Valuable Compounds of the Initial Red
Wine (Egri Bikaver)
Compound Concentration
Alcohol (% v/v) 12.0
Sugar (g/L) 3.5
Acid (%) 5.35
SO2 free (mg/L) 4.0
SO2 total (mg/L) 47.0
Total extract (g/L) 28.58
Sugarless extract (g/L) 26.08
Volatile acid (g/L) 0.63
Anthocyanin (mg/L) 228.0
trans-Resveratrol (mg/L) 2.24
Source: Adapted from Banvolgyi, S. et al.: Desalination,

Vol. 198, 8–15, 2006.
Anthocyanin concentration (mg/L) 800

700
600
500
400
300
200
100
0
Original 1 2 3 4 5 6 7
wine
Experimental run
FIGURE 5.18 Anthocyanin concentration in the original red wine and in the wine concen-
trates prepared by nanofiltration. (From Banvolgyi, S. et al.: Food Science and Technology
(in press).)
In the different experiments, the original 200 mg/L anthocyanin concentration

increased to 500–680 mg/L, the 2 mg/L trans-resveratrol concentration reached
4.0–4.5 mg/L, and the total resveratrol concentration grew from 4.2 to 7–11.5 mg/L
in the retentate (Figures 5.18 and 5.19).
Temperature was found to be very effective for the retention of resveratrol and
anthocyanins, the lowest temperature (20°C) produced the highest increase in the
valuable components.
12 Trans-resveratrol Total resveratrol

Resveratrol concentration (mg/L)
10
0
Original 1 2 3 4 5 6 7
wine
Experimental run
FIGURE 5.19 Resveratrol concentration in the original red wine and in the wine concen-
trate prepared by nanofiltration. (From Banvolgyi, S. et al.: Food Science and Technology (in
press).)
TABLE 5.11
Ethanol Reduction in Wine Samples (Prepared from Egri Bikaver) Used
for Sensorial Evaluations
Number Sample Ethanol (% v/v)
1 Original wine 12.0
2 Wine concentrate + water in 1:1 ratio 6.0
3 Wine concentrate + water + grape juice in 1:1.90:0.10 ratio 4.0
4 Wine concentrate + water + grape juice in 1:1.85:0.15 ratio 4.0
Source: Adapted from Banvolgyi, S. et al.: Desalination, Vol. 198, 8–15, 2006.
The retentate had about the same concentration of alcohol than that of the original
wine. The reconstituted retentate had low concentration of alcohol and high content
of valuable components. For reconstitution, clean water and water + must mixture
were applied according to Table 5.11.
The trained panel of 10 experts qualified the color intensity, odor intensity, acidic
taste, sweet taste, alcoholic aspect, and general impression. The comparison of the
sensorial profiles of original wine with the concentrated wine obtained by NF and
reconstituted in different ways is shown in Figure 5.20.
The sensorial analysis also showed that the taste of the wine concentrate—
using different forms of reconstitution—was aromatic, and there was no consid-
erable difference between the original wine and reconstituted samples obtained
from wine concentrate by the dilution with either water or water together with
grape juice.
5.5.3.2 Increase of Wine Ingredients Content by RO and Other Methods

The RO membrane permeates the water, partly the ethanol, and a low percent of the
valuable components. The advantage of RO is the high retention of the valuable com-
ponents, while disadvantages are the lower permeation of the ethanol, a lower per-
meate flux, a higher transmembrane pressure difference, and consequently a higher
energy consumption, compared with NF (Mermelstein, 2000).
When the musts have no sufficient sugar content to reach a proper alcohol percent
during the fermentation, concentration of grape must can be used. Mietton-Peuchot
et al. (2002) applied an RO to increase the sugar content in must, and consequently
improve the wine quality. According to their experiments
• Low temperature (about 10°C) and high pressure (about 75 bar) are the
proper conditions to prevent the must components from crossing the
membrane.
• Higher temperature (15 → 28°C) enhances the migration of aromatic com-
ponents through the membrane, and increases the permeate flux.
• Higher pressure (55 → 75 bar) provokes equilibrium modification and tar-
tarate precipitates at the membrane surface.
Color intensity
100
80
60
General impression Odor intensity
40
20
Alcoholic aspect Acidic taste
Sweet taste
Original wine
Concentrated wine + water in 1:1 ratio
Concentrated wine + water + grape juice in 1:1.90:0.10 ratio
Concentrated wine + water + grape juice in 1:1.85:0.15 ratio
FIGURE 5.20 Comparison of the sensorial profiles of original wine with the concentrated
wines obtained by nanofiltration and reconstituted in different ways. (From Banvolgyi, S.
et al.: Food Science and Technology (in press).)
The best compromise can be achieved at 10–15°C and 75 bar. Red wines, pre-
pared from the must, concentrated by RO were more structured, aromatic, soft, with
improved full color, and with increased phenolic stability.
Lopez et al. (2009) used pulsed electric field (PEF) treatment to freshly fermented
Cabernet Sauvignon model wine in order to increase the anthocyanin concentration of
wine. PEF is a nonthermal method that involves the application of microsecond pulses
of high electric field strength to a material located between two electrodes. The grape
pomace was treated at different parameters and different maceration times were applied.
The application of a PEF treatment to the grape pomace produced an increase in
the color intensity, anthocyanin content, polyphenol index, and tannin concentration.
The enhancement of the extraction of phenolic compounds occurs even after short
maceration times. The total anthocyanin content was higher in freshly fermented
model wines obtained from PEF-treated grapes at different maceration times, com-
pared to the control wine.
Sensorial analyses conducted by a triangle test indicated that judges did not detect
any difference between the freshly fermented model wine obtained from untreated
and PEF-treated pomace. These mild requirements indicate very low treatment costs
of the process.
A patented technique of Norrie (2009) involves extracting resveratrol from the

grape skins. With his new patent, very high (more than 50%) increase of resveratrol
was obtained in the wine.
5.5.4 Special Wine Products, By-Products: Wastewater in Wineries

5.5.4.1 Special Wine Products
The preparation of wines and the application of membranes in the wine production
are detailed in Sections 5.4 and 5.5. The natural white and red wines—produced in
the traditional way—can be
• Light table wines, made from must having 13% w/w sugar
• Quality wines, made from must having 15% w/w sugar
• High-quality wines, made from must having 19% w/w sugar
Besides these classical products, some special wines are produced applying spe-
cial grapes, or using some additive techniques in must preparation.
For special wine production, the MF is an obvious technique; the main techno-
logical steps are similar to that of the natural wine preparation.
5.5.4.1.1 Tokaji Aszu Wine (Tokay Wine)

The Tokaji aszu is the best-known wine produced in the Tokaj region, Hungary. The
raw material is a quality white grape, which is harvested after the Botrytis cinerea
fungi attack the ripe grape in autumn. This course is called “noble rot”: the grape
loses water and obtains a brownish color. The berries with botrytis are collected
from the cluster by hand, then put into the must or wine of the same sort of fresh
grape. The scenery of wine preparation is continued in a traditional way: by fermen-
tation and maturation in oak barrels for 3–5 years. The Tokaji aszu contains about
12% v/v alcohol; this is a sweet, toothsome, extra-fine-quality wine, which is an
excellent source of valuable components.
5.5.4.1.2 Ice Wine

This type of wine is produced in the Nordic countries (Canada, Northern Germany),
where the grape is left on the plant during the winter to freeze; the ripe grape is
harvested in a frosty form. During the pressing of the grape, the ice crystals of water
remain in the press; therefore, higher sugar content can be reached in the must. The
production of ice wine is increasing permanently (Robinson, 2003).
Fifty-one Canadian ice wines were investigated by Nurgel et al. (2004). Different
varieties, origins, and vintages were compared chemically and 20 of them sensorially
as well. The wines had diverse titratable acidity, acetic acid, glucose, and ethyl acetate
content. The Ontario wines had apricot, raisin, honey, and oak aromas, while the
British Columbia ice wines had higher intensity of pineapple and oxidized aromas.
5.5.4.1.3 Wine from Dried Grape

Moreno et al. (2007) in Spain let the grape dry in the sun for 12 days. A significant
increase in the total antioxidant activity was observed during the drying process,
besides an increase of sugar concentration, and a significant loss of water was also
observed.
5.5.4.1.4 Porto, Madeira, Malaga, Marsala Wines

All are sweet wines with 3%–13% w/w sugar content and 17%–20% v/v ethanol. The
high sugar concentration is achieved by stopping the fermentation (the sugar cannot
be converted to ethanol after stopping). The high ethanol content is gained by addi-
tion of alcohol (Robinson, 2003).
5.5.4.1.5 Sherry Wines

In this case, the fermentation takes place under a yeast layer on top of the must/wine.
The stoppage of fermentation is done by adding alcoholic additive, originated from
wine distillate. The alcohol content of the sherry wine reached 15.5%–17% v/v , which
is enough to stabilize the dry (sometimes sweet) wine product (Robinson, 2003).
5.5.4.1.6 Resveratrol Enhanced Wine

The healthy components of wine are the various antioxidants, such as the polyphe-
nols quercetin, epicatechin, and resveratrol. Resveratrol is not only an antioxidant,
but also stimulates the gene that allows organisms to live longer. A study by Norrie
(2009) followed 1400 males for the past 40 years. All wine drinkers, in moderation,
lived an average of 5 years longer than abstainers did.
A patented technique of Norrie (2009) involves extracting resveratrol from the
grape skins and adding Vitis vinifera grape-derived resveratrol back into the bulk
wine. With this new patent, much higher than 50% increase of resveratrol was gained
in the wine, instead of the average 1–2 mg/L (white) and 3–6 mg/L (red wine) res-
veratrol content.
5.5.4.1.7 Vermouths
These are mixed sweet wines; the additives are wine distillate, sugar, and different
drugs.
5.5.4.1.8 Dry Wine

The dry wine has low sugar concentration, ≤4 g/L.
In the study of Masamitsu Takaya et al. (2002), dry wine was prepared by con-
trolled yeast growth in a double-vessel bioreactor with continuous fermentation. The
dilution rate was changed to observe its influence on the fermentation. The initial
sugar in grape must was 200 g/L; during the fermentation, most of the sugar was
converted to ethanol to obtain a low sugar content (≤4 g/L) in the wine, while the
ethanol concentration increased till 100∼110 g/L. The batch fermentation needs
about 12 days; this continuous fermentation needed only 10 hours.
5.5.4.1.9 Champagne and Sparkling Wine

These wines are prepared mostly from light white wines. In case of champagne, the
CO2 bubbles arose in the closed bottles during a secondary fermentation. In case of
the cheaper sparkling wine, this secondary fermentation takes place in stainless-
steel vessels (Robinson, 2003).
Many researchers deal with the investigation of fruit wines, for example, apple
wine (Robinson, 2003), litchi wine (Zeng et al., 2008), mao wine (Puangpronpitag
et al., 2009), etc.
5.5.4.2 By-Products in Wineries

5.5.4.2.1 Spirits from Wine
From the fermented grape, mostly wine is produced, but the fermented grape can be
the raw material of spirits, as well.
For spirit production in the industry, batch or continuous distillation is applied.
The continuous distillation consists of two steps: dealcoholization and distillation.
For dealcoholization, the ethanol is steam-stripped from the fermented grape to give
a product of 10%–20% v/v ethanol in water. This product is fed to the distillation
column for ethanol concentration until 80% v/v (Robinson, 2003).
Cortella and Da Porto (2003) developed an industrial-size column with rotating
arms on the heated plates, and this modification made it possible to feed the must
with 5%–6% solid matter directly to the top plate of this new type of distillation
column. The main product was ethanol with 80% v/v concentration.
The design of such a distillation plant needs the data of vapor–liquid equilibrium,
but the description of the vapor–liquid phase equilibrium is not solved yet. Faundez
and Valderrama (2004) investigated the equilibrium of two component mixtures;
these were water + one wine component, or ethanol + one wine component. Three
different equilibrium models were compared. It was found that the NRTL model is
a very good tool for correlating both ethanol- and water-based binary mixtures, and
can be extended for multicomponent mixtures.
Other by-products of grape fermentation and wine making, such as grape mark or
wine mark, are also proper for spirit production.
5.5.4.2.2 Application of Grape Seeds, Skins, and Lees

The food and beverage industry is forced to minimize waste and convert food by-
products to valuable products that would otherwise be lost.
Two of the main sensory parameters of wine are astringency and bitterness, which
are influenced by proanthocyanidins and condensed tannins. These components are
in grape seeds and skins and extracted into red wine during fermentation. Fontoin
et al. (2008) investigated model wine for experiments: distilled water + 80 g/L grape
seed tannin extract + ethanol. The pH was fixed by NaOH. This study reveals that
pH, ethanol, and tartaric acid modify the oligomeric tannin astringency and bitter-
ness. The ethanol content plays an important role in enhancing the bitterness of wine.
Hwang et al. (2009) successfully applied a by-product, the black grape wine lees.
The grape wine lees (GWL) is the sediment in the bottom of the barrel and it con-
tains yeast lees and grape stalks, grape pomace, grape peel, and grape seed. Low
concentration of GWL (50, 100, 150 g/kg wet weight basis) was added to ice cream.
With the addition of GWL, the total anthocyanins and phenolics in the ice cream
increased with the amount of GWL. Therefore, GWL could contribute anthocya-
nins to enhance the antioxidant activity of ice cream. Nevertheless, GWL contents
showed unpleasant effects such as the increase of particle size of fat globule. Based
on experiments, a low-level (50 g/kg) GWL is advised to be added to the ice cream;

it improves the quality without disadvantages.
Naziri et al. (2014) described the utilizable by-products of the agrifood industry
in Greece (oil, wine, rice) and proposed chemical and biotechnological tools for the
recovery/production of food, feed, or energy.
5.5.4.3 Wastewater in Wineries

Peak wastewater generation in wineries occurs during the “cruch,” when grapes are
actively processed into juice for fermentation. This process requires large amounts of
clean water for washing newly harvested grapes, and results in a high wastewater output.
Wastewater is generated during the cleaning of wine-making equipment and facilities,
as well. The quantity and quality of wastewater shows seasonal variations. Wastewater
handling involves collection, possible treatment, then disposal, and/or reuse.
Wineries traditionally treat their wastewater with aerobic (aerated) bioreactors to
biologically degrade the biological oxygen demand (BOD). The treated wastewater
from these ponds needs to have a BOD of 40 ppm or less (depending on the location
of the winery) before the winery can discharge the water. Reducing the BOD value,
as efficiently and inexpensively as possible is the main goal of all the wastewater
treatment suppliers. (http://wecleanwater.com/html/success/winery_wastewater.htm).
The membrane technology market is growing permanently about 5% per year.
The greatest user is the food and beverage industry, followed by the wastewater treat-
ment sector. For food and beverage applications, it was US$ 230 million in 2011.
UF with membranes enables large volumes of heavily contaminated wastewater
to be treated without structural extensions to existing plants. One problem, however,
is a fine sludge with a special composition, which has to be dewatered and disposed
(www.westfalia-separator.com).
NF membrane was applied by Miao et al. (2008). A new composite NF mem-
brane was developed to treat the wastewater of wineries. The color, chemical oxygen
demand (COD), total organic carbon (TOC), and conductivity of the effluent was
retained by 95.5%, 70.7%, 72.6%, and 31.6%, respectively. Room temperature and
0.4 MPa transmembrane pressure were applied in a 10 h run.
The theory, working methods, and machinery of bioreactors for wastewater treat-
ment are detailed in Chapter 9.
REFERENCES
Abril, M., A.I. Negueruela, C. Pérez, T. Juan, G. Estopanan: Preliminary study of resveratrol
content in Aragón red and rosé vines. Food Chemistry, Vol. 92, 729–736, 2005.
Anstey, K.J., N. Cherbuin: Is it wine, alcohol in general, or the social context of alcohol
drinking that confers health benefit? International Journal of Wine Research, Vol.
2010(2), 9–10, 2010.
Artero, A., A. Artero, J.J. Tarin, A. Cano: The impact of moderate wine consumption on
health. Maturitas, Vol. 80, 3–13, 2015.
Bacchin, P., P. Aimar, R.W. Field: Critical and sustainable fluxes: Theory, experiments and
applications. Journal of Membrane Science, Vol. 281, 42–69, 2006.
Bagul, P.K., S.K. Banerjee: Application of resveratrol in diabetes: Rationale, strategies and
challenges. Current Molecular Medicine, Vol. 15(4), 312–330, 2015.
Balestrieri, M.L., C. Schiano, F. Felice, A. Casamassimi, A. Balestrieri, L. Milone, L.

Servillo, C. Napoli: Effect of low doses of red wine and pure resveratrol on circulating
endothelial progenitor cells. Journal of Biochemistry, Vol. 143, 179–186, 2008.
Banvolgyi, S., K.S. Bahceci, G. Vatai, S. Bekassy, E. Bekassy-Molnar: Partial dealcoholiza-
tion of red wine by nanofiltration and its effect on anthocyanin and resveratrol levels.
Food Science and Technology, Vol. 22(8), 677–687, 2016.
Banvolgyi, S., I. Kiss, E. Bekassy-Molnar, G. Vatai: Concentration of red wine by nanofiltra-
tion. Desalination, Vol. 198, 8–15, 2006.
Biagi, M., A.A.E. Bertelli: Wine, alcohol and pills: What future of French paradox? Life
Sciences, Vol. 131, 19–22, 2015.
Bogianchini, M., A.B. Cerezo, A. Gomis, F. Lopez, M.C. Garcia-Parrilla: Stability, antioxi-
dant activity and phenolic composition of commercial and reverse osmosis obtained
dealcoholized wines. LWT—Food Science and Technology, Vol. 44, 1369–1375, 2011.
Boissier, B., F. Lutin, M. Moutounet, A. Vernhet: Particle deposition during the cross-flow
microfiltration of red wines—Incidence of the hydrodynamic conditions and of the
yeast to fines ratio. Chemical Engineering and Processing, Vol. 47, 276–286, 2008.
Buffon, P., H. Heimann, D.E. Block: Sensory and chemical effects of cross-flow filtration on
white and red wines. American Journal of Enology and Viticulture, Vol. 65(3), 305–
314, 2014.
Careri, M., C. Corradini, L. Elviri, I. Nicoletti, I. Zagnoni: Direct HPLC analysis of quer-
cetin and trans-resveratrol in red wine, grape and winemaking byproducts. Journal of
Agricultural and Food Chemistry, Vol. 51, 5226–5231, 2003.
Catarino, M., A. Mendes: Dealcoholizing wine by membrane separation process. Innovative
Food Science and Emerging Technologies, Vol. 12, 330–337, 2011.
Chanukya, B.S., N.K. Rastogi: Extraction of alcohol from wine and color extracts using liquid
emulsion membrane. Separation and Purification Technology, Vol. 105 41–47, 2013.
Cliff, M.A., M.C. King, J. Schlosser: Anthocyanin, phenolic composition, colour measure-
ment and sensory analysis of BC commercial red wines. Food Research International,
Vol. 40, 92–100, 2007.
Cortell, J.M., M. Halbleib, A.V. Gallagher, T.L. Righetti, J.A. Kennedy: Influence of vine
vigor on grape (Vitis vinifera L. cv. Pinot noir) anthocyanins. 2. Anthocyanins and
pigmented polymers in wine. Journal of Agricultural and Food Chemistry, Vol. 55,
6585–6595, 2007.
Cortella, G., C. Da Porto: Design of continuous distillation plant for the production of spirits
originating from fermented grape. Journal of Food Engineering, Vol. 58, 379–385, 2003.
Czekaj, P., F. López, C. Güell: Membrane fouling by turbidity constituents of beer and wine:
Characterization and prevention by means of infrasonic pulsing. Journal of Food
Engineering, Vol. 49, 25–36, 2001.
Diban, N., A. Arruti, A. Barcelo, M. Puxue, A. Urtiaga, I. Ortiz: Membrane dealcoholization
of different wine varieties reducing aroma losses. Modeling and experimental valida-
tion. Innovative Food Science and Emerging Technologies, Vol. 20, 259–268, 2013.
Diban, N., V. Athes, M. Bes, I. Souchon: Ethanol and aroma compounds transfer study for
partial dealcoholization of wine using membrane contactor. Journal of Membrane
Science, Vol. 311, 136–146, 2008.
El Rayess, Y., C. Albasi, P. Bacchin, P. Taillandier, J. Raynal, M. Mietton-Peuchot, A.
Devatine: Cross flow microfiltration applied to oenology: A review. Journal of
Membrane Science, Vol. 382, 1–19, 2011.
Eperjesi, I., M. Kallay, I. Magyar: Boraszat (Oenology), Mezogazda Kiado, Budapest, 1998
(in Hungarian).
Fang, F., J.-M. Li, P. Zhang, K. Tang, W. Wang, Q.-H. Pan, W.-D. Huang: Effects of grape
variety, harvest date, fermentation vessel and wine ageing on flavonoid concentration
in red wines. Food Research International, Vol. 41, 53–60, 2008.
Faundez, C.A., J.O. Valderrama: Phase equilibrium modeling in binary mixtures found in
wine and must distillation. Journal of Food Engineering, Vol. 65, 577–583, 2004.
Fedrizzi, B., E. Nicolis, F. Camin, E. Bocca, C. Carbognin, M. Scholz, P. Barbieri, F. Finato,
R. Ferrarini: Stable isotope ratios and aroma profile changes induced due to innova-
tive wine dealcoholization approaches. Food and Bioprocess Technology, Vol. 7(1),
62–70, 2014.
Field, R.W., D. Wu, J.A. Howell, B.B. Gupta: Critical flux concept for microfiltration fouling.
Journal of Membrane Science, Vol. 100, 259–272, 1995.
Fontoin, H., C. Saucier, P.-L. Teissedre, Y. Glories: Effect of pH, ethanol and acidity on
astringency and bitterness of grape seed tannin oligomers in model wine solution. Food
Quality and Preference, Vol. 19, 286–291, 2008.
Gambuti, A., D. Strollo, M. Ugliano, L. Lecce, L. Moio: Trans-Resveratrol, quercetin, (+)-cat-
echin, and (–)-epicatechin content in south Italian monovarietal wines: Relationship
with maceration time and marc pressing during winemaking. Journal of Agricultural
and Food Chemistry, Vol. 52, 5747–5751, 2004.
Garcia-Martin, N., S. Perez-Magarino, M. Ortega-Heras, C. Gonzales-Huerta, M. Mihnea,
M.L. Gonzales-Sanjose, L. Palacio, P. Pradanos, A. Hernandez: Sugar reduction in
musts with nanofiltration membranes to obtain low alcohol content wine. Separation
and Purification Technology, Vol. 76, 158–170, 2010.
Gerogiannaki-Christopoulou, M., P. Athanasopoulos, N. Kyriakidis, I.A. Gerogiannaki,
M. Spanos: trans-Resveratrol in wines from the major Greek red and white grape vari-
eties. Food Control, Vol. 17, 700–706, 2006.
Gil, M., S. Estevez, N. Kontoudakis, F. Fort, J.M. Canals, F. Zamora: Influence of partial
dealcoholization by reverse osmosis on red wine composition and sensory characteris-
tics. European Food Research and Technology, Vol. 237, 481–488, 2013.
Gomez-Plaza, E., J.M. Lopez-Nicolas, J.M. Lopez-Roca, A. Martinez-Cutillas:
Dealcoholization of wine. Behaviour of the aroma components during the process.
Lebensmittel Wissenschaft und Technology—Food Science and Technology, Vol. 32,
384–386, 1999.
Goncalves, F., C. Fernandes, P. Cameira dos Santos, M.N. de Pinho: Wine tartaric stabiliza-
tion by electrodialysis and its assessment by the saturation temperature. Journal of
Food Engineering, Vol. 59, 229–235, 2003.
Gonzalez, R., M. Quiros, P. Morales: Yeast respiration of sugars by non-Sacccharomyces
yeast species: A promising and barely explored approach to lowering alcohol content of
wines. Trends in Food Science and Technology, Vol. 29, 55–61, 2013.
Gurbuz, O., D. Gocmen, F. Dagdelen, M. Gursoy, S. Aydin, I. Sahin, L. Buyukuysal, M. Usta:
Determination of flavan-3-ols and trans-resveratrol in grapes and wine using HPLC
with fluorescence detection. Food Chemistry, Vol. 100, 518–525, 2007.
Hackman, R.M., J.A. Polagruto, Q.Y. Zhu, B. Sun, H. Fujii, C.L. Keen: Flavanols: digestion,
absorption and bioactivity. Phytochemistry Reviews, Vol. 7(1), 195–208, 2008.
http://wecleanwater.com/html/success/winery_wastewater.htm.
Hwang, J.Y., Y.S. Shyu, C.K. Hsu: Grape wine lees improves the rheological and adds anti-
oxidant properties to ice cream. LWT—Food Science and Technology, Vol. 42, 312–318,
2009.
Jimenez, J.B., J.M. Orea, A. Gonzalez Urena, P. Escribano, P. Lopez de la Osa, A.
Guadarrama: Short anoxic treatments to enhance trans-resveratrol content in grapes
and wine. European Food Research and Technology, Vol. 224, 373–378, 2007.
Juan, M.E., U. Wenzel, H. Daniel, J.M. Planas: Resveratrol induces apoptosis through ROS-
dependent mitochondria pathway in HT-29 human colorectal carcinoma cells. Journal
of Agricultural and Food Chemistry, Vol. 56, 4813–4818, 2008.
Kallay, M.: Boraszati kemia (Wine Chemistry), Mezogazda Kiado, Budapest, 2012 (in
Hungarian).
Kelebek, H., A. Canbas, T. Cabaroglu, S. Selli: Improvement of anthocyanin content in the cv.
Öküzgözü wines by using pectolytic enzymes. Food Chemistry, Vol. 105, 334–339, 2007.
Kelebek, H., A. Canbas, S. Selli, C. Saucier, M. Jourdes, Y. Glories: Influence of different
maceration times on the anthocyanin composition of wines made from Vitis vinifera L.
cvs. Bogazkere and Öküzgözü. Journal of Food Engineering, Vol. 77, 1012–1017, 2006.
Labanda, J., S. Vichi, J. Llorens, E. López-Tamames: Membrane separation technology for
the reduction of alcoholic degree of a white model wine. LWT—Food Science and
Technology, Vol. 41, 1390–1395, 2009.
Lachman, J., M. Sulc, M. Schilla: Comparison of the total antioxidant status of Bohemian
wines during the wine-making process. Food Chemistry, Vol. 103, 802–807, 2007.
Lee, J., R.W. Durst, R.E. Wrolstad: Determination of total monomeric anthocyanin pigment con-
tent of fruit juices, beverages, natural colorants, and wines by the pH differential method:
Collaborative study. Journal of AOAC International, Vol. 88(5), 1269–1278, 2005.
Liguori, L., P. Russo, D. Albanese, M. Di Matteo: Evolution of quality parameters during red
wine dealcoholization by osmotic distillation. Food Chemistry, Vol. 140, 68–75, 2013a.
Liguori, L., P. Russo, D. Albanese, M. Di Matteo: Effect of process parameters on partial
dealcoholization of wine by osmotic distillation. Food Bioprocess Technology, Vol. 6,
2514–2524, 2013b.
Lipnizki, F., C.-E. Nielsen, R. Betcke, J.D. Caprio: Food & Bev: Anyone for a tasty beverage?
Filtration and Separation, Vol. 43(March), 14–18, 2006.
Lipnizki, F., J. Olsson, G. Tragardh: Scale-up pervaporation for the recovery of natural aroma
compounds in the food industry. Part 1: Simulation and performance. Journal of Food
Engineering, Vol. 54., 183–195, 2002.
Lisanti, M.T., A. Gambuti, A. Genovese, P. Piombino, L. Moio: Partial dealcoholisation of red
wines by membrane contactor technique: Effect on sensory characteristics and volatile
composition. Food and Bioprocess Technology, Vol. 6(9), 2289–2305, 2013.
Lopez, N., E. Puertolas, P. Hernandez-Orte, I. Alvarez, J. Raso: Effect of a pulse electric field
treatment on the anthocyanins composition and other quality parameters of Cabernet
Sauvignon freshly fermented model wines obtained after different maceration times.
LWT—Food Science and Technology, Vol. 42, 1225–1231, 2009.
Lopez-Vélez, M., F. Martinez-Martinez, C. del Valle-Ribes: The study of phenolic compounds
as natural antioxidants in wine. Critical Reviews in Food Science and Nutrition, Vol.
43, 233–244, 2003.
Mannapperuma, J.D.: Membrane application in grape juice and wine processing, 2003. Internet
document, www.energy.ca.gov/reports2003-03-21_400-02-020F.PDF. Accessed 20/01/04.
Manninger, K., E. Bekassy-Molnar, Gy. Vatai, M. Kallay: Pretreatment effect on the quality
of white and red wines using cross-flow ceramic membrane filtration. Acta Alimentaria,
Vol. 27, 377–387, 1998.
Marel, A.-K., G. Lizard, J.-C. Izard, N. Latruffe, D. Delmas: Inhibitory effect of trans-resve-
ratrol analogs molecules on the proliferation and the cell cycle progression of human
colon tumoral cells. Molecular Nutrition and Food Research, Vol. 52(5), 538–548,
2008.
Masamitsu Takaya, Nobuya Matsumoto, Hideshi Yanase: Characterisation of membrane bio-
reactor for dry wine production. Journal of Bioscience and Bioengineering, Vol. 93(2),
240–244, 2002.
Massot, A., M. Mietton-Peuchot, C. Peuchot, V. Milisic: Nanofiltration and reverse osmosis
in winemaking. Desalination, Vol. 231, 283–289, 2008.
Mermelstein, N.H.: Removing alcohol from wine. Food Technology, Vol. 54, 89–92, 2000.
Miao, J., L. Li, G. Chen, C. Gao, S. Dong: Preparation of N,O-carboxymethyl chitosan com-
posite nanofiltration membrane and its rejection performance for the fermentation
effluent from a wine factory. Chinese Journal of Chemical Engineering, Vol. 16(2),
209–213, 2008.
Mietton-Peuchot, M., V. Milisic, P. Noilet: Grape must concentration by using reverse osmo-
sis. Comparison with chaptalization. Desalination, Vol. 148, 125–129, 2002.
Minussi, R.C., M. Rossi, L. Bologna, L. Cordi, D. Rotilio, G.M. Pastore, N. Durán: Phenolic
compounds and total antioxidant potential of commercial wines. Food Chemistry, Vol.
82, 409–416, 2003.
Mi Oh, Ji-Hye Lee, Seon Young Bae, Jong Hyeon Seok, Sella Kim, Yeon Bin Chung, Kang
rok Han, Kyung Hyun Kim, Mi Sook Chung: Protective effects of red wine and resve-
ratrol for foodborne virus surrogates. Food Control, Vol 47, 502–509, 2015.
Mokni, M., F. Limam, S. Elkahoui, M. Amri, E. Aouani: Strong cardioprotective effect of
resveratrol, a red wine polyphenol, on isolated rat hearts after ischemia/reperfusion
injury. Archives of Biochemistry and Biophysics, Vol. 457, 1–6, 2007.
Moreno, J., J. Peinado, R.A. Peinado: Antioxidant activity of musts from Pedro Ximénez
grapes subjected to off-vine drying process. Food Chemistry, Vol. 104, 224–228,
2007.
Mori, K., N. Goto-Yamamoto, M. Kitayama, K. Hashizume: Loss of anthocyanins in red-
wine grape under high temperature. Journal of Experimental Botany, Vol. 58(8), 1935–
1945, 2007.
Murias, M., M. Miksits, S. Aust, M. Spatzenegger, T. Thalhammer, T. Szekeres, W. Jaeger:
Metabolism of resveratrol in breast cancer cell lines: Impact of sulfotransferase 1A1
expression on cell growth inhibition. Cancer Letters, Vol. 261, 172–182, 2008.
Naziri, E., N. Nenadis, F.Th. Mantzouridou, M.Z. Tsimidou: Valorization of the major agri-
food industrial by-products and waste from Central Macedonia (Greece) for the recov-
ery of compounds for food application. Food Research International, Vol. 65, 350–358,
2014.
Norrie, P.A.: Resveratrol-enhanced wine. International Journal of Wine Research, Vol.
2009(1), 187–188, 2009.
Nurgel, C., G.J. Pickering, D.L. Inglis: Sensory and chemical characteristics of Canadian ice
wines. Journal of the Science of Food and Agriculture, Vol. 84(13), 1675–1684, 2004.
Paixao, N., R. Perestrelo, J.C. Marques, J.S. Camara: Relationship between antioxidant
capacity and total phenolic content of red, rosé and white wines. Food Chemistry, Vol.
105, 204–214, 2007.
Palacios, V.M., I. Caro, L. Perez: Comparative study of crossflow microfiltration with conven-
tional filtration of sherry wines. Journal of Food Engineering, Vol. 54, 95–102, 2002.
Palliotti, A., S. Tombesi, O. Silvestroni, V. Lanari, M. Gatti, S. Poni: Changes in vineyard
establishment and canopy management urged by earlier climate-related ripening: A
review. Scientia Horticulturae, Vol. 178, 43–54, 2014.
Pilipovik, M.V., C. Riverol: Assessing dealcoholization systems based on reverse osmosis.
Journal of Food Engineering, Vol. 69, 437–441, 2005.
Pour Nikfardjam, M.S., L. Mark, P. Avar, M. Figler, R. Ohmacht: Polyphenols, anthocyanins,
and trans-resveratrol in red wines from the Hungarian Villany region. Food Chemistry,
Vol. 98, 453–462, 2006a.
Pour Nikfardjam, M.S., G. Laszlo, H. Dietrich: Resveratrol-derivatives and antioxidative
capacity in wines made from botrityzed grapes. Food Chemistry, Vol. 96. 74–79, 2006b.
Puangpronpitag, D., P. Areejitranusorn, P. Boonsiri, M. Suttajit, P. Yongvanit: Antioxidant
activities of polyphenolic compounds isolated from Antidesma thwaitesianum Müll.
Arg. seeds and marcs. Journal of Food Science, Vol. 73(9), C648–C653, 2009.
Quiros, M., V. Rojas, R. Gonzales, P. Morales: Selection of non-Saccharomyces yeast strains
for reducing alcohol levels in wine by sugar respiration. International Journal of Food
Microbiology, Vol 181, 85–91, 2014.
Regitz, C., E. Fitzenberger, F.L. Mahn, L.M. Dussling, U. Wenzel: Resveratrol reduces amyloid-
beta (Aβ1-42)-induced paralysis through targeting proteostasis in an Alzheimer model of
Caenorhabditis elegans. European Journal of Nutrition, Vol. 55(2), 741–747, 2016.
Ribeiro de Lima, M.T., P. Waffo-Téguo, P.L. Teissedre, A. Pujolas, J. Vercauteren, J.C.

Cabanis, J.M. Merillon: Determination of stilbenes (trans-astringin, cis- and trans-
piceid, and cis- and trans-resveratrol) in Portuguese wines. Journal of Agricultural and
Food Chemistry, Vol. 47, 2666–2670, 1999.
Robinson, J.: Winecourse. BBC Worldwide Ltd., London, 2003.
Ruiz-Rodriguez, A., T. Fornani, L. Jaime, E. Vazquez, B. Amador, J.A. Nieto, M. Yuste, M.
Mercader, G. Reglero: Supercritical CO2 extraction applied toward the production of
functional beverage from wine. The Journal of Supercritical Fluids, Vol. 61, 92–100,
2012.
Saiko, P., A. Szakmary, W. Jaeger, T. Szekeres: Resveratrol and its analogs: Defense against
cancer, coronary disease and neurodegenerative maladies or just a fad? Mutation
Research, Vol. 658, 68–94, 2008.
Salazar, F.N., J.P.F. de Bruijn, L. Seminario, C. Guell, F. Lopez: Improvement of wine cross-
flow microfiltration by a new hybrid process. Journal of Food Engineering, Vol. 79,
1329–1336, 2007.
Serafini, M., G. Maiani, A. Ferro-Luzzi: Alcohol-free red wine enhances plasma antioxidant
capacity in humans. Journal of Nutrition, Vol. 128, 1003–1007, 1998.
Stervbo, U., O. Vang, C. Bonnesen: A review of the content of the putative chemopreventive
phytoalexin resveratrol in red wine. Food Chemistry, Vol. 101, 449–457, 2007.
Takacs, L., G. Vatai, K. Korany: Production of alcohol free wine by pervaporation. Journal
Food Engineering, Vol. 78, 118–125, 2007.
Ulbricht, M., W. Ansorge, I. Danielzik, M. Konig, O. Schuster: Fouling in microfiltration of
wine: The influence of membrane polymer on adsorption of polyphenols and polysac-
charides. Separation and Purification Technology, Vol. 68, 335–342, 2009.
van der Bruggen, B., C. Vandecasteele: Flux decline during nanofiltration of organic compo-
nents in aqueous solution. Environmental Science and Technology, Vol. 35, 3535–3540,
2001.
Varavuth, S., R. Jiraratananon, S. Atchariyawut: Experimental study on dealcoholization of
wine by osmotic distillation process. Separation and Purification Technology, Vol. 66,
313–321, 2009.
Vernhet, A., D. Cartalade, M. Moutounet: Contribution to the understanding of fouling build-up
during microfiltration of wines, Journal of Membrane Science, Vol. 211, 357–370, 2003.
Vingtdeux, V., U. Dreses-Werringloer, H. Zhao, P. Davies, P. Marambaud: Therapeutic poten-
tial of resveratrol in Alzheimer’s disease. BMC Neuroscience, Vol. 9, Article number
S6, 2008.
Wollan, D.: The Memstar AA process for alcohol adjustment. www.memstar.com.au,
Accessed 2004.
www.westfalia-separator.com
Xiuzhi Tian, Baoku Zhu, Youyi Xu: P(VDF-co-HFP) membrane for recovery of aroma
compounds from aqueous solutions by pervaporation. Journal of Membrane Science,
Vol. 248, 109–117, 2005.
Xuan Yang, Xun Li, Jinyu Ren: From French paradox to cancer treatment: Anti-cancer activi-
ties and mechanisms of resveratrol. Anti-Cancer Agents in Medicinal Chemistry, Vol.
14(6), 806–825, 2014.
Yoo, Y.J., A.J. Saliba, P.D. Prenzler: Should red wine be considered a functional food?
Comprehensive Reviews in Food Science and Food Safety, Vol. 9(5), 530–551, 2010.
Zeng, X.A., X.D. Chen, F.G.F. Qin, L. Zhang: Composition analysis of litchi juice and litchi
wine. International Journal of Food Engineering, Vol. 4, Article 7, 2008.
6 Fruit and Vegetable Juice
Processing Applications
Gyula Vatai
CONTENTS
6.1 Introduction................................................................................................... 195
6.2 Conventional Technology for Fruit Juice Production.................................... 196
6.2.1 Juice Extraction by Pressing.............................................................. 197
6.2.2 Juice Extraction by Water as Solvent................................................. 198
6.2.3 Juice Clarification.............................................................................. 198
6.3 Conventional Technology for Fruit Juice Concentrate Production................ 201
6.4 Fruit Juice Concentration by Membrane Separation Processes....................202
6.5 Other Applications of Membrane Separation Processes in
Fruit Juice Production Technologies.............................................................. 223
6.5.1 Aroma Recovery................................................................................ 223
6.5.2 Deacidification................................................................................... 230
6.5.3 Novel Products................................................................................... 231
6.6 Vegetable Juice Processing and Concentration by Membrane
Separation Processes..................................................................................... 232
References............................................................................................................... 234
6.1 INTRODUCTION
With changing nutrition patterns in the last 20 years, the focus of interest is on plants
that have many valuable components. Fruit juices play a very important role in this
phenomenon. Fruits can be consumed fresh in their natural form, some of them even
during winter (apples, oranges, etc.) when they are stored in a proper way. In the last
century, drinking of fruit juices extracted from fruits was the privilege of rich peo-
ple, but nowadays, most customers seek high-quality fruit juices (Hui et al., 2006).
The raw materials for the production of fruit juices can be grouped into citrus
fruits, pomaceous fruits, stone fruits, grapes, and berries. Some of these raw mate-
rials are suitable for direct juice production, such as apple and orange, where the
produced juice can be consumed without any additive, but the juices of some berries
(black and red currant, sea buckthorn) are very acidic and can be used only when
blended with sugar syrup or a concentrate of apple juice or grape must. Fruit juice-
based drinks are classified into three categories on the basis of fruit content: juices
or fruit musts, fruit nectars, and soft drink with fruit content.
Juices are extracted by mechanical procedures, mainly pressing, and the
extracted juice has the same taste, color, and aroma as that of the original fruit, and
195
the composition is also identical with that of the original fruit. Juices may not con-
tain food additives (preservatives, aromas, and coloring agents). They are consumed
fresh soon after extraction or are used as raw material for concentration. Fruit juices
can be divided into two categories: juices without colloids, that is, clarified to be
transparent (apple, grape), or cloudy juices that contain colloids and fibers such as all
citrus-based juices and apricot juice (Rizvi, 2010).
Fruit nectars usually contain only one fruit such as apple, orange, or peach, but they
can be made from blends of more than one fruit juice or pulp. Usually, they are made
from fruit pulps or fruit juices diluted with sugar syrup. The preparation of blends and
minimum fruit content are regulated by standards, industrial specifications, and other
requirements (Hui et al., 2006). These standards conform to the Codex Alimentaria
of the FAO/WHO Food Standard Program in order to ensure international trade.
Today, to consume some kind of fruit juice during the whole year, the production
of a concentrate with high dissolved solids is necessary, for storing the concentrate
frozen in the refrigerator or at room temperature, depending on the dissolved solid
content. The concentrate after dilution with water can be used as a fruit drink or fruit
juice with the same characteristics as that of the original fresh juice if the concentra-
tion process has been carried out in a proper way (Rizvi, 2010).
The industrial concentration of fruit juices is usually performed by multistage
vacuum evaporators. In most of the cases, volatile components are recovered by
rectification and added back to the concentrated product. The evaporation mainly
causes heat degradation of many valuable compounds. To avoid this remarkable
decrease in quality, nonthermal concentration methods are needed, such as freeze
concentration systems and membrane separation processes (Barta and Körmendy,
2007; Jiao et al., 2004; Kiss et al., 2004).
6.2 CONVENTIONAL TECHNOLOGY FOR

FRUIT JUICE PRODUCTION
Juice extraction, the removal of juice from fibrous solid particles, is the basic opera-
tion in fruit juice production. For this operation, that is, the separation step, the
fruit has to be prepared. This preparation step depends on the type of the fruit;
in some cases, the fruit has to be chopped (apple, peach, etc.), but in certain other
cases (cherry, sour cherry, plum, apricot, etc.), stem elimination is very important
before chopping. A typical flow diagram of the natural juice and juice concentrate
production is shown in Figure 6.1. In this scheme of concentrate production, several
conventional separation processes can be recognized:
• Mechanical pressing of the juice from the fruit pulp

• Juice extraction from the marc by using water as solvent
• Clarification of the fruit juice by centrifugation or filtration
• Concentration of the fruit juice by multistep vacuum evaporation
The presented fruit juice production technology is a typical one (Barta and
Körmendy, 2007) for the production of fresh natural fruit juice and concentrate for
longer storage.
Fruit and Vegetable Juice Processing Applications 197
Reception of the fruits
Cleaning of the
Washing
washing water
Stem elimination
Marc
Juice extraction—pressing
Secondary juice Clarification by

extraction centrifugation
Aroma extraction
Pasteurization
Enzyme treatment
Storage
Clarification by
centrifugation
Natural, unfiltered
Concentration by juice
evaporation
Storage
Fruit juice concentrate
FIGURE 6.1 Production of natural fruit juice and fruit juice concentrate using conventional
separation processes. (From Barta, J., Körmendy, I. 2007. Basic Processes of Vegetable and
Fruit Processing Technologies (in Hungarian). Mezőgazda Kiadó, Budapest.)
In last few decades, some of the conventional separation processes have been
replaced by newer ones such as the clarification step, where the traditional clarifica-
tion by centrifugal separation or filtration has been replaced by ultrafiltration (UF),
especially in the case of clarified or “transparent” juice production from fruits such
as apple and grape (Barta and Körmendy, 2007).
6.2.1 Juice Extraction by Pressing

In this separation process, the liquid phase of fruits is separated from the solid par-
ticles. The most common method for this separation is mechanical pressing of the
juice from the fruit pulp. The type of equipment used for this separation depends
on the fruit species; in case the hard parts of the fruit (stem) have been previously
removed (cherry, plum, apricot), typical mechanical pressing at higher pressure can
be used, while in case of pressing of berry-type fruits such as grapes and currants,
mild pneumatic pressing is more advantageous (Barta and Körmendy, 2007). In both
cases, pressing needs outside forces to create a tension in the system, draining out
the liquid, which results in shape modification. In batch systems, the solid phase will
remain in the pressing vessel, while the liquid will be drained out across a sieve and/
or filter media. The remaining solid phase with low liquid content is called marc.
The most important parameter of pressing is the liquid, for example, juice yield,
which means the percentage of juice pressed out compared to the raw material that
entered the system. The juice yield is determined basically by the preparation and
pretreatment (enzymatic hydrolysis or not, etc.) of the fruit before pressing and the
applied pressure (Barta and Körmendy, 2007; Hui et al., 2006). In the fruit juice pro-
cessing industry, basket-type batch pressing machines are commonly used in which
a decrease in the press machine volume by mechanical or hydraulic forces is often
used as well as a decrease in the space for fruit pulp/marc by pneumatic interaction
at lower pressure, up to 2–3 bars applied.
In this conventional technology, the yield of the juice can be improved by using
enzyme treatment for pectin degradation as well as by the extraction of the residual
fruit juice from the marc using hot water (50–90°C) (Hui et al., 2006).
6.2.2 Juice Extraction by Water as Solvent

The fruit juice yield can be improved by solid–liquid extraction. In this operation,
mass transfer is usually controlled by the molecular diffusion of certain components,
which can be improved by increasing the temperature of the operation. In order to
increase the diffusion coefficient and the permeability of the cell walls, the solid–
liquid extraction is performed at 50–70°C. Another method to improve mass transfer
is to increase the specific area for transport, in most cases, by decreasing the particle
size of the solid phase, that is, chopping the fruits. By increasing the concentration
gradient for mass transfer with a higher solvent–solid ratio, or multistep cocurrent
or countercurrent operation mode, the yield of the valuable components can also be
increased. Diffusion juice extraction is usually carried out in double-screw extractor
devices or sometimes in presses (Hui et al., 2006).
6.2.3 Juice Clarification

The pressed and/or solvent-extracted fruit juices are usually turbid, containing plant
particles (fibers, cellulose, starch, lipids) and colloids such as pectin, proteins, and
polyphenols. Depending on the type of the final product, these substances must
be partially or totally removed to avoid further turbidity and precipitation and to
improve sensory attributes such as taste, color, and odor. This clarification step can
be performed with physicochemical or mechanical methods as well as using combi-
nations of these methods (Rizvi, 2010).
The aim of mechanical clarification is also the removal of suspended solids
using only mechanical separation processes such as centrifugation or filtration.
This separation process is performed in settling centrifuges; eliminating fibers from

cloudy juices. Filtration is the next step of fruit juice production. The traditional
method is by using slurry layer-based devices and operation mode using silica or
perlite as additives. The filtration equipment should be frame filter press, continu-
ous vacuum drum filter, or others. For the clarification of filtered juice membrane
filtration, UF or microfiltration (MF) has been widely applied in the last two decades
(Bélafiné Bakó, 2002; Carvalho et al., 2008; Cassano et al., 2007a,b; Fonyó and
Fábry, 1998). These membrane filtrations are able to solve the problem of clarifica-
tion and filtration in one step (Cheryan, 1998; Rautenbach, 1997).
These clarified and filtered or cloudy juices are ready for consumption. The juice
can be packed and pasteurized and released to the market, or it can be a good raw
material for the production of semifinished products.
Cassano et al. (2007b) investigated the influence of operation parameters on the
quality of blood orange juice and membrane fouling. The pilot plant they used was
the same as that used by Galverna et al. (2008), a tube-type KOCH membrane mod-
ule made from polyvinylidene difluoride (PVDF) with a 15 kDa nominal molecular
weight cut-off (NMWCO) with a filtration area of 0.23 m2. The UF system was oper-
ated at a low transmembrane pressure (TMP) of 0.85 bar, with a volume reduction
factor (VRF) of 6.0. Besides total soluble solid (TSS) measurements, the total anti-
oxidant activity (TAA) of each product and raw juice as well as the total anthocyanin
content were determined. Two flavonones (hesperidin and narirutin) were also deter-
mined. The mathematical model developed by Field et al. (1995) was applied for the
results of the experiments with three parameters: the limiting flux (Jlim), exponent in
the equation (n), and parameter (k). The values of n are 0, which means cake filtra-
tion; 1, which means partial pore blocking; and 2, which means total pore blocking.
Using the limiting TMP of 0.85 bar, they observed partial pore blocking (n = 1) at the
lowest flow rate and value of Reynolds number (5800), while at higher Re numbers
(7000–9300), the total blocking mechanism (n = 2) was observed, as well as a lin-
ear trend between the permeate flux and recirculation flow rate. On the basis of the
analysis, TAA, ascorbic acid, total anthocyanins, and narirutin as well as hesperidin
content more than 80% in the permeate, which means there is only a 20% loss of
these components when clarified by the 15 kDa NMWCO UF membrane.
Cassano et al. (2007b) investigated the UF of kiwifruit juice, using pilot plant UF
equipment with tubular KOCH membranes. In the UF process, they analyzed the
resistances during the clarification of the kiwifruit juice. Besides membrane resis-
tance, they supposed a cake resistance and fouling resistance composed of revers-
ible and irreversible parts. They observed that in the total resistance, membrane
resistance contributed 70%, while cake and fouling resistances contributed 30%, in
which cake resistance and reversible fouling resistance were negligible, 2.2% and
2.8%, respectively. They selected the best conditions for kiwifruit juice clarification:
90 kPa TMP at 25°C and 700 L/h recirculation flow rate.
The effect of changes in the hydrodynamic conditions and external electric field
on the permeate flux during the UF of synthetic and mosambi juice in a cross-flow
channel has been studied by Rai et al. (2010). The hydrodynamic conditions inside
the cross-flow channel were changed from laminar flow, laminar flow with turbu-
lent promoters, and flow in the transition and turbulent regime. They reached the
steady-state permeate flux in the range of 17.5–18.5 L/(m2h) at Re = 657, laminar

flow) for operating pressures of 276–552 kPa). This range was between 18 and
22.5 L/(m2h) using turbulent promoters at the same Reynolds number and between
35 and 43 L/(m2h) in the transition flow regime at the same operating pressure. In
the third case, they investigated the effects of external electric field (a body force) on
the permeate flux. For actual depectinized mosambi juice, about 50% enhancement
of steady-state flux was achieved with an external electric field of strength 500 V/m
(Rai et al., 2010).
Membrane fouling is a major obstacle in the application of MF (Laorko et al.,
2011). Several techniques have been proposed to enhance the permeate flux during
MF. Gas sparging is a hydrodynamic method for improving the performance of the
membrane process by Laorko et al. (2011). In the study, a 200-nm hollow fiber MF
membrane was used to study the effect of cross-flow velocity (CFV) and gas injec-
tion factor (c) on the critical and limiting flux during the MF of pineapple juice. In
addition, the phytochemical properties of clarified juice were investigated. In the
absence of gas sparging, the critical and limiting flux increased as the CFV or shear
stress number increased. The use of gas sparging led to a remarkable improvement
in both the critical and limiting flux but it was more effective at lower CFV (1.5 m/s),
compared to those at higher CFV (2.0 and 2.5 m/s). When the gas injection factor
was applied at 0.15, 0.25, and 0.35 with a CFV of 1.5 m/s, enhancements of 55.6%,
75.5%, and 128.2% were achieved for the critical flux, while enhancements of 65.8%,
69.7%, and 95.2% were achieved for the limiting flux, respectively. The researchers
also indicated that the use of gas sparging was an effective method to reduce revers-
ible fouling and external irreversible fouling rather than internal irreversible fouling.
In addition, the CFV and gas sparging did not affect the color, the total phenolic con-
tent, and the antioxidant property of the clarified juice. The l-ascorbic acid and total
vitamin C were significantly decreased when higher CFV and high gas injection
factor were applied. The results also indicated that the use of gas sparging with low
CFV was beneficial for flux enhancement while most of the phytochemical proper-
ties of the clarified juice were preserved (Laorko et al., 2011).
Neifar et al. (2011) investigated the possibility of the removal of phenolic com-
pounds of pomegranate juice, which are responsible for haze formation and brown-
ing during storage. They investigated selective removal by a combined enzyme–UF
process. They treated the pomegranate juice with Fomes fomentarius laccase at vari-
ous enzyme concentrations (0.5–5 U/mL), temperatures (20–50°C), and processing
times (30–300 min). Their application led to a 40% reduction of total phenol content,
but on the other hand, the clarity of the juice was decreased threefold at optimum
treatment conditions: enzyme concentration 5 U/mL; time 300 min; and temperature
20°C. This drawback was removed by UF of the laccase-treated juice. The pome-
granate juice obtained using this combination was clear, stable, and characterized by
high total phenolics, good clarity, and color compared to untreated juice; the changes
were 30%–40% (Neifar et al., 2011).
Domingues et al. (2014) investigated passion fruit juice clarification by MF when
the influence of some pretreatments (centrifugation, enzymatic liquefaction, and
chitosan coagulation) before passion fruit juice MF was studied. They concluded
that enzymatic treatment reduced the juice viscosity, and the centrifugation step
was important for color and turbidity reductions. Chitosan addition was the most
promising pretreatment, since it provided the highest reductions of color and tur-
bidity, enabling the highest permeate flux in the MF process of pretreated passion
fruit juice. The MF process with hollow fiber membranes resulted in a clean passion
fruit juice, almost free of turbidity. The applied pretreatment did not influence the
characteristics of the permeate produced. The researchers investigated the fouling
mechanism at different pretreatments and concluded that the mechanism depends on
the applied pretreatment: in centrifuged and enzyme-treated samples, cake forma-
tion was found to be the major fouling factor, while internal pore blocking occurred
during the filtration of the chitosan-pretreated sample (Domingues et al., 2014).
6.3 CONVENTIONAL TECHNOLOGY FOR FRUIT

JUICE CONCENTRATE PRODUCTION
As shown in Figure 6.1, after the production of the fruit juice by either pressing or
solid–liquid extraction and certain posttreatments, for longer shelf life, by decreasing
the water content and increasing the TSS content, the fruit juice can be concentrated.
This concentration improves storage and transportation properties and costs. The
operation has to be carried out very carefully to avoid loss of aroma components and
valuable ingredients, and to minimize changes in the sensory properties. The most
common method of concentration is by evaporation (Barta and Körmendy, 2007).
Evaporation is the most common method of fruit juice concentration, and from
a physical point of view, it means water evaporation from boiling liquid phase. This
unit operation is carried out in devices such as an evaporator and usually requires
steam as the energy for boiling and water evaporation. Since the valuable fruit com-
ponents are mostly heat sensitive, to avoid this phenomenon, in the case of fruit
juice concentrate production, vacuum evaporation is the right solution (Ashurst,
2005). To decrease energy consumption, batteries of 3–4 evaporator elements are
commonly used (Fonyó and Fábry, 1998). The chemical, rheological, and thermal
characteristics of juices play an important role in this evaporation–condensation
process. Because of varying of these parameters from juice to juice, the operation
parameters should be different for different fruits or juices. The type of evaporators
should be chosen for certain juice(s) based on the juice characteristics. The most
widely used types of evaporator are the film, pipe, plate, and centrifugal-based ones
(Barta and Körmendy, 2007). Evaporators are usually combined with aroma recov-
ery units—in most cases, a distillation column. The condensed aroma components
are often remixed into the concentrate to improve the flavor, or can be concentrated
and applied as natural aroma extracts for other fruit products.
Another mild method for fruit juice concentration is freezing. During this separa-
tion process, the fruit juice is cooled under the freezing temperature of water (0°C
at atmospheric pressure), in which case the water forms ice crystals, and by separat-
ing these ice crystals from the suspension, the water content is lowered, that is, the
concentration of TSS will be higher. Unfortunately, owing to the high cost of produc-
tion of “cold energy,” this technology should be used only for the concentration of
very valuable and heat-sensitive fruit juices. By using this technology, only clarified
juices should be concentrated, because during the separation of unclarified juices,
fibers and colloids will be removed together with ice. This concentration technology
can be completed in one or several steps, and using this technology, we can reach
the euthecticum concentration of the fruit juice–water system (Barta and Körmendy,
2007). The separation of the solid phase (ice) and the liquid phase (concentrated
juice) should be carried out by mechanical methods: settling, filtration, and cen-
trifugation. However, this type of concentration is a very gentle process because
there is no loss of aroma, color, and vitamin during this operation due to the low
temperature. Its disadvantages are high energy consumption and lower concentra-
tion efficiency compared to evaporative concentration (Barta and Körmendy, 2007).
6.4 FRUIT JUICE CONCENTRATION BY

MEMBRANE SEPARATION PROCESSES
For the mild method of concentration of fruit juices, reverse osmosis (RO) (Kozak,
2005; Rektor et al., 2004) and/or nanofiltration (NF) can be used (Kiss et al., 2004;
Porter, 1990). The only problem is that during this concentration process, on the
retentate side of the membrane, the concentration of the TSS becomes increasingly
higher, causing higher osmotic pressure that decreases the driving force of the con-
centration process, which is the difference between the TMP and osmotic pressure
of the retentate (fruit juice concentrate) and permeate (practically water). Using the
usual TMP (40–50 bar), the fruit juice should be concentrated in this way up to
23%–26% TSS (Belafi-Bako, 2002; Belafi-Bako et al., 2000). The advantages of this
concentration technology are better-quality juice concentrate (valuable components
such as aroma, vitamins, and polyphenols are concentrated and not destroyed), lower
energy consumption, and lower cost in comparison to evaporation (Ashurst, 2005;
Kiss et al., 2004).
After reaching the final concentration (45%–65% TSS) for storing the concen-
trate at room temperature, the semiproduct produced by RO (23%–26% TSS) should
be further concentrated by membrane distillation (MD) (El-Bourawi et al., 2006;
Laeson and Lloyd, 1997; Lagana et al., 2000), osmotic distillation (OD) (Courel
et al., 2000; Lefebvre, 1988; Thanedgunbaworn et al., 2007), or NF (Kiss et al.,
2004; Porter, 1990; Vatai, 2007). From the previous statements, fruit juice concen-
tration by membrane technology could be done in a three-step process: clarification
(UF or MF), production of “half-concentrate” by pressure-driven membrane process
(RO), and production of “final concentrate.” The production technology is shown in
Figure 6.2, with three different alternatives for the final concentration (Vatai, 2007).
Using membrane separation processes, the sterilization of the fruit juice can
be done without heating, by mechanical removal of microbes during clarification;
on the other hand, water removal—concentration of the fruit juice—can be done
at near room temperature (Jiao et al., 2004). For clarification, UF or MF is suit-
able (Carvalho et al., 2008; Cassano et al., 2007a,b; He et al., 2007); even with
UF, some valuable components (polyphenols) are removed, more than what is
required.
Apart from its energy- and quality-saving advantages, this technology for the
production of fruit juice concentrate has some other benefits. Food safety can be
improved by cold sterilization and the impact on the environment will be much
Colloids,
microrganisms ~ Water
Fruit juice Clarified juice Concentrate

MF RO
8%–16% TSS 8%–16% TSS 23%–26% TSS
NF MD OD
Concentrate Concentrate Concentrate

45%–60% TSS 55%–65% TSS 55%–65% TSS
FIGURE 6.2 Alternatives of fruit juice concentration by complex membrane processes.
lower. Practically, this is a clean technology—the main product is the juice concen-
trate, and the by-products are the membrane-filtered water and the concentrate of the
clarification, which can be added to the marc for “pálinka” or spirit production, or
also used as a raw material for the production of valuable products with high antioxi-
dant capacity by conventional or supercritical extraction.
In the proposed fruit juice concentration technology, the first step is clarifica-
tion by MF. The aim of this step is the removal of suspended solids, which causes
a decrease in the viscosity and results in higher filtration capacity. In the next
step of the membrane filtration process for concentration, the clogging of the
circulation canals, especially in spiral wound membrane modules, will be mini-
mized. In this way, the microorganisms are also removed, which results in juice
sterilization.
In Figure 6.3, typical experimental data of permeate flux change during the clari-
fication of a typical Hungarian berry fruit black currant (Ribes nigrum) MF is pre-
sented. Figure 6.3 shows the influence of the TMP (a) and recirculation flow rate
(b) on the permeate flux during the clarification of black currant juice by MF on
a laboratory apparatus. From this presentation, it can be seen that after a certain
period of time, the flux decreasing rate is stabilized, reaching a steady-state flux.
From the diagram, it is also obvious that there are differences between the permeate
fluxes at different TMPs, before the steady-state permeate flux is reached, in which
the differences are quite smaller than the differences in energy consumption due to
higher pressure. In the case of recirculation flow rates, a higher recirculation flow
rate resulted in higher fluxes and shorter treatment periods, which is true for the
steady-state fluxes reached (Banvolgyi, 2009).
From the clarified fruit juice, the so-called “half concentrate” can be produced by
NF or RO, with TSS between 23% and 28%, which can be stored frozen for a longer
time, retaining the valuable component concentration. Some results of the concen-
tration of clarified black currant juice on a laboratory-scale high-pressure membrane
filtration plant in the laboratory of Food Engineering, Corvinus University of Budapest
are presented in Figure 6.4. In Figure 6.4a, a comparison of the concentration of black
(a) 400
Permeate flux (L/(m2 h))
350
300
250 3.9 bar
200 2.4 bar
150 1 bar
100
50
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Tim e (h)
T = 30°C Qrec = 500 L/h
(b) 400
350
300
250
500 L/h
200
300 L/h
150
100 L/h
100
50
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Tim e (h)
ΔpTM = 3.9 bar T = 30°C
FIGURE 6.3 Influence of the transmembrane pressure (a) and recirculation flow rate (b) on
permeate flux during the clarification of black currant juice by microfiltration.
currant juice by NF and RO at different TMPs and the reached final content of TSS in
these concentration procedures are presented using RO and NF membranes at different
TMPs. As it can be seen from the diagram, for producing concentrate over 20% TSS,
the application of RO at higher TMP is recommended. The change in the permeate flux
and TSS in the retentate during the preconcentration of clarified black currant juice
by RO on laboratory-scale equipment at different recirculation flow rates, and con-
stant temperature and TMP, presented in Figure 6.4b, shows that there is practically no
influence of recirculation flow rate on the permeate flux and final concentration of the
retentate. The flux of the permeate in all cases decreases during this process because
of lower driving force, caused by a decrease in the osmotic pressure of the concentrate,
as well as due to an increase in the viscosity. From the figure, it is also obvious that the
final concentration at room temperature, 50 bar TMP, and all investigated volumetric
recirculation flow rates was a little bit over 28% TSS, and at the end of the experiment,
the permeate flux decreased practically to zero value (Banvolgyi, 2009).
The produced “half-concentrate” can be stored frozen for a longer time, but in
this case, the storing costs will be high, as well as the cost of transportation of the
semiproduct from the producer to the fruit drink producer, if the concentration has
(a) 30
25
TSS content (°Brix)
20
RO_50 bar
15 RO_30 bar
NF_25 bar
10
0
0 1 2 3 4 5 6
Time (h)
(b)
25 35
30
20
TSS content (°Brix)

25
15 20
10 15
10
5
5
0 0
0 2 4 6 8 10
Time (h)
Flux 500 L/h Flux 400 L/h Flux 300 L/h

TSS 500 L/h TSS 400 L/h TSS 300 L/h
FIGURE 6.4 (a) Comparison of the concentration of black currant juice by NF and RO at
different transmembrane pressures and the final content of TSS reached in these concentra-
tion procedures. (b) Change of the permeate flux and TSS in the retentate during precon-
centration of clarified black currant juice by RO on laboratory-scale equipment at different
recirculation flow rates.
been made near to the fruit-growing place. To optimize this cost, the next step of
the concentration of the fruit juice can be applied, using conventional concentration
technology (evaporation), or membrane technology, which has the benefit of lower
energy cost and better concentrate quality (Jiao et al., 2004). The alternatives of
further concentration procedures are also shown in Figure 6.2. The first option is NF,
because in case of NF, the osmotic pressure on the permeate side due to higher TSS
concentration will be higher, resulting in lower osmotic pressure difference, which
causes a better driving force (Kiss et al., 2004; Porter, 1990).
Another possibility for the final concentrate production is MD. The driving force
of this separation process is the temperature, that is, vapor pressure difference on the
two sides of the membrane. The separation process can be carried out in hydropho-
bic hollow fiber membrane modules, characterized by a large specific mass transfer
area up to 10,000 m2/m3. The membrane materials are polypropylene (PP), polyvi-

nylidene fluoride, polytetrafluoroethylene, etc. (Lagana et al., 2000). The size of the
micropores can range from 0.2 and 1.0 micrometer. The porosity of the membrane
is usually in the range from 60% to 80% of the volume and the overall membrane/
fiber wall thickness is 80–250 micrometers, depending on the absence or presence
of support. The general rule is, the thinner the membrane and greater the porosity of
the membrane, the greater the flux of the permeate.
Experimental results of the concentration of a typical and valuable berry juice
black currant are shown in Figure 6.5. From the figure, it is obvious that the driving
force—temperature difference—has a main role in this separation process, espe-
cially at the beginning of the batch concentration process. In the second part of the
(a) 0.9
0.8
Distillate flux (kg/(m2 h))
0.7
0.6
0.5
0.4
0.3
0 2 4 6 8 10 12
Time (h)
(b) 70 3
Concentration 2.8
60
Retentate concentration (°Brix)
Concentration ratio 2.6

50
Concentration ratio, f
2.4
2.2
40
2
30
1.8
20 1.6
1.4
10
1.2
0 1.0
0 2 4 6 8 10 12
Time (h)
FIGURE 6.5 (a) Change of the permeate flux during the batch concentration of black cur-
rant juice by membrane distillation at 20 ± 1°C overall temperature difference. (b) Change of
the retentate TSS concentration of black currant juice by membrane distillation at 20 ± 1°C
overall temperature difference.
concentration process, when the retentate concentration is over 40–50° Brix, a sig-
nificant drop in the permeate flux was observed, due to an increase in the viscosity
of the retentate and decrease in the mass transfer rate (Banvolgyi, 2009).
OD is a recent membrane process (Lefebvre, 1988), also known as osmotic evapo-
ration (OE), membrane evaporation, isothermal MD, or gas membrane extraction,
which has been successfully applied to the concentration of liquid foods and various
nonfood aqueous solutions (Hongvaleerat et al., 2008; Mosshammer et al., 2006;
Nene et al., 2002; Ravindra Babu et al., 2008). This process can be used to selec-
tively remove water from aqueous solutions under atmospheric pressure and at room
temperature, which prevents the thermal degradation of the solutions. It is suitable
for the concentration of heat-sensitive products such as fruit juices (Lefebvre, 1988).
The basic idea of the process is to use a microporous hydrophobic membrane for the
separation of two circulating aqueous solutions with different solute concentrations:
a dilute solution and a hypertonic solution, in most cases, a salt solution. Keeping
the operating pressure below the capillary penetration pressure of the liquid into the
pores, the membrane cannot be wetted by the aqueous solutions. This difference in
solute concentrations causes a vapor pressure difference, resulting in vapor transfer
from the dilute solution toward the hypertonic solution. This water transport through
the membrane can be summarized in three steps:
• Evaporation of water at the dilute vapor–liquid interface

• Diffusion or convective vapor transport through the membrane pore
• Condensation of water vapor at the membrane–brine interface
The typical OD process involves the use of a concentrated brine at the down-
stream side of the membrane as the stripping solution. A number of salts such as
MgSO4, CaCl2, and K2HPO4 are suitable. Potassium salts of phosphoric acid offer
several advantages, including low equivalent weight, high water solubility, posi-
tive temperature influence on solubility, and safe use in foods and pharmaceuticals
(Courel et al., 2000; Lefebvre, 1988). In Figure 6.6, the change in the permeate flux
Concentration of juice by OD (24°C, 30 L/h)

1.2 90
1 75
0.8 60
J (kg/(m2 h))
CR (°Brix)
0.6 45
0.4 30
0.2 Flux 15
Con.
0 0
0 1 2 3 4 5 6
t (h)
FIGURE 6.6 Change of the permeate flux and the TSS content during the concentration
process of raspberry juice by osmotic distillation (OD).
and the TSS concentration during the concentration process of raspberry juice by
OD is presented. The experiment was carried out on a laboratory-scale OD appara-
tus, with a membrane area of 0.1 m2, using PP hollow fibers circulating a saturated
solution of CaCl2 (Molnar et al., 2009).
Compared to RO and MD, OD has the potential advantage that might overcome
the drawbacks of RO and MD for concentrating fruit juice, because RO suffers
from a high osmotic pressure limitation, while in MD, some loss of volatile compo-
nents and heat degradation may still occur due to the heat requirement for the feed
stream in order to maintain the water vapor pressure gradient. OD, on the other
hand, does not suffer from any of the problems mentioned above when operated at
room temperature. The most well-known module designed for OD is the Hoechst-
Celanese Liqui-Cel membrane contactor with an effective area/volume 2930 m2/
m3, maximum transmembrane differential pressure 4.08 bar, temperature operating
range 1–40°C, and containing microporous PP hollow fibers of Celgard membrane.
These fibers are approximately 0.3 mm in external diameter with a wall thickness
of about 0.03 mm; they have a mean pore diameter of about 30 nm and a porosity
of about 40%.
Galaverna et al. (2008) investigated the clarification and multistep concentration
of orange juice. Blood orange juice (Tarocco variety) from Sicily was used as raw
material, pressed by a local company. The TSS of the raw juice was 12.0–12.5°
Brix and the pH was 3.5. Traditionally, the company produced the concentrate by a
multiple evaporation system up to a final concentration of 56.30° Brix. The pressed
juice was clarified by KOCH tubular UF membrane HFM-251, made from PVDF
with an NMWCO of 15 kDa. On the laboratory-pilot scale with a module area of
0.23 m2, they reached a yield of clarified juice of average 85%, calculated to the
original juice volume. In the next step, the clarified juice was preconcentrated by
using pilot-size RO unit equipped with a spiral wound module of Hydronautics made
for seawater desalination SWC2–2521, with a batch mode of operation applying a
pressure of 1–69 bar. Further concentration of the RO concentrate was carried out on
a laboratory-scale osmotic distillation unit using CaCl2 as the osmotic solution, with
a Hoechst-Calanese liquid cell hollow fiber module of 1.2 m2 area. The OD system
was operated at a slightly higher pressure (0.28 bar) on the juice side—shell side—to
avoid leaking of the saturated (60%) CaCl2 solution into the juice. Besides TSS and
pH measurements, for certain samples, the TAA, ascorbic acid, antioxidant com-
pounds, flavonones, anthocyanins, and others were determined or identified. These
results were compared with the values of the original juice and juice concentrated
by evaporation. With RO, the final concentration was 25–30° Brix, while with OD,
it reached 60° Brix. During this integrated membrane-based concentration process,
a slight decrease of TAA (−15%) was observed, and the anthocyanin content also
decreased slightly (−20%). In case of multiple evaporation, the TAA and anthocya-
nins decreased by 26% and 36%, respectively.
Cassano and Drioli (2007d) used OD for kiwifruit juice concentration. The
enzyme-treated kiwifruit juice yield was 75%–80% (w/w). It has been clarified by
an UF membrane (tube type KOCH HFM-251) where the clarified juice had 9.4°
Brix TSS, at 0.9 bar TMP and a yield of 75%. The next step was the concentration
step using Liqui-Cel membrane module with CaCl2 as the osmotic solution. The
0.6
0.5
0.4 Thermal evaporation

Ascorbic acid (g/L)
Osmotic distillation
0.3
0.2
0.1
0.0
0 10 20 30 40 50 60 70
TSS (°Brix)
FIGURE 6.7 Change of ascorbic acid content during the concentration of kiwifruit juice by
osmotic distillation and thermal evaporation. (From Cassano, A., Drioli, E. 2007d. Journal
of Food Engineering 79, 1397–1404.)
OD process was carried out at room temperature, reaching 66.6° Brix. A parallel
experiment with a multistep evaporation system was also carried out. On analyz-
ing the concentrates in the product made by evaporation, 87% of vitamin C was
destroyed as presented in Figure 6.7 (Cassano and Drioli, 2007d), in comparison
to the initial clarified juice, while in case of concentration by OD, 100% of vitamin
C was retained in the concentrate. The TAA values of the concentrate produced by
evaporation were half that in the initial clarified juice. On the basis of the experi-
mental results and modeling, Cassano and Drioli proposed an integrated membrane
process for kiwifruit juice concentration, including UF for clarification and OD for
the concentration step.
Rodriques et al. (2004) concentrated camu-camu juice (Myrciaria dubia) using
RO and OE/OD. Camu-camu is an Amazonian fruit with a very high vitamin C
content (9–50 g/kg). The RO concentration experiments were carried out at room
temperature on a Der Danske Sukkerfabrikker (DDS) laboratory apparatus applying
TMP from 20 to 60 bar. In OD experiments, they used plate-and-frame membrane
module with Pall-Gellman TF 200 made from polytetrafluoro ethylene (PTFE) on
PP support. Before the RO concentration step, clarification by MF was done using
KOCH tubular membranes with pore size of 0.3 μm. The pre-concentration step by
RO was carried out up to 250 g/kg TSS, while the final concentration by OD was
done up to 600 g/kg TSS. In RO experiments, the higher TMP increased the perme-
ate flux and decreased the ascorbic acid (vitamin C) losses; especially at 60 bar, it
was 7.6%. In case of OE, besides the driving force of the osmotic pressure between
the osmotic solution (CaCl2) and the juice, a slight temperature gradient of 10–15°C
was used to improve the permeate fluxes, which were extremely high in some cases
(9–12 kg/m2 h). The ascorbic acid losses were very low (2.1%–4.4%) reaching 63.4°
Brix in some experiments.
Cassano et al. (2004) investigated the production of kiwifruit juice concentrate by
using membrane separation processes: UF for the clarification step and OD for the
concentration step. The apparatus and methods were the same as in the other article
of Cassano and Drioli (2007d). The final concentrate made by OD had a TSS of 65.8°
Brix, and there was practically no loss of ascorbic acid during the concentration pro-
cess from the fresh juice with 12.5° Brix.
Barbe et al. (1998) investigated the retention of the fruit juice aroma components
(volatile organic flavor/fragrance) during the concentration of model solutions by
OD. For the experiments, a water solution of seven organic components, ethanol,
2-methylbutanol, ethyl acetate, limonene, alpha-pinene, beta-myrcene, and ethyl
hexanoate, were used. They screened nine different membranes made from PP (4),
PVDF (2), and PTFE (3) with different pore sizes from 0.19 to 1.29 μm as well as
different thicknesses from 25 to 150 μm. They observed an increase in the volatile
component flux to water flux by an increase in membrane pore as shown in Figure
6.8, where relative fluxes of volatile components compared to water flux using model
solutions with different membranes (Barbe et al., 1998) are presented. Using grape
juice as the raw material, the loss of the main aroma components was the lowest
using a large-pore-size PTFE membrane, while the small-pore-size (0.27 μm) PP
membrane had 10–30 times higher aroma fluxes than the previous one. In case of
orange juice concentration, they had similar behavior of the membranes, but losses
of some components were higher (alpha-pinene, limonene).
3.5
Increasing pore size at membrane surface
3
Ethanol (×10E2)
2.5 3-methylbutanal (×10E6)
Ethyl acetate (×10E4)
Jv/Jw
2 Alpha-pinene (×10E6)
Beta-myrcene (×10E6)
1.5 Ethyl hexanoate (×10E6)
Limonene (×10E4)
1
0.5
0
Goretex L31189
Celgard 2400
Celgard 2500
Accurel 1E-PP
Accurel 2E-PP
Durapel VVSP
Durapel GVSP
Sumitomo 020–40
Sumitomo 045–40
FIGURE 6.8 Relative fluxes of volatile components compared to water flux using model
solutions with different membranes. (From Barbe, A. M. et al., 1998. Journal of Membrane
Science 145, 67–75.)
Cassano et al. (2003) proposed an integrated membrane process for the clari-
fication and concentration of citrus and carrot juices. For the clarification step,
a pilot-scale UF equipment was used, built with KOCH tubular UF membrane
HFM-251, made from PVDF with an NMWCO of 15 kDa on the laboratory-pilot
scale with a module area of 0.23 m 2. The preconcentration of the UF-clarified juice
was performed in a laboratory RO apparatus, reaching 15–20° Brix in TSS. The
final OD step of the concentration process resulted in a 60–63° Brix juice concen-
trate, at an average permeate flux of 1 kg/(m 2 h). The results of the experimental
tests as well as the cleaning procedures of different membranes are reported. The
performance of the membrane modules and operation conditions was evaluated
on the basis of productivity, quality of the product (measurement of the antioxi-
dant activity), and fouling characteristics. It was demonstrated in blood orange
juice samples that the TAA of juices concentrated by evaporation is lower than the
initial juice, while in the concentrate made by an integrated membrane process
(UF–RO–OD), the TAA as well as the aroma and color of the juice was retained.
Based on the experimental results, they proposed an integrated membrane tech-
nology for the production of fruit juice and vegetable juice (carrot) concentrate as
shown in Figure 6.9. In the preconcentration step by RO, 22–23° Brix was reached
with blood orange juice, while in the case of carrot juice, 5° Brix initial juice was
concentrated to 14° Brix. In the OD process with both juices, 65° Brix was the
final concentration, using different times in batch concentration processes, due to
different TSS of the RO concentrates.
Cassano et al. (2006a,b) developed an integrated membrane process for the pro-
duction of highly nutritional kiwifruit juice, concentrating the TSS of the juice by
OD and recovering the aroma components by pervaporation (PV). The main goal
Pulp
Fruit
juice Permeate
(10–11° Brix) UF RO
Preconcentrated CaCl2 CaCl2

juice
(25–26° Brix)
OD
PV Concentrated
Aromatic compounds juice
(63–65° Brix)
FIGURE 6.9 Integrated membrane process for citrus and carrot juice concentrate produc-
tion proposed by Cassano, A. et al., (2003). (From Cassano, A. et al., 2003. Journal of Food
Engineering 57, 153–163.)
Pulp
Clarified
juice
Fresh kiwifruit
juice UF
Diluted Concentrated
brine brine
PV
OD
Aroma recovery
Concentrated
juice
FIGURE 6.10 The technology proposed. (From Cassano, A. et al., 2006a. Desalination
189, 21–30.)
of the proposed production scheme was to add the pulp of the clarification by UF
to the final concentrate, producing a concentrate of high nutritional value, rich in
aroma components too. Studying the rejection of the main aroma compounds during
clarification, they observed a high level of rejection of some components, even up
to 80%, and that was the reason for the proposal of aroma recovery by PV from the
fresh juice, adding it to the end product. The flow diagram of the proposed technol-
ogy is shown in Figure 6.10.
Jesus et al. (2007) investigated experimentally the concentration of fresh pressed
orange juice by RO. They used a laboratory RO unit equipped with HR98PP mem-
branes. The applied TMP was 20, 40, and 60 bar and the final concentrations were
16, 28, and 36° Brix, respectively. The vitamin C content increased from 29.3 mg/kg
to 101.3 mg/kg in the 36° Brix concentrated juice. Simulating the continuous con-
centration process at 60 bar TMP, a permeate flux of 28 L/(m2h) was calculated,
which shows a high feasibility of this concentration technology. On comparison of
the sensory characteristics of the fresh juice and juice reconstituted from the RO
concentrate, they observed some loss of aroma components, but compared to the
drink produced from the concentrate made by evaporation, the sensory characteris-
tics of the RO concentrate were significantly better.
Jiao et al. (2004) in a review paper collected the recent advances in membrane
processes for the concentration of fruit juices. They revised and studied the state of
the art in fruit juice concentration by RO, direct osmosis concentration (DOC), MD,
and OD. They included a discussion on integrated membrane processes, suitable for
the production of a final concentrate with 60–70° Brix TSS. In case of concentra-
tion by RO, they discussed the aroma component rejection of the RO membranes
TABLE 6.1
Advantages and Disadvantages of RO Applied to the Concentration of Fruit
Juices
Advantages Disadvantages
Technical Aspects
• Broad industrial-scale application • Fouling phenomena
• Low temperatures • High pressures
• Combination with vacuum evaporation and • Necessity of an inactivation enzyme
with systems of vapor recompression, pretreatment
already commercially available • Juice concentration limited at 22–23° Brix
• Loss of aroma compounds during the process
• Difficulty to concentrate solutions with high
levels of suspended solids
Economic Aspects
• Energetically and economically convenient in • Membrane replacement at high cost
comparison with the thermal evaporation • High cost of working process
Source: Adapted from Jiao, B., Cassano, A., Drioli, E. 2004. Journal of Food Engineering 63,
303–324.
and concluded that the rejection of oil-soluble aromas was better than that of water-
soluble aromas, but the values in both cases are over 90%. The advantages and dis-
advantages of concentration by RO are summarized in Table 6.1.
DOC is another membrane process suitable for concentrating fruit juice at low
temperature and low pressures, maintaining the original flavor and color charac-
teristics of the fruit. The DOC was introduced by Popper et al. in 1966. The basic
principle of the process is using RO membranes with osmotic pressure difference on
different sides of the membrane, which causes water to flow from the lower to the
higher osmotic pressure solution. It means that fruit juice can be concentrated using
OA on the other side like brine glycerin, sucrose, etc. The basic principles of the
process are shown in Figure 6.11.
The process uses an OA solution to establish an osmotic pressure gradient across
a semipermeable membrane and thus remove water from a single-strength fruit juice.
An OA is generally a solid that is highly soluble in water, hygroscopic, nontoxic,
and inert toward the flavor, odor, and color of the foodstuff, and which does not
pass through the membrane. The most frequently employed constituents are sodium
chloride, sucrose or glycerol, cane molasses, or corn syrup. The OA solutions must
have an osmotic pressure greater than the concentrated fruit juice, for example, the
osmotic pressure of 47° Brix pulpy orange juice is 90 bar, while the 74° Brix fructose
corn syrup as OA has 270 bar osmotic pressure. The advantages and disadvantages
of the DOC process are summarized in Table 6.2.
The industrial thermal processing of foods may have a severe negative impact on
the sensorial and nutritional properties of the final product. Membrane technologies
Membrane Sugar (OA)

Product
concentrate flow
Water
Heat
exchanger
Concentration
cells Evaporator
Recirculation Water
Product loop
inlet
FIGURE 6.11 Basic principles of direct osmosis concentration. (From Jiao, B., Cassano, A.,
Drioli, E. 2004. Journal of Food Engineering 63, 303–324.)
such as RO membrane or OD have been extensively studied as alternative processes.

The problem is that the above-mentioned processes have certain disadvantages.
Forward osmosis (FO) is a promising membrane technology to be used in food
industries. The only driving force of the process is the osmotic pressure difference
between the two solutions that flow in countercurrent mode on opposite sides of a
permeable membrane. Thus, the main advantages of FO, compared to both thermal
and conventional membrane processing, include low hydraulic pressure, low treat-
ment temperature, low fouling tendency, high solids content processing capability,
and easy scale-up. A detailed, up-to-date summary of potential FO applications for
concentrating liquid foods is presented in a review article by Sant’Anna et al. (2012).
The effect of the main process parameters on the mass transfer performance and
their impact on the sensorial and nutritional factors of the final product are described
and discussed for a broad spectrum of foods.
Rektor et al. (2004) investigated the possibility of the application of membrane
filtration for must processing and to carry out a complex method for preservation and
concentration of white and red juice must with a combination of MF and RO. Wine
is a very important food item because of its health effects. Grape must is also used in
soft drinks, or as a sweetener, and in certain case, to improve the must sugar content
in poor vintage. But the preservation of this grape must is very difficult. So, the aim
of the study was to find an application for grape must processing and preservation
with the assistance of a complex membrane filtration. For the study, two different
white grape must (Furmint and Szamorodni) and one type of red grape must (Egri
Kekfrankos) were used. The MF process uses two modules, a hollow fiber, and a
ceramic. The microbiological measurements took place in a sterile laboratory after
48 h of incubation at 37°C. Then the sensory analyses was realized by an indepen-
dent panel in a sensory laboratory.
The MF brings something to light—the permeate flux increases with pressure. It
was established that MF was successful as the suspended solid content of the must
samples was retained (with Furmint and Szamorodni grape must).
TABLE 6.2
Advantages and Disadvantages of DOC Applied to the Concentration of
Fruit Juices
Advantages Disadvantages
Technical Aspects
• Low temperatures, low pressures • New technology that requires an evaluation at
industrial level, flexibility to be evaluated
• No fouling problems, constant permeate flux • The long life of the membrane to be
in time evaluated
• Possibility to obtain high TSS concentration • Relatively low permeation 1.8–2.5 L/(m2h)
in the final product
• Modularity, easy scale-up
• Possibility to treat solutions with high level
of suspended solids
• Possibility of using modules in series, the
same unit can concentrate several different
products
Economic Aspects
• Low cost of membrane replacement • High investment costs
• High energy consumption
Source: Adapted from Jiao, B., Cassano, A., Drioli, E. 2004. Journal of Food Engineering 63,
303–324.
The sensory analyses show us three important results:
• The appearance of the filtered musts was more attractive.

• A certain extent of loss in flavor and odor intensity was observed in the
treated samples.
• Tasters preferred the treated samples as they found the off-flavor less
intense.
With these microbiological results, and after a sufficient incubation time, the
number of colonies in the permeate was small. The results proved that MF is efficient
for sterilization, and the total cell number decreased by six orders of magnitude.
The flux of the two RO membranes in a function of refraction showed a significant
deviation. The TS retention plays an important role in successful concentration. With
RO membranes the TS retention was about 90% for both types of membranes in the
case of Furmint and very high (99%) in the case of Kekfrankos must. The retention
of anthocyanin is measured by absorbance with a spectrophotometer.
To conclude, sensory analysis preferred samples that were filtered, but it was
found that through the filtration procedure, must samples lost their typical odor
to some extent. Based on microbiological experiments, we can state that MF is an
effective process for the clarification and sterilization of must samples. The two
RO membranes (HR-30 and ACM-2) have a significant deviation in permeate flux.
The membranes retain anthocyanin and the value is 99.5%. Three possibilities are
offered: for the soft drink industry and healthier juice without sugar addition, for
the wine industry in order to upgrade the poor vintage, or for a new “bio syrup”
product.
Patil and Raghavarao (2007) concluded that membrane technologies offer the
potential of pigment concentration. They compared UF, RO, and OMD operating
individually and in combination of with each other in order to concentrate anthocy-
anin from red radish. An attempt has been made to concentrate anthocyanin from
the red radish extract by using different membrane processes. In the UF process,
a PVDF membrane was used. Hydrophobic PP membrane was used for the OMD
process. In case of the RO process, a polyamide membrane was used. The extracting
solvent was water. The crude contained 40 mg/100 mL of anthocyanin.
Reverse osmosis: The concentration of anthocyanin increased with an increase in
process time. A decline of the permeate flux with respect to an increase in processing
is due to the increase of concentration polarization and also due to the increase of
osmotic pressure of the color. Anthocyanin content was 180 mg/100 mL.
Ultrafiltration: The concentration of the extract remained almost the same,
whereas the obtained color extract was much clear than that of the RO. Anthocyanin
content was 35 mg/100 mL.
Osmotic membrane distillation: The transmembrane flux decreased with an
increase in process time. This decrease in flux is mainly due to the dilution of OA and
the concentration of the feed solution. The maximum concentration was achieved at
20 h using minimum using CaCl2 and at 30 h using K2HPO4. The anthocyanin con-
tent was 565 mg/100 mL.
OMD has shown better results as compared to other processes. However, the time
taken by the process is relatively more (20 h) and the retention of undesirable radish
flavor/odor is to high.
In order to obtain the results, various combinations were made: UF + OMD,
RO + OMD, and UF + RO + OMD.
• UF + OMD: The process time was 10 h, and the anthocyanin content was
580 mg/100 mL.
• RO + OMD: The process time was 9 h, and the anthocyanin content was
810 mg/100 mL.
• UF + RO + OMD: The process time was 8.5 h, and the anthocyanin content
was 798 mg/100 mL. But the continuation of this process resulted in a final
anthocyanin content of 980 mg/100 mL.
The increase in the concentration of the extracts decreased the value of L, hue
angle, and also chroma. The integrated membrane process involving clarification
by UF, preconcentration by RO, and final concentration using OMD was observed
to be an attractive alternative process when compared to the membrane processes
operated alone. Moreover, this combination increased the hue angle and chroma of
the color extract.
Gilewicz-Lukasik et al. (2007) investigated the influence of process conditions on

the retention of anthocyanins in aronia solutions. Filtration (NF) of aronia solution
with and without Na2SO3 or Na2SO4 has also been performed. As it is well known,
food additives can cause various diseases such as cancer or heart disease. As antho-
cyanins can be extracted using different chemicals, one of the components of aronia
solution was sodium sulfite (Na2SO3). Comparisons of the concentration of aronia
solutions containing sodium sulfate (Na2SO4) and pure aronia solutions have also
been performed. The recovery of anthocyanins from aronia fruits by means of NF is
effective. Aronia solutions containing sodium sulfite (Na2SO3) had a high retention
of anthocyanins (>0.99). Also, the presence of sodium sulfite (Na2SO3) increases the
efficiency of anthocyanin recovery. The filtration of pure aronia solution or aronia
solution containing sodium sulfate (Na2SO4) is not so effective (R = 0.91–0.95). The
decrease of hydrodynamic permeability compared to pure electrolyte solutions is
significant. Compared to pure aronia solution, the presence of Na2SO3 does not influ-
ence the volume flow. The complete rejection of anthocyanins suggests using a more
leaky membrane in order to increase its hydrodynamic permeability.
Warczok et al. (2004) investigated the concentration of apple and pear juices
by NF at low pressures. They found that the most adequate process conditions to
reach the highest concentration of juices were with pressures between 8 and 12 bar
and temperatures of 25–35°C. NF has properties that are between those of UF and
RO, and it can separate fine particles. Membrane techniques make it possible to
obtain a product that is very similar to fresh juice, and this reduces and simplifies
the clarification process. Two tubular membranes (AFC80 and MPT-34) and two flat-
sheet membranes (Desal-5DK and MPT-34) were examined.
Tubular membranes: The permeate flux decreases slowly for the AFC80
membrane and the results for juice concentration suggest that each membrane was
formed from a different type of polyamide.
Flat-sheet membranes: Desal-5DK membrane achieves a very high permeate
flux, high retention, and a higher concentration degree than MPT-34 membrane.
The decrease in permeate flux is greater in juice solutions than in fructose solu-
tions. Scanning electron microscope (SEM) characterization showed two types of
changes that affected the structure of the membrane: blocked pores and a layer of
deposited particles can be observed, and the support undergoes modifications as
delamination or compaction (caused by pressure or other conditions).
Concentration of black currant (Ribes nigrum L.) juice with NF has been
investigated experimentally by Banvolgyi and coworkers (2006). They found that
black currant contains mineral salt and vitamins in a large amount and are rich
in pigment. The advantage of NF is that it can be carried out at low temperature
and in low p ressure, and it retains the above-mentioned important components.
The concentration was carried out at 30°C, at 20 bar pressure, and at 400 L/h recycle
flow rate. The permeate flux is higher at higher flow rates. The volumetric reduction
rate reached was 2.23. The retention of total extract content is 96.72%.
Sometimes, musts do not have sufficient alcohol content. So, it is necessary to
increase their sugar concentration by chaptalization (adding sugar into must) or by
subtractive methods (RO, vacuum evaporation) in order to reduce the water content.
Mietton-Peuchot et al. (2002) compared grape must concentration by using RO with
chaptalization. They investigated the influence of operating parameters on the qual-

ity of extracted water. However, they found that high pressure may provoke tartaric
acid precipitation at the membrane surface. RO should not be used in the palliation
of lack of fruit maturity. High temperature improves the permeate flux whereas high
pressure decreases the flux (due to the precipitation of tartaric acid at the mem-
brane surface). During the concentration of must, the reduction volume factor (RVF)
increases and provokes permeate flux down. Aroma precursors are not spoiled by
RO, contrary to chaptalization. Red wine issued from RO is often considered as
more structured, aromatic, soft, and full. For white wine, there was a slight increase
in the acidity of the RO concentrate. Concentration by using RO technique enables
to increase the sugar content in grape musts without spoiling their quality. Operating
parameters should be adapted to wine characteristics.
Concentrated must is a natural sweetener in wine production. The classical form
of conservation is the concentration of must by evaporation but the membrane separa-
tion is less expensive. Kiss et al. (2004) investigated the concentration of grape must
using multistep membrane processes. The first step of the process is MF, then RO,
and the last step is NF to reach the final concentration. A complex membrane process
and optimal process parameters were calculated to produce 45° Brix sugar concen-
tration in the retentate. An increase in the pressure and the recycle rate increased
the sugar concentration in the retentate and the permeate flux while an increase in
the temperature decreased them. Optimum values of sugar concentration were at the
highest recycle rate, highest pressure, and lowest temperature. The maximum per-
meate flux was obtained at the highest recycle rate and pressure but the temperature
must be low for RO and high for NF. The total cost (investment costs and operational
cost) of evaporation is much higher than that of the membrane system.
Concentrated grape juice is an unfermented product obtained by the process of
concentration from the raw juice. RO membrane techniques allow winemakers to
partially concentrate the sugar. Rektor et al. (2007) used RO on laboratory-scale
equipment and pilot plant equipment. The new pilot plant filtration results of grape
juice were compared with laboratory experiments. During RO, for the model solu-
tion, the permeate flux decreases as the sugar content increases (due to an increase
in the osmotic pressure). The flux of the must of red grape was much lower than that
of the model solution. The composition of the model solution was only sugar and
deionized water, whereas the must was composed of sugar, salt, mineral, organ-
ics, colloids, colors, etc. The osmotic pressure is a linear function of the retentate
concentration for both (laboratory apparatus and pilot-plant). For the retentate sugar
concentration, there is no significant difference between the laboratory experiment
and pilot experiments. So, the permeate fluxes have not been improved by MF. The
concentrated must cannot achieve more than 23° Brix sugar concentrations. The
prefiltration of the must by MF did not influence either the permeate flux or the con-
centration rate of the RO (for flat sheet or tubular membrane).
The experiments on the final concentration of must by OD in the laboratories of
Corvinus University of Budapest were carried out using PP hollow fiber modules
with CaCl2 as the osmotic solution. The details of this experiments are described
elsewhere (Kozak, 2005; Rektor et al., 2006). On laboratory and pilot scale, the final
must concentration was over 65° Brix (Kozak et al., 2008; Rektor et al., 2006).
Membrane separation represents a potentially efficient and cost-effective tech-

nology to separate the phenolic fraction of fruit juice in a form suitable for use as a
functional ingredient. Membrane filtration is desirable as a processing technology
because it does not require the addition of chemicals to the process stream. However,
the main disadvantage of membrane filtration is membrane fouling, resulting in a
decline in permeate flux. Saleh et al. (2006) investigated the separation and concen-
tration of health compounds by membrane filtration. They found that the maximum
concentration of phenolics in the retentate decreased as the temperature increased
(from 30°C to 50°C). The flux declined immediately after the start of each run and
the decrease was faster at lower temperature. Increasing the temperature reduced the
amount of polyphenolics fouled on the membrane. The concentration on the reten-
tate side decreased with increasing feed pH. It was the formation of a secondary
membrane that restricted the flow and reduced the pore size or the cut-off of the
membrane. Increasing the acidity of the solution improved the separation behavior
of the phenolic compounds. The flux reduced over the run duration and the decrease
was more rapid at lower pH values. The polyphenolics concentration on the retentate
side increased linearly with increasing initial sugar concentration. It may have been
due to the formation of a secondary membrane that plugs the pores or reduces the
pore size and restricts the flow across the membrane. The flux declined rapidly from
the start of the experiment and the decline was more severe at higher concentrations.
The concentration of phenolic compounds on the retentate side increased signifi-
cantly with increasing transmembrane pressure. It is explained by higher pressure
compressing the rejected solutes into a thicker and denser fouling layer and lower
CFV removing retained materials because of lower shear forces. The decline in the
flux was rapid at the early stages of the experiment but was gradual and limited
afterward. The increase in fouling paralleled the decrease in the amount of polyphe-
nols found in the permeate solution. Fouling was caused by larger-molecular-weight
phenolic compounds and pretreatment or removal of these compounds is essential
in such processes. Therefore, higher-molecular-weight polyphenolics in feed are
expected to have a significant role in membrane fouling.
Certain herbs such as sea buckthorn (Elaegnaceae) cured a number of illnesses
and aided healing. Its fruits contain many vitamins. Vincze et al. (2006) investigated
the concentration of sea buckthorn (Hippophae rhamnoides L.) juice using NF and
RO. They found that the solid content of the retentate by NF was four times higher
than the starting concentration. With RO, the solid content of the juice increased
by two times. The sea buckthorn can be concentrated with membrane separation.
Because of the total fouling of the membrane, another method has to be found for the
separation of the suspended solids. For NF, the removal of suspended solids has to be
done. The general conclusion was that the flux can be increased with the removal of
the suspended solids (Vincze et al., 2007).
As reported by Vaillant et al. (2001), for economic reasons (reduced transport
and storage costs), fruit juices are routinely concentrated. This is especially true in
the case of tropical fruit juices where the centers of production and consumption are
normally far apart geographically. Classical thermal concentration techniques lead
to subsequent losses of aromatic compounds and vitamins. Especially for tropical
fruits, which are usually valued for their distinctive aromas, these losses are a serious
marketing problem (Vaillant et al., 2001). They tried out OE to concentrate clari-
fied passion fruit juice on an industrial scale. A pilot plant that was equipped with a
module containing 10.2 m2 of PP hollow fibers was used to concentrate passion fruit
juice to a TSS content higher than 60 g/100 g at 30°C. It has been observed from
experiments that tangential velocity, temperature, and concentration of solutions sig-
nificantly influenced evaporation flux. They obtained an average evaporation flux of
almost 0.75 kg/h m2 with water, but 0.65 kg/h m2 when the juice was concentrated to
40 g TSS/100 g and 0.50 kg/h m2 when concentrated to 60 g TSS/100 g. A long-term
trial, lasting 28 h, was successfully carried out without membrane fouling. They con-
cluded that OE can also be conducted as a multistage procedure, giving a constant
evaporation flux of around 0.62 kg/h m2 when the juice was concentrated from 14 to
60 g TSS/100 g. Sensory quality and vitamin C content were well preserved in the
concentrated juice. The evaporation flux obtained by Vaillant et al. (2001) with OE
is nonetheless low when compared with RO where fluxes are almost 10 times higher.
These low values were explained by the high membrane thickness (0.8 mm). The
hydrophobic membrane used by them was not optimized for this application because
in the laboratory evaporation fluxes that were 10–20 times higher were attained with
other membranes (Vaillant et al., 2001). Even so, they stated that OE can be applied
on an industrial level and thus be as an alternative for concentrating thermosensitive
products to the high concentration values required by markets with less changes to
the original nutritional and sensorial qualities. Further developments of OE applica-
tions now need the input of membrane manufacturers to design industrial modules
with hydrophobic membranes that are much more suited to the process.
The interest of consumers on healthier and more natural products has been grow-
ing and contributing to the increase of the consumption of juices and fruit-based
drinks such as nectars, cocktails, and drinks that are lighter and refreshing, present-
ing new flavors and mixtures of fruits. In Europe, the nonalcoholic market showed
a 6.6% annual growth between 1985 and 1995 (Matta et al., 2004). Exotic tropical
fruits are adequate for increasing the market of fruit juices and fruit-based drinks
due to their diversity of aromas and flavors and their nutritional value. In such a
group, acerola appears to be potentially attractive due to its high ascorbic acid con-
tent. The use of acerola juice is potentially attractive for that market due to its high
vitamin C content, ranging from 800 to 4000 mg/100 g (Matta et al., 2004). The
objective of the work of Matta and coworkers was to develop a process for obtain-
ing clarified and concentrated acerola juice, maintaining its nutritional and sensory
characteristics. The experimental procedure consisted of fruit pulping followed by
enzymatic hydrolysis, clarification by MF, and concentration by RO. The use of
membrane processes associated with enzymatic hydrolysis resulted in clarified and
concentrated acerola juices with high nutritional and sensory quality. The clarifica-
tion of the juice by MF was effective in removing the substances that cause haze,
resulting in a clear juice free of pulp or suspension particles. Using MF, they reduced
molds and yeast, assuring that the clarified juice will be fit for consumption (Matta
et al., 2004). The RO conducted at 6 MPa TMP permitted the concentration of clari-
fied juice from 7° Brix to 29.2° Brix. The vitamin C content of the integral juice
(1234 mg/100 g) was maintained in the clarified juice. The concentrated juice had
its vitamin C content improved by 4.2-folds, reaching 5229 mg/100 g. The obtained
products presented the required microbiological counts and nutritional quality due
to ascorbic acid preservation. In an acceptability test, most of the consumers (84%)
liked the drink prepared with the clarified juice (Matta et al., 2004).
The aim of the study of Onsekizoglu et al. (2010) was to evaluate the potential
of integrated membrane processes for the clarification and concentration of apple
juice, taking into account the impact on the product quality. The fresh apple juice,
with a TSS content of about 12° Brix, was previously clarified by a combined appli-
cation of fining agents (gelatin and bentonite) and UF through 10 kDa or 100 kDa
molecular weight cut-off (MWCO) membranes on a laboratory scale. The clarified
juice was then concentrated by OD, MD, coupled operation of OD and MD, or con-
ventional thermal evaporation up to 65° Brix. The effect of different clarification
and concentration processes on the formation of 5-hydroxymethylfurfural (HMF),
retention of bioactive compounds (phenolic compounds, organic acids, glucose,
fructose, and sucrose), and their efficiency in preserving the natural color and aroma
(trans-2-hexenal, the most relevant compound in apple juice aroma) were evaluated
in order to maintain a high-quality product. The new membrane-based concentration
techniques were very efficient since the product characteristics were very similar
to that of the initial apple juice, especially regarding the retention of bright natural
color and pleasant aroma, which are significantly lost during thermal evaporation.
Furthermore, among all the concentration treatments applied, only thermally evapo-
rated samples resulted in the formation of HMF. Phenolic compounds, organic acids,
and sugars were very stable against all concentration processes, including thermal
evaporation. The coupled operation of OD and MD reduced trans-2-hexenal losses
drastically, tending toward that of the initial juice and hence can be proposed as
the most promising alternative to the conventional thermal evaporation technique
(Onsekizoglu et al., 2010).
Acerola is a tropical fruit with a high antioxidant activity, which may be attributed
to its high vitamin C and anthocyanin content. The aim of the work of Pagani et al.
(2011) was to produce a high-quality concentrated acerola juice by an integrated
membrane process, alternative to thermal evaporation. In the preliminary step, acer-
ola juice was clarified by MF. The clarified juice was preconcentrated by the RO pro-
cess up to a TSS content of 28° Brix and after that the OE process was used to reach
a TSS up to 55° Brix, corresponding to a concentration factor of 1.93. The vitamin
C, anthocyanin content, and antioxidant activity increased in accordance with the
concentration factor, except for the anthocyanin content, probably due to the great
instability of this pigment (Pagani et al., 2011).
Watermelon is a much-appreciated fruit due its good sensory characteristics such
as flavor and aroma. Watermelon juice was concentrated by RO process by Gomes
et al. (2011). They carried out RO on a pilot plant unit equipped with polyamide
composite membranes with an effective permeation area of 0.72 m2. The concentra-
tion tests were carried out in a fed-batch mode at 30°C, 60 bar TMP, and 650 L/h
recycle flow rate. The average permeate flux was 21.7 L/h m2. The volumetric con-
centration factor and the soluble solids concentration factor reached were 4.4 and
3.6, respectively. They detected an increase in some properties of the concentrated
juice, like in the lycopene content and in the antioxidant capacity (Gomes et al.,
2011).
The investigation of the influence of the process parameters during the concentra-
tion of grape juice by RO was experimentally carried out by Santana et al. (2011).
The following parameters were analyzed by them: acidity and pH, soluble solids
content, concentration of phenolic compounds and concentration of monomeric and
total anthocyanins, color index, color density, as well as the permeate flux. They
concluded that under the evaluated conditions, the process conducted at 50°C and 60
bar presented higher permeate flux and maintenance of all the physical and chemical
parameters of the product (Santana et al., 2011).
The production of concentrated pomegranate juice was investigated by using a
two-step membrane process by Cassano et al. (2011). They investigated (1) a clari-
fication step of the fresh non-depectinized juice by hollow fiber UF and (2) a con-
centration step of the clarified juice by using an OD apparatus. Both processes were
performed at ambient temperature (25 ± 2°C), producing a clear juice and a concen-
trated juice with a TSS content of 162 and 520 g/kg, respectively. The performance
of UF and OD operations was evaluated in terms of productivity (permeate and
evaporation fluxes) and quality of the processed juice. Suspended solids were com-
pletely removed in the clarification step, while soluble solids and organic acids were
recovered in the permeate stream of the UF process. Rejections of the UF membrane
toward polyphenols and anthocyanins were 16.5% and 11.7%, respectively.
The antioxidant activity of pomegranate aril juice, attributed to a great extent to
total phenols and anthocyanin content, was efficiently preserved during the concen-
tration step, independently of the achieved level of TSS. An integrated membrane
process scheme for the production of concentrated pomegranate juice with potential
applications for food, pharmaceutical, and cosmetic sectors was proposed by the
researchers (Cassano et al., 2011).
Sotoft et al. (2012) prepared a conceptual process design with the use of inte-
grated membrane processes for black currant juice concentrate (BCJC) production
to replace traditional multiple-step evaporators and aroma recovery. They proposed
a combination of membrane processes and included aroma recovery with vacuum
MD and water removal by RO, NF, and direct contact MD. The process design has
been combined with optimization of membrane performance and juice quality. The
calculated annual production scale is 17,283 ton of 66° Brix out of single-strength
juice. The operation cost is lower than the price of a traditional operation by about
43%. Therefore, the economic potential of the process is very promising and could
compete with conventional evaporators.
An integrated membrane process for the production of highly concentrated ber-
gamot juice was investigated by Cassano et al. (2013). The depectinized bergamot
juice, with an initial TSS content of 95 g/kg was previously clarified by UF by using
polysulfone hollow fiber membranes having an NMWCO of 100 kDa. They analyzed
the flux decay according to fouling models reported in the literature, and concluded
that the resistance of a cake layer covering the entire surface of the UF membrane
well describes the fouling phenomenon in the treatment of bergamot juice. In the
next step, they concentrated the clarified juice in an OMD system by using a hollow
fiber membrane contactor and calcium chloride dehydrate as the extraction brine.
In isothermal conditions (25°C), transmembrane vapor water fluxes were between
0.4 and 1.45 kg/m2 h producing a concentrated juice with a final TSS content of
540 g/kg. Flavonoids and ascorbic acid as well as TAA were recovered in the UF
permeate and well preserved during the subsequent concentration processes.
Forero et al. (2013) reported the first work on cholupa juice processing by using
membrane technology. Cholupa is an exotic fruit that has excellent organoleptic
characteristics but is highly sensitive to thermal treatments. For juice clarification,
a Pellicon2 UF system with 10 kDa flat membranes and a filtration area of 0.5 m2
was used. The used osmotic evaporator had a PP hydrophobic hollow fiber module
MD020CP2N® with an area of 0.104 m2. Prior to UF, in order to obtain a higher per-
meate flow, the juice was subjected to enzymatic pretreatment with commercial mix-
tures prior to the clarification step. They found that doses of Maxoliva (50 µL/100 g)
and Rapidase (40 µL/100 g) had a significant effect on viscosity reduction and
increased soluble solids concentration. In the clarification process by UF, the perme-
ate flux rate was changed from 19.4 to 6.0 L/(m2h). Finally, with the OE process, they
produced a concentrate of 65.15 ± 0.36° Brix. They showed that UF and OE proved
to be effective and were synergistic technologies to obtain a good-quality concen-
trate, which preserve much of the original characteristics of the juice.
The objective of the work of Souza et al. (2013) was to evaluate the technical
feasibility of coupling, RO, and OE, in order to concentrate clarified camu-camu
juice. They focused on the conditions to retain the valuable components such as
vitamin C, phenolic compounds, and antioxidant activity of the final product. In
the first step of RO they reached 285 g/kg of soluble solids. In the second step,
juice was concentrated by OE, reaching 530 g/kg of soluble solids. Vitamin C, total
phenolics, and antioxidant activity levels of 94.6 g/kg ascorbic acid, 105.2 g/kg gal-
lic acid, and 762 mmol/kg Trolox, respectively, were achieved in the final product.
They concluded that the use of integrated membrane processes proved to be an
interesting alternative to the concentration of thermosensitive juices, reaching con-
centration levels up to 7 times for camu-camu juice’s bioactive compounds (Souza
et al., 2013).
The OD of cranberry juice (Vaccinium macrocarpon Ait.) was studied by Zambra
et al. (2015) with CaCl2 solution as the osmotic agent. They varied the flow rates
from 0.5 to 1.5 L/min at temperatures between 30°C and 40°C. The transmembrane
flux of water vapor was ranged between 0.25 and 1.21 L/h m2. The comparative low
content of TSS in feed cranberry juice and a big membrane surface/feed tank ratio
allowed fast water removal from juice, achieving concentrations from 8.6 to 48°
Brix in a relatively short time. They concluded that the total phenolic content was
preserved after the concentration process. They developed a mass transfer model for
explanation of the concentration kinetics of the juice.
6.5 OTHER APPLICATIONS OF MEMBRANE SEPARATION

PROCESSES IN FRUIT JUICE PRODUCTION TECHNOLOGIES
6.5.1 Aroma Recovery
Aroma is one of the most important features of food, and is directly connected to the
quality of the product and consumer’s acceptance. Aroma is a large combination of
substances that are directly responsible for its odor and taste. Today, the analysis of
different kinds of fruits indicates more than 6000 compounds as participants of their
aroma. For instance, juices of passion fruit and orange have about 200 compounds
responsible for their aroma. However, during industrial processing of drinks (bever-
ages, juices) and foods, such as in the concentration by evaporation process (Pereira
et al., 2005), losses or chemical modification of these aroma compounds can occur.
This fact leads to a lower-quality product.
When we are working with aroma compounds, it is important to distinguish
between natural, nature-identical, and artificial aromas:
• Natural aromas are isolated directly from the natural source, plant or animal
• Nature-identical aromas are produced synthetically, but they are chemi-
cally identical to their natural counterparts
• Artificial aromas are also produced synthetically
While artificial aromas have the same sensory profile and other features as natu-
ral aromas, their chemical structure is different (Lipnizki et al., 2002a). It is also
important to mention that in the literature, a less strict definition of natural aroma
compounds is often used, which includes aromas produced biologically by solid-
state or submerged fermentation.
The prices of naturally, biologically, and synthetically produced aromas vary sig-
nificantly, for example, c-decalactone (peach aroma) costs 1400 $/kg as a natural
extract but only 75 $/kg as a synthetic product, and raspberry ketone (raspberry
aroma) costs 3000 $/kg as a natural extract and 58 $/kg when produced synthetically
(Lipnizki et al., 2002a). The prices of biologically produced aromas, if available,
range between these two prices, but are generally one order of magnitude lower than
those of natural aromas.
The focus of the investigations in this project is on natural aromas extracted from
the original natural source. To recover aromas from natural sources, conventional
separation processes, such as adsorption, steam distillation, solvent extraction, or air
stripping, are often applied. However, these processes have disadvantages (Schafer
and Crespo, 2007), which might affect the quality of the product, such as
• The requirement of a solvent or adsorbent, which must be separated from

the aroma compounds in a purification/desorption step to avoid contamina-
tion of the product
• Deterioration of the aroma due to high temperatures and oxidation
• High energy consumption
• Limited range of applicability
The possibility of using PV for the recovery of natural aroma compounds in the
food industry has been widely recognized. The use of hydrophobic membranes to
recover aroma compounds from aqueous model solutions has been successfully dem-
onstrated for over 50 aroma compounds, covering groups such as alcohols, lactones,
esters, aldehydes, ketones, sulfur compounds, pyrazines, and hydrocarbons (Baudot
et al., 1999). The number of publications covering aroma recovery by hydrophobic
PV using the original natural source as feed is far more limited (Lipnizki et al.,
2002a).
Overall, the research on PV for aroma recovery has so far been mainly based on
experimental studies with model solutions, and the testing and selection of mem-
branes (Baudot et al., 1999; Börjesson et al., 1996; Ribeira et al., 2004; Tan et al.,
2005). The second group of studies deal with some special fruits and/or fruit juices,
using natural product or model solutions composed of the “key components” on the
basis of the aroma profile of the natural juice, such as apple (Börjesson et al., 1996),
bilberry (Diban et al., 2008), strawberry (Isci et al., 2005), pineapple (Pereira et al.,
2005), and pomegranate (Raisi et al., 2008). The third group of studies are connected
to the modeling of the aroma recovery process, dealing strictly with the modeling of
the selectivity and flux of the PV (Fontalvo et al., 2006; Ghoreysi et al., 2008); only
few of the studies (Lipnizki et al., 2002a,b) build a bridge between the experimental
studies of multicomponent systems and potential applications of PV on an industrial
scale. The fourth group of studies has some overlaps between aroma compounds
recovery or reviewed and the applications of PV in food processing (Karlsson and
Tragardh, 1996). In the next part of this chapter, some of the most important research
dealing with aroma recovery in general and aroma recovery from certain fruit or
juices will be discussed in detail.
Börjesson et al. (1996) stated that the production of concentrated apple juice is
associated with major physical and chemical losses of aroma compounds, mainly
due to evaporation, which results in a product with an inferior sensory quality. They
proposed a method of improving the sensory quality of the juice—to recover the
lost aromas by PV and to feed them back to the final product. They investigated the
performance of six different PV membranes for the recovery of apple juice aromas
by PV. Apple juice aroma consists of about 300 different volatile components, of
which the total concentration amounts to approximately 200 ppm. In comparison
with other fruit juice aromas, apple juice aroma is different in that the whole aroma
complex is highly volatile. Esters are numerically the largest group of components.
Owing to their contribution to the fruity aroma, esters are considered to be the most
important group of apple aromas. Esters of a molecular weight of typically 100–
130 g/mol are responsible for most of the fruity part in apple aroma. Alcohols are
the quantitatively largest group of volatiles in apple aroma, of which ethanol is the
dominating component, present at typically 50–100 ppm. The third major group of
volatiles consists of aldehydes. Apart from the esters, both C-6 alcohols and C-6
aldehydes contribute to the fruity aroma. Other types of compounds such as ethers,
fatty acids, lactones, terpenes, and ketones are also present in apple aroma to vari-
ous degrees (Börjesson et al., 1996). To avoid the analysis problem of natural apple
juice, a model apple juice aroma solution has been developed, by the identification of
aroma compounds in apple juice by GC and GC-MS, gas chromatography with mass
spectrophotometer as detector and used in the experiments. They chose two polyoc-
tylmethyl siloxane (POMS) membranes with different porous support layers and a
polydimethyl siloxane (PDMS) membrane proved to have very good performance,
resulting in 100-fold to 1000-fold enrichment of aromas from the model apple juice
aroma solution with mass transfer coefficients up to 300 kg/m2 h.
Tan et al. (2005) studied the behavior of aroma compounds and ethanol during
PV using a model solution with six components. They supposed that in the PV of
alcoholic beverages, complicated interactions between ethanol and aroma com-
pounds often exist and affect their PV performance. The chosen series of model
solutions containing ethanol and six typical aroma compounds (ethyl acetate, metha-
nol, n-propanol, i-butanol, n-butanol, i-amyl alcohol) in alcoholic beverages were
experimented. The permeability coefficient was introduced to discuss the coupling
effects. The results showed that the solubility thermodynamics, with the feed solu-
tion activity coefficient had a dominant effect on the permeability rather than the
diffusion factor. They concluded that the presence of aroma compounds decreased
the permeability coefficient and separation factor of ethanol from those in ethanol–
water binary solutions, while it had little effect on the fluxes. The effect of ethanol
feed concentration on the mass transfer of each compound was much related to the
solubility properties of the compound in ethanol and water. Little interactions exist
in the PV process of diluted solution containing these aroma compounds within
1000 ppm (Tan et al., 2005).
The recovery of strawberry aroma compounds by PV has been studied by Isci
et al. (2005). The main objective of the study was to determine the effects of opera-
tional parameters, concentration, composition (different strawberry model solu-
tions), and permeate pressure on the recovery of strawberry aroma compounds by
PV. PV was performed using a hydrophobic membrane, PERVAP 1070 (PDMS).
They concluded that as the feed temperature increased or the downstream pres-
sure decreased, the mass flux and selectivity increased in the PV of methyl butyrate
(MTB) aqueous solution. Increase in feed concentration led to higher organic fluxes
but lower selectivity in binary aqueous solutions of both MTB and ethyl butyrate
(ETB). PERVAP 1070 showed higher selectivity toward MTB than ETB and MTB
flux was affected negatively by the presence of ETB in the feed solution. The pres-
ence of other aroma compounds adversely affected the selectivities of MTB and
ETB. They also concluded that PV is a promising technique for the recovery of
strawberry aroma compounds.
Pereira and coworkers (2005) investigated aroma recovery of tropical fruit juice
by the PV process using model solutes and different kinds of composite membranes.
Binary and quaternary synthetic aqueous solutions, as well as the single-strength and
clarified pineapple juices, were used as the feed solution. Composite membranes (flat
or hollow fiber), prepared in the laboratory or commercial ones, were used for com-
parison. The evaluation of different membrane materials with typical tropical fruit
aroma components showed that when the organic solute concentration is reduced in
the feed, it is advantageous to choose a very selective polymer. They also found that
if the feed concentration is high enough to induce phase separation in the permeate
after its condensation, the simulation results indicate that it is more advantageous to
use more permeable membranes, such as that made of PDMS. In the case of single-
strength fruit juices, the organic solute concentration is very reduced, which led to
the selection of EPDM as the membrane material. The PV of synthetic and single-
strength pineapple juice using composite EPDM hollow fiber showed a very high
enrichment of the most volatile components. The water permeability and the overall
mass transfer coefficient for each organic solute were determined. The results also
indicate that the lower the organic solute miscibility in water, the higher the over-
all mass transfer coefficient. The experimental PV results were used as input for a
simulation of a permeation unit, allowing a preliminary comparison of the different
membranes investigated. Experimental and simulation results indicated that EPDM
membranes presented the best performance (Pereira et al., 2005).
Pomegranate (Punica granatum L.) is one of the oldest known edible fruits.
It is cultivated extensively in Iran, Afghanistan, India, Mediterranean countries
(Tunisia, Turkey, Egypt, Spain, and Morocco), and to some extent in the United
States (California), China, Japan, and Russia. Iran is the native land of pomegranate
where it is grown in both coastal and mountainous areas. The edible part of the fruit
contains considerable amount of acids, sugars, vitamins, polysaccharides, polyphe-
nols, and important minerals. It has been reported that pomegranate juice has potent
antiatherogenic effects on healthy humans and atherosclerotic effects on mice that
could be attributed to its antioxidative properties. The fruit is consumed directly as
fresh seeds as well as fresh juice, which can also be used in beverages, in jellies,
and as a flavoring and coloring agent (Raisi et al., 2008). They studied the possibil-
ity of using the PV process to recover the pomegranate aroma compounds from an
actual pomegranate juice and a model aroma solution. Four different chemicals rep-
resenting four major kinds of aroma compounds, namely, 3-methyl butanal, isopen-
tyl acetate, n-hexanol, and β-ionone, were utilized in the experimental work. They
tested three POMS membranes and two PDMS membranes for PV and compared for
their separation performance. The influence of various operating parameters such as
feed flow rate, feed temperature, and permeate pressure on the permeation flux and
aroma compound enrichment factor was investigated. Feed flow rate was shown to
have no significant effect on both total flux and aroma enrichment factor, whereas
feed temperature and permeate pressure had highly significant effects. They con-
cluded that an increase in feed temperature led to higher flux and enrichment factor.
As the permeate pressure increased, the flux and enrichment factor of some aroma
compounds decreased. Some of the aroma compounds showed higher enrichment
factor at higher permeate pressures. Finally, the activation energy of permeation and
the membrane permeability for each aroma compound were determined (Raisi et al.,
2008).
The demand for processing bilberries (Vaccinium myrtillus L.) has increased in
the last few years. Although these fruits can be eaten fresh, they are more usually
processed to obtain products such as jams, fools, juices, or pies. Therefore, the cul-
tivation of this wild fruit has begun, mainly in North America. Important bilberry
producers among the European countries are France, Holland, Germany, Poland,
and Spain (Diban et al., 2008). PV, a membrane technology requiring low energetic
demands, is considered to substitute the conventional distillation unit employed in
the beverage industry in order to recover the key aroma compounds, and that would
avoid the damages to the quality of the flavor profile. Diban et al. (2008) analyzed
the separation and recovery of some selected aroma compounds belonging to bil-
berry juice made by employing a mathematical model previously developed for the
PV of volatile organic carbon (VOC). A PV hollow fiber module provided with a
PDMS commercial membrane was considered. For each compound, the characteris-
tic mass transfer parameters are the permeability of the membrane and the diffusion
coefficient in the aqueous phase. Enrichment factors over 100 were achieved for the
aroma compounds with higher permeabilities. They concluded that the membrane
thickness influenced the enrichment factor and flux. The bilberry impact aroma com-
pound ((E)-2-hexen-1-ol) was studied observing higher enrichment factors and lower
fluxes with higher membrane thicknesses until an asymptotic value was reached.
The predicted permeate composition achieved under the simulated conditions did
not keep the same proportion of that in the feed composition (Diban et al., 2008).
The aroma of apple juice is a highly volatile fraction consisting of over 300 dif-
ferent compounds, including mainly esters, aldehydes, and alcohols, but also ethers,
fatty acids, lactones, terpenes, and ketones. The total aroma concentration in apple
juice is about 200 ppm, but can vary significantly depending on the variety and ori-
gin of the apples, as well as factors such as storage and ripening conditions. The
processing of apple juice on an industrial scale often requires an evaporation step.
This step is inevitably associated with the deterioration of sensoric characteristics
due to physical and chemical losses as a result of evaporation and chemical changes
of aroma compounds. Therefore, aroma recovery is an important feature in bever-
age processing. Complex process combinations are often employed to reduce aroma
losses during processing by recovering lost aroma compounds from process side-
streams. Conventional processes such as adsorption and steam stripping are applied
to recover the aroma compounds. Alternatively, PV can be used to recover the aroma
compounds, either before processing or from the side-stream. The focus of the stud-
ies (Lipnizki et al., 2002a,b) was on eight aroma compounds with high aroma values
and, therefore, of great importance to the aroma complex. These components also
represent the major chemical groups in the apple juice complex, namely, alcohols,
aldehydes, and esters. Among these different groups, the recovery of esters is par-
ticularly important since they are most likely to evaporate or react chemically during
heat treatment.
Lipnizki et al. (2002a,b) published two articles in series about the application of
the experimental studies of multicomponent systems for the design and development
PV on an industrial scale. In the first part of the study (Lipnizki et al., 2002a), a
simulation program for hydrophobic PV, previously developed for binary systems in
wastewater treatment (Lipnizki and Field, 1999, 2001), has been extended and modi-
fied for aqueous multicomponent mixtures of up to 20 different aroma compounds
relevant to food. The program is based on the resistance-in-series model and covers
the mass transfer through the membrane and the feed-side concentration boundary
layer. The simulation also includes the influence of the heat balance and perme-
ate side pressure gradient using a finite-element-in-succession method. Using this
model, PV units can be sized and reheaters can be placed in the process to optimize
the process performance. Plate-and-frame modules have been considered since these
are the most widely used modules for PV (Lipnizki et al., 2002a). In the first part of
the study, the applicability of PV for aroma recovery was demonstrated under dif-
ferent process conditions using process simulation. The aim of this part of the study
was to optimize hydrophobic PV for aroma recovery in the food industry, taking
technical aspects and cost engineering into account. In order to demonstrate the
potential of hydrophobic PV within the food industry, the recovery of natural apple
aroma was studied. Two different feed-sized juice streams were investigated. For a
feed stream of 50 kg/h, a semibatch process was designed, and for a feed stream of
1000 kg/h, a continuous process was designed.
In the second study (Lipnizki et al., 2002b), the integration and optimization of
hydrophobic PV for the recovery of natural aroma compounds in the food industry
has been studied. The simulation developed in the first part of the study (Lipnizki
et al., 2002a) was applied to the design and scale-up of PV units for the recovery of
natural apple juice aroma. Both semibatch and continuous process configurations
were considered and the process conditions were optimized taking the cost of the
process into account. For the semibatch process, the cost per kilogram of concen-
trated aroma was between 31.30EUR and 33.60EUR, depending on the membrane
type. When returning the recovered aroma to the apple juice after heat treatment,
the cost of aroma recovery per kilogram concentrate was between 0.31EUR and
0.34EUR. In the case of the continuous process, the cost for the apple juice aroma
recovery was between 2.19EUR and 5.38EUR, while the cost of aroma recovery per
kilogram of apple juice was between 0.03EUR and 0.05EUR (Lipnizki et al., 2002b).
PV is a membrane technology utilizing a dense nonporous homogeneous poly-
meric film as a selective separation barrier. In recent years, PV using dense mem-
branes has emerged as a promising remediation method for trace organic removal
from dilute aqueous solutions. The mathematical model commonly used to deter-
mine liquid and polymer phase resistances is the resistance-in-series model. In most
studies, the concentration or pressure gradient is considered as the driving force
(Huang, 1991). In the study by Ghoreysi and coauthors (2008), a model was devel-
oped based on a resistance-in-series model considering the chemical potential gradi-
ent as the true driving force in which the total resistance to mass transfer is defined
as the sum of the liquid, membrane, and vapor resistance. The model was validated
by the experimental data available in the literature for various organic solutions
and different membranes, including PDMS and composite membranes. The results
obtained showed that the liquid-phase boundary layer plays a significant rule in over-
all mass transport for all cases under study and ignoring this contribution could lead
to a significant error in design and scale-up applications. It was also shown by them
that the flux of the permeating component is unaffected by the downstream pressure
at low pressures up to 10 mmHg, which indicates that for such systems, the operating
condition can be economically designed based on a moderate vacuum at downstream
side instead of using a full expensive vacuum system (Ghoreyshi et al., 2008).
Chanchai et al. (2010) studied the coating of hydrophobic membrane PVDF with
chitosan, a highly hydrophilic polymer, for protection against wetting by oils from
fruit juice and for the reduction of flavor losses in the OD process. Fourier transform
infrared (FTIR) spectroscopy and SEM results indicated that chitosan was well coated
on a PVDF membrane surface. The protection against wetting of the membranes was
tested by the OD of an oil solution (limonene 2%, v/v) for 5 h. The results indicated
that the coated membrane was able to protect the membrane against wetting-out and
could maintain a stable flux. An uncoated membrane was obviously wetted, which
was supported by the existence of CaCl2 in the retentate solution and the decrease
of the permeate flux. Coating of a membrane with chitosan resulted in a membrane
with higher water flux. For the membrane coated with chitosan cross-linked by form-
aldehyde, water flux decreased with increasing formaldehyde concentration. In the
OD of flavors (ethyl acetate and ethyl hexanoate)–limonene–water mixtures, when

the limonene concentration was increased, water flux decreased significantly while
flavor fluxes and flavor losses increased. Coated membranes not only gave higher
water flux but they also gave lower flavor flux. The results suggested that the coated
membrane was appropriate for feed containing high limonene oil.
Rafia et al. (2011) used a PV process to recover volatile aroma compounds from
lemon juice with a POMS membrane. They stated that in order to successfully opti-
mize the PV process, it is essential to work with actual fruit juice. They studied the
influences of various operating parameters such as feed flow rate, feed temperature,
and permeate pressure on the permeate flux, and the selectivity of the above-men-
tioned membrane using three compounds that make significant contribution to lemon
juice aroma, namely, alpha-pinene, beta-pinene, and limonene, was studied. They
showed that decreasing the permeate pressure increased both the permeation flux
and the enrichment factor, while an increase in feed temperature increased the water
flux more significantly than the aroma compound flux, resulting in a lower enrich-
ment factor. Also, the results indicated that feed flow rate had no significant effect on
the performance of the process. They concluded that the membrane used was very
selective toward alpha-pinene, beta-pinene, and limonene (Rafia et al., 2011).
6.5.2 Deacidification
Tropical fruit juices are appreciated for their intense aroma and flavor. Their quality
could be improved further by reducing their acidity. Electrodialysis (ED) is an inter-
esting method for the deacidification of fruit juice, relative to calcium salt precipita-
tion, which involves the addition of chemical reagents, and relative to ion-exchange
resins, which strongly modify the aroma and provide effluents during the regenera-
tion step (Vera et al., 2009). Many ED assays are achieved by using a lab-cell. Fouling
is the main limiting factor of this membrane technique. Results obtained in this study
showed that the use of a preindustrial stack reduced fouling and allowed the deacidi-
fication of passion fruit juice even at the initial pulpy state. The reduction of acidity
of passion fruit juice was investigated by ED with bipolar membranes (BM) at the
laboratory and preindustrial scale by Vera et al. (2009). Four states of juice were
tested: initial pulpy juice, juice clarified by tangential MF, twice-concentrated clari-
fied juice, and centrifuged juice. The ED performances were compared in terms of
deacidification rate, current efficiency, and energy consumption. The deacidification
was carried out up to pH 4.5 with satisfactory results. ED performances were lower
with the pulpy and concentrated juices because of fouling of the anion-exchange
membrane, which increased the voltage. The differences in acidity between the
juices was reduced by the preindustrial ED stack, which involved better hydrody-
namics through high flow rates and low compartment thickness. Whatever the juices,
physicochemical analysis showed that the color changed only slightly. Nevertheless,
the best ED performances were obtained with the clarified and centrifuged passion
fruit juice. Thus, if the production of a pulpy deacidified juice is analyzed, the per-
formance of the process could be improved by combining the ED technique with
centrifugation, instead of a direct deacidification of the pulpy juice, because of the
high fouling observed during the ED of this kind of juice (Vera et al., 2009).
6.5.3 Novel Products
As stated by Cassano et al. (2008), foods characterized by protective and health-
promoting potential, in addition to their nutritive value, are recognized as functional
foods. The beneficial components in functional foods have been called by various
terms such as phytochemicals, functional components, and bioactive components.
These components may exert their effects by acting as antioxidants, activating liver
detoxification enzymes, blocking the activity of bacterial or viral toxins, inhibiting
cholesterol adsorption, decreasing aggregation, or destroying harmful gastrointesti-
nal bacteria (Cassano et al., 2008). As pointed out by them, epidemiological stud-
ies have shown that there is a significant positive association between the intake
of fruits and vegetables and the reduced risk of chronic diseases, such as cancer,
cardiovascular disease, diabetes, osteoporosis, Alzheimer’s disease, and immune
disorders. The fruit of the Actinidia plant is known more commonly as kiwifruit. Its
cultivation is very significant in Italy, the world’s largest producer of kiwifruit, with
a production of about 330,000 tons/year (about 33% of the worldwide production).
Instead of the production of derivatives addressed to the consumers or for the food
industry (nectars, syrup, whole or dried kiwifruit, powder of dried puree, clarified
juice to be used in juice blending, jams, sugared and dried pulp, concentrated juices,
fermented beverages, and wine), kiwifruit can be exploited as a source of interesting
components (Cassano et al., 2008). It is characterized by a high content of beneficial
substances for human health such as vitamins, minerals, and polyphenols. Among
the different substances contained in the kiwifruit, a primary role in the safeguard
of human health is carried out by some bioactive compounds such as ascorbic, folic,
citric, and glutamic acids. Considering this, Cassano et al. (2008) studied the influ-
ence of UF on the composition of some bioactive compounds of kiwifruit juice in
order to develop a natural product, which can be used to fortify foods and bever-
ages. They investigated the influence of the process parameters such as the effect of
TMP and temperature on the permeate flux in order to identify the optimal operating
conditions for the processing of the juice. They found that an optimal TMP value
occurred at 0.6–0.65 bar in different conditions of CFVs. Steady-state permeate
fluxes increased linearly with temperature in the 20–30°C range. The kiwifruit juice
was clarified in optimal operating conditions, according to the batch concentration
mode, up to a final VRF of 2.76. The analyses of flux decay according to fouling
models reported in the literature revealed that the formation of a cake layer covering
the entire surface of the membrane is the main cause of membrane fouling. Most bio-
active compounds of the depectinized kiwifruit juice were recovered in the clarified
fraction of the UF process. The rejection of the UF membrane toward total phenolics
was 13.5%. The recovery of glutamic, folic, ascorbic, and citric acids in the clari-
fied juice, with respect to the initial feed, was dependent on the final VRF of the UF
process: an increase of the VRF determines an increase of these compounds in the
clarified juice. They concluded that the rejections of the UF membrane toward these
compounds were in the range 0%–4.3%.
Nayak and Rastogi (2010) compared the OMD and FO membrane processes
for the concentration of anthocyanin extract and also studied the effect of various
process parameters such as osmotic agent concentration and flow rates of feed and
osmotic agent on the transmembrane flux. The mechanism of mass transfer in the
case of OMD and FO has been explained by them. Mass and heat transfer coef-
ficients for feed side, osmotic agent side, membrane mass transfer coefficient, and
overall transfer coefficient have been determined. In case of FO, the anthocyanin
extract was concentrated from 49.63 mg/L to 2.69 g/L in 18 hours; however, it was
coupled with the migration of sodium chloride (0.21 moles/m2 s). However, in case of
the OMD process, the concentration of anthocyanin was achieved up to 72 mg/L for
the same time without any transfer of osmotic agent. The transmembrane flux in case
of OMD was low as compared to FO. These may prove to be potential techniques
for the concentration of natural colorants. The concentration of kokum extract using
the FO membrane process has advantages over thermal concentration in terms of
higher stability, lower browning index, and less conversion of hydroxycitric acid to
its lactone form (Nayak and Rastogi, 2010).
Concentration and purification of bioactive compounds have become a subject of
increased interest in the last several decades. Bergamot is the common name of the
fruit Citrus bergamia Risso, an endemic plant of the Calabrian region in Southern
Italy, whose volatile fraction is widely used in the cosmetic and perfumery industries
(Conidi et al., 2011). The juice, as a waste of the essential oil production, contains
a considerable amount and variety of flavonoids and flavonoid glycosides having
important health implications. Conidi et al. (2011) investigated a membrane-based
process for the separation and concentration of polyphenols in the bergamot juice, in
order to develop a natural product enriched in polyphenols suitable for nutraceutical
applications. The process was based on the initial clarification of depectinized ber-
gamot juice by UF, devoted to the removal of suspended solids. The clarified juice
was then submitted to membrane screening, using different UF and NF membranes
in order to evaluate the effect of the nominal MWCO on the rejection of the mem-
branes toward sugars, organic acids, and polyphenols. The performance of selected
membranes was also evaluated in terms of productivity and composition of produced
permeate and retentate fractions (Conidi et al., 2011).
6.6 VEGETABLE JUICE PROCESSING AND CONCENTRATION

BY MEMBRANE SEPARATION PROCESSES
The food industry represents a significant part of the turnover of the membrane man-
ufacturing industry worldwide. Among the numerous applications on an industrial
scale, a few of the main separations that represent the latest advances in food pro-
cessing are reported. Clarification of fruit, vegetable, and sugar juices by MF or UF
allows the flow sheets to be simplified or the processes made cleaner and the final
product quality improved. Enzymatic hydrolysis combined with selective UF can
produce beverages from vegetable proteins (Daufin et al., 2001).
The concentration of tomato pulp of high organoleptic quality by UF and by
RO (4.5%–9% dissolved solids [DS]) are the major industrial membrane processes
applied to vegetable juices. Other vegetables (cucumber, carrot, mushroom, celery,
etc.) are clarified and concentrated by UF and RO and even demineralized by NF
(nitrates, nitrites, etc.), which stabilizes the concentrate of red beetroot, among
others (Daufin et al., 2001).
Petrotos et al. (1998) and Petrotos and Lazarides (2001) investigated the DOC of
tomato juice in a tubular membrane. They studied the effect of certain basic process
parameters on the process performance. They used a novel tubular module to inves-
tigate the DOC process in the case of tomato juice. The module was constructed
according to given specifications, by PCI UK and consisted of an external stain-
less-steel shroud accommodating, internally, a set of two identical RO membrane
tubes having no support lengthwise and properly sealed at their ends. The process
performance was measured in terms of water permeation flux and its response to
changes of the process parameters was experimentally assessed and established. The
process parameters that were investigated in the course of this study were the kind
of osmotic medium, viscosity of osmotic medium, osmotic medium concentration,
juice temperature, juice flow rate, juice concentration, and membrane thickness.
Sodium chloride brine was found to be the best osmotic medium, among the six that
were tried, and this was due to its very low viscosity. The above parameter appears
to be of paramount importance regarding the effectiveness of an osmotic medium.
They concluded that the higher osmotic medium concentrations yield higher osmotic
permeation rates. Increasing the juice temperature was found to markedly increase
the permeation flux. However, only a slight enhancement of flux was observed by
increasing the juice flow rate. Moreover, higher juice concentrations up to approxi-
mately 12° Brix led to a lowering of the osmotic flux. Finally, as far as the membrane
thickness was concerned, a strong trend was revealed for an exponential increase
of permeation by shifting toward lower membrane thicknesses. They concluded
that this trend however needs to be further investigated as an inadequate number of
experimental points were obtained due to lack of additional membranes.
Petrotos et al. (1998) and Petrotos and Lazarides (2001) investigated several
parameters believed to affect the performance in the operation of the DOC of tomato
juice. Initially, a comparison was carried out by using six different osmotic media,
including sodium chloride brine, calcium chloride brine, calcium nitrate brine,
sucrose solution, glucose solution, and polyethylene glycol 400 solution. The most
effective among them was the sodium chloride solution. Additionally, the measured
osmotic flux values with different osmotic media were not in correlation to the cor-
responding overall osmotic pressure difference but to the viscosity of the osmotic
medium used each time. Accordingly, this was considered to be a clear evidence
of the importance of using low-viscosity osmotic media in direct osmotic applica-
tions. Also, the increase of the osmotic medium concentration, despite the fact that it
resulted in higher osmotic fluxes due to increased osmotic pressure at high concen-
trations, led to a reduced overall mass transfer coefficient. This overall mass transfer
coefficient was found to be inversely proportional to the osmotic medium concentra-
tion and the parameter that was responsible for this particular relationship was iden-
tified to be the viscosity of the osmotic medium. An increase in juice temperature
led to a positive effect on the DOC flux. However, the well-known and anticipated
Arrhenius relationship, which exists between flux and temperature in other mem-
brane processes, was not found to be valid in this present case. On the other hand,
the juice flow rate did not substantially affect the direct osmosis flux and this was
attributed to the rheological particularities of the tomato juice, which caused a phe-
nomenon previously identified as the tubular pinch effect. The increase in the tomato
juice concentration had a reducing effect on the direct osmosis flux. The increase in
juice osmotic pressure at higher concentration along with the changes in the physical
properties of the juice (higher viscosities and lower diffusivities at high concentra-
tion) both contributed to the observed reduction. Finally, a parameter of paramount
importance for the operation of DOC was proved to be the overall thickness of the
used membrane, as a trend of an exponential increase of flux with reducing overall
thickness was revealed for a certain range of membrane thicknesses. However, addi-
tional work is needed in order to ascertain whether this trend is consistent at even
lower membrane thicknesses.
Razi et al. (2012) investigated the effect of TMP and axial flow rate on membrane
fouling during tomato juice clarification, studied by cross-flow MF using flat-sheet
polyvinylidenefluoride membranes. The effect of fouling on permeate flux was mod-
eled using a classical constant-pressure dead-end filtration equation and its modified
form for cross-flow filtration. The main physicochemical properties of tomato juice
were analyzed. They concluded that the clarified juice was very similar to the feed
except for insoluble solids and lycopene, which were concentrated in the retentate. They
stated that in case of different axial flow rates, the fouling mechanism evolves from
cake filtration to an intermediate pore blocking mechanism with increasing pressure.
REFERENCES
Ashurst, P. R. 2005. Chemistry and Technology of Soft Drinks and Fruit Juices. Blackwell
Publishing Ltd., Oxford, UK.
Banvolgyi, S. z. 2009. Concentration of Black Currant Juice and Red Wine by Integrated
Membrane Processes (in Hungarian). PhD thesis, Corvinus University of Budapest.
Banvolgyi, S. z., Horváth, S. z., Békássy-Molnár, E., Vatai, G. 2006. Concentration of black-
currant (Ribes nigrum L.) juice with nanofiltration. Desalination 200, 535–536.
Barbe, A. M., Bartley, J. P., Jacobs, A. L., Johnson, R. A. 1998. Retention of volatile organic
flavour/fragrance components in the concentration of liquid foods by osmotic distilla-
tion. Journal of Membrane Science 145, 67–75.
Barta, J., Körmendy, I. 2007. Basic Processes of Vegetable and Fruit Processing Technologies
(in Hungarian). Mezőgazda Kiadó, Budapest.
Belafi-Bako, K., Gubicza, L., Mulder, M. 2000. Integration of Membrane Processes into
Bioconversation. Kluwer Academic/Plenum Publishers, New York, USA.
Belafi-Bako, K. 2002. Membrane Separation Processes (in Hungarian). Veszprémi Egyetemi
Kiadó, Veszprém.
Börjesson, J., Karlsson, H. O. E., Trägardh, G. 1996. Pervaporation of a model apple juice
aroma solution: Comparison of membrane performance. Journal of Membrane Science
119, 229–239.
Baudot, A., Souchon, I., Marin, M. 1999. Total permeate pressure influence on the selectivity
of the pervaporation of aroma compounds. Journal of Membrane Science 158, 167–185.
Carvalho, L. M. J., de Castro, I. M., da Silva, C. A. B. 2008. A study of retention of sugars in
the process of clarification of pineapple juice (Ananas comosus, L. Merril) by micro-
and ultra-filtration. Journal of Food Engineering 87, 447–454.
Cassano, A., Conidi, C., Drioli, E. 2011. Clarification and concentration of pomegranate juice
(Punica granatum L.) using membrane processes. Journal of Food Engineering 107,
366–373.
Cassano, A., Conidi, C., Drioli, E. 2013. A membrane-based process for the valorization of
the bergamot juice. Separation Science and Technology 48, 527–546.
Cassano, A., Donato, L., Conidi, C., Drioli, E. 2008. Recovery of bioactive compounds in
kiwifruit juice by ultrafiltration. Innovative Food Science and Emerging Technologies
9, 556–562.
Cassano, A., Donato, L., Drioli, E. 2007c. Ultrafiltration of kiwifuit juice: Operating
parameters, juice quality and membrane fouling. Journal of Food Engineering 79,
613–621.
Cassano, A., Drioli, E. 2007d. Concentration of clarified kiwifruit juice by osmotic distilla-
tion. Journal of Food Engineering 79, 1397–1404.
Cassano, A., Drioli, E., Galaverna, G., Marchelli, R., Di Silvestro, G., Cagnasso, P. 2003.
Clarification and concentration of citrus and carrot juices by integrated membrane pro-
cesses. Journal of Food Engineering 57, 153–163.
Cassano, A., Figoli, A., Tagarelli, A., Sindona, G., Drioli, E. 2006a. Integrated membrane
process for the production of highly nutritional kiwifruit juice. Desalination 189,
21–30.
Cassano, A., Jiao, B., Drioli, E. 2004. Production of concentrated kiwifruit juice by inte-
grated membrane process. Food Research International 37, 139–148.
Cassano, A., Marchio, M., Drioli, E. 2007b. Clarification of blood orange juice by ultra-
filtration: Analyses of operating parameters, membrane fouling and juice quality.
Cassano, A., Tasselli, F., Drioli, E. 2007a. Ultrafiltration of kiwifruit juice using modi-
fied poly(ether ether ketone) hollow fibre membranes. Separation and Purification
Technology 57, 94–102.
Chanachai, A., Meksup, K., Jiraratananon, R. 2010. Coating of hydrophobic hollow fiber
PVDF membrane with chitosan for protection against wetting and flavor loss in osmotic
distillation process. Separation and Purification Technology 72, 217–224.
Cheryan, M. 1998. Ultrafiltration and Microfiltration Handbook. Technomic, Lancaster,
Basel.
Conidi, C., Cassano, A., Drioli, E. 2011. A membrane-based study for the recovery of poly-
phenols from bergamot juice. Journal of Membrane Science 375, 182–190.
Courel, M., Dornier, M., Herry, J. M., Rios, G. M., Reynes, M. 2000. Effect of operating
conditions on water transport during the concentration of sucrose solutions by osmotic
distillation. Journal of Membrane Science 170, 281–289.
Daufin, G., Escudier, J.-P., Carre Á Re, H., Be Â Rot, S., Filaudeau, L., Decloux, M. 2001.
Recent and emerging applications of membrane processes in the food and dairy indus-
try. Transactions of the Institution of Chemical Engineers 79, Part C, 89–102.
Diban, N., Urtiaga, A., Ortiz, I. 2008. Recovery of key components of bilberry aroma using a
commercial pervaporation membrane. Desalination 224, 34–39.
Domingues, R. C. C., Ramos, A. A., Cardoso, V. L., Reis, M. H. M. 2014. Microfiltration
of passion fruit juice using hollow fibre membranes and evaluation of fouling mecha-
nisms. Journal of Food Engineering 121, 73–79.
El-Bourawi, M. S., Ding, Z., Ma, R., Khayet, M. 2006. A framework for better understanding
membrane distillation separation process. Journal of Membrane Science 285, 4–29.
Field, R. W., Wu, D., Howel, J. A., Gupta, B. B. 1995. Critical flux concept for microfiltration
fouling. Journal of Membrane Science 100, 250–272.
Fontalvo, J., Cuellar, P. C., Wijers, J. G., Keurentjes, J. T. F. 2006. Study of the hydrodynam-
ics in a pervaporation module and implications for the design of multi-tubular systems.
Journal of Membrane Science 281, 219–227.
Fonyó, Z. s., Fábry, G. y. 1998. Basic Principles of Unit Operations (in Hungarian). Nemzeti
Tankönyvkiadó, Budapest.
Forero, L. F., Vélez, P. C. A., Sandoval, A. A. P. 2013. Ultrafiltration and osmotic evapora-
tion applied to the concentration of cholupa (Passiflora maliformis) juice. Ingeniería e
Investigación 33, 35–40.
Galaverna, G., Di Silvestro, G., Cassano, A., Sforza, S., Dossena, A., Drioli, E., Marchelli,
R. 2008. A new integrated membrane process for the production of concentrated blood
orange juice: Effect on bioactive compounds and antioxidant activity. Food Chemistry
106, 1021–1030.
Ghoreyshi, A. A., Jahanshahi, M., Peyvandi, K. 2008. Modeling of volatile organic com-
pounds removal from water by pervaporation process. Desalination 222, 410–418.
Gilewicz-Lukasik, B., Koter, S., Kurzawa, J. 2007. Concentration of anthocyanins by the
membrane filtration. Separation and Purification Technology 57, 418–424.
Gomes, F. D., da Costa, P. A., de Campos, M. B. D. Couri, S., Cabral, L. M. C. 2011.
Concentration of watermelon juice by reverse osmosis process. Desalination and Water
Treatment 27, 120–122.
He, Y., Zhijuan, Ji., Shunxin, L. i. 2007. Effective clarification of apple juice using membrane
filtration without enzyme and pasteurization pretreatment. Separation and Purification
Technology 57, 366–373.
Hongvaleerat, C., Cabral, L. M. C., Dornier, M., Reynes, M., Ningsanond, S. 2008.
Concentration of pineapple juice by osmotic evaporation. Journal of Food Engineering
88, 548–552.
Huang, R. 1991. Pervaporation Membrane Separation Processes. Elsevier, Amsterdam, The
Netherlands.
Hui, Y. H., Barta, J., Cano, M. P., Gusek, T. W., Sidhu, J. W., Sinha, N. Editors. 2006.
Handbook of Fruits and Fruit Processing. Blackwell Publishing, Oxford, UK.
Isci, A., Sahin, S., Sumnu, G. 2005. Recovery of strawberry aroma compounds by pervapora-
tion. Journal of Food Engineering 75(1), 36–42.
Jesus, F. D., Leite, M. F., Silva, L. F. M., Modesta, R. D., Matta, V. M., Cabral, L. M. C.
2007. Orange (Citrus sinensis) juice concentration by reverse osmosis. Journal of Food
Engineering 81, 287–291.
Jiao, B., Cassano, A., Drioli, E. 2004. Recent advances on membrane processes for the con-
centration of fruit juices. Journal of Food Engineering 63, 303–324.
Karlsson, H. O. E., Tragardh, G. 1996. Applications of pervaporation in food processing.
Trends in Food Science & Technology 7, 78–83.
Kiss, I., Vatai, G. y., Bekassy-Molnar, E. 2004. Must concentration using membrane technol-
ogy. Desalination 162, 295–300.
Kozak, A. 2005. Experimental Investigation of Must Concentration by Reverse Osmosis
and Membrane Distillation (in Hungarian). MSc thesis, Corvinus University of
Budapest.
Kozak, A., Bánvölgyi, S. z., Vincze, I., Kiss, I., Békássy-Molnár, E., Vatai, G. y. 2008.
Comparison of integrated large scale and laboratory scale membrane processes for the
production of black currant juice concentrate. Chemical Engineering and Processing
47, 1171–1177.
Laeson, K. W., Lloyd, D. R. 1997. Membrane distillation. Journal of Membrane Science 124,
1–25.
Lagana, F., Barbieri, G., Drioli, E. 2000. Direct contact membrane distillation: Modelling
and concentration experiments. Journal of Membrane Science 166, 1–11.
Laorko, A., Li, Z. Y., Tongchitpakdee, S., Youravong, W. 2011. Effect of gas sparging on flux
enhancement and phytochemical properties of clarified pineapple juice by microfiltra-
tion. Separation and Purification Technology 80, 445–451.
Lefebvre, M. S. M. 1988. Method of performing osmotic distillation. US Patent 4,781,837, 1
November.
Lipnizki, F., Field, R. W. (1999). Simulation and process design of pervaporation plate-and-
frame modules to recover organic compounds from waste water. Transactions of the
Institution of Chemical Engineers Part A 77, 231–240.
Lipnizki, F., Field, R. W. 2001. Integration of vacuum and sweep gas pervaporation to recover
organic compounds from wastewater. Separation and Purification Technology 22–23,
347–360.
Lipnizki, F., Olsson, J., Trägårdh, G. 2002a. Scale-up of pervaporation for the recovery of
natural aroma compounds in the food industry. Part 1: Simulation and performance.
Journal of Food Engineering 54, 183–195.
Lipnizki, F., Olsson, J., Trägårdh, G. 2002b. Scale-up of pervaporation for the recovery of
natural aroma compounds in the food industry. Part 2: Optimisation and integration.
Matta, V. M., Moretti, R. H., Cabral, L. M. C. 2004. Microfiltration and reverse osmosis
for clarification and concentration of acerola juice. Journal of Food Engineering 61,
477–482.
Mietton-Peuchot, M., Milisic, V., Noilet, P. 2002. Grape must concentration by using reverse
osmosis. Comparison with chaptalization. Desalination 148, 125–129.
Molnar, Z. s., Bánvölgyi, S. z., Kozak, A., Kiss, I., Békássy-Molnár, E., Vatai, G. y. 2009.
Raspberry (Rubus idaeus L.) juice concentration by membrane processes. 1st Conference
on Applied Biocatalysis and 5th Meeting of Students and University Professors from
Maribor and Zagreb. Maribor, Slovenia. Full text on CD. ISBN 978-961-248-153-7.
Mosshammer, M. R., Stintzing, F. C., Carle, R. 2006. Evaluation of different methods for the
production of juice concentrates and fruit powders from cactus pear. Innovative Food
Science and Emerging Technologies 7, 275–287.
Nayak, C. A., Rastogi, N. K. 2010. Comparison of osmotic membrane distillation and for-
ward osmosis membrane processes for concentration of anthocyanin. Desalination and
Water Treatment 16, 134–145.
Neifar, M., Ellouze-Ghorbel, R., Kamoun, A., Baklouti, S., Mokni, A., Jaouani, A., Ellouze-
Chaabouni, S. 2011. Effective clarification of pomegranate juice using laccaze treat-
ment optimized by response surface methodology followed by ultrafiltration. Journal
of Food Process Engineering 34, 1199–1219.
Nene, S., Kaur, S., Sumod, K., Joshi, B., Raghavaro, K. S. M. S. 2002. Membrane distil-
lation for the concentration of raw cane-sugar syrup and membrane clarified juice.
Onsekizoglu, P., Bahceci, K. S., Acar, M. J. 2010. Clarification and the concentration of
apple juice using membrane processes: A comparative quality assessment. Journal of
Pagani, M. M., Rocha-Leao, M. H., Couto, A. B. B., Pinto, J. P., Ribeiro, A. O., Gomes, F. D.,
Cabral, L. M. C. 2011. Concentration of acerola (Malpighia emarginata DC) juice by inte-
grated membrane separation process. Desalination and Water Treatment 27, 130–134.
Patil, G., Raghavarao, K. S. M. S. 2007. Integrated membrane process for the concentration
of anthocyanin. Journal of Food Engineering 78, 1233–1239.
Pereira, C. C., Rufino, J. R. M., Habert, A. C., Nobrega, R., Cabral, C. P. B. L.M.C. 2005.
Aroma compounds recovery of tropical fruit juice by pervaporation: membrane mate-
rial selection and process evaluation. Journal of Food Engineering 66, 77–87.
Petrotos, K. B., Lazarides, H. N. 2001. Osmotic concentration of liquid foods. Journal of
Food Engineering 49, 201–206.
Petrotos, K. B., Quantick, P., Petropakis, H. 1998. A study of the direct osmotic concentration
of tomato juice in tubular membrane—Module configuration. I. The effect of certain
basic process parameters on the process performance. Journal of Membrane Science
150, 99–110.
Popper, K., Camirand, W. M., Nury, F., Stanley, W. L. 1966. Dialyzer concentrates beverages.
Food Engineering 38(4), 102–104.
Porter, M. C. l990. Handbook of Industrial Membrane Technology. Noyes Data, Park Ridge.
Rafia, N., Aroujalian, A., Raisi, A. 2011. Pervaporative aroma compounds recovery from
lemon juice using poly(octyl methyl siloxane) membrane. Journal of Chemical
Technology and Biotechnology 86, 534–540.
Rai, P., Majumdar, G. C., Dasgupta, S., De, S. 2010. Flux enhancement during ultrafiltration
of depectinized mosambi (Citrus sinensis [L] Osbeck) juice. Journal of Food Process
Engineering 33, 554–567.
Raisi, A., Aroujalian, A., Kaghazchi, T. 2008. Multicomponent pervaporation process for
volatile aroma compounds recovery from pomegranate juice. Journal of Membrane
Science 322, 339–348.
Rautenbach, R. 1997. Membranverfahren. Verlag, Berlin.
Ravindra Babu, B., Rastogi, N. K., Raghavarao, K. S. M. S. 2008. Concentration and temper-
ature polarization effects during osmotic membrane distillation. Journal of Membrane
Science 322, 146–153.
Razi, B., Aroujalian, A., Fathizadeh, M. 2012. Modeling of fouling layer deposition in cross-
flow microfiltration during tomato juice clarification. Food and Bioproduct Processing
90, 841–848.
Rektor, A., Kozak, A., Vatai, G. y., Bekassy-Molnar, E. 2007. Pilot plant RO-filtration of
grape juice. Separation and Purification Technology 57, 473–475.
Rektor, A., Pap N., Kókai, Z., Szabó, R., Vatai, G. y., Bekassy-Molnar, E. 2004. Application
of membrane filtration methods for must processing and preservation. Desalination
162, 271–277.
Rektor, A., Vatai, G. y., Békássy-Molnár, E. 2006. Multi-step membrane processes for the
concentration of grape juice. Desalination 191, 446–453.
Riberia, C. P., Jr., Paolo, L. C., Borges, L., Cristiano P. 2004. A combined gas-stripping vapour
permeation process for aroma recovery. Journal of Membrane Science 238, 9–19.
Rizvi, S. S. H. 2010. Separation, Extraction and Concentration Processes in the Food,
Beverage and Nutraceutical Industries. Woodhead Publishing, Cambridge, UK.
Rodrigues, R. B., Menezes, H. C., Cabral, L. M. C., Dornier, M., Rios, G. M., Reynes, M.
2004. Evaluation of reverse osmosis and osmotic evaporation to concentrate camu-
camu juice (Myrciaria dubia). Journal of Food Engineering 63, 97–102.
Saleh, Z. S., Stanley, R., Wibisono, R. 2006. Separation and concentration of health com-
pounds by membrane filtration. International Journal of Food Engineering 2, 1–14.
Santana, I., Gurak, P. D., da Matta, V. M., Freitas, S. P., Cabral, L. M. C. 2011. Concentration
of grape juice (Vitis labrusca) by reverse osmosis process. Desalination and Water
Treatment 27, 103–107.
Sant’Anna, V., Marczak, L. D. F., Tessaro, I. C. 2012. Membrane concentration of liquid foods by
forward osmosis: Process and quality view. Journal of Food Engineering 111, 483–489.
Schafer, T., Crespo, J. G. 2007. Study and optimization of the hydrodynamic upstream condi-
tions during recovery of a complex aroma profile by evaporation. Journal of Membrane
Science 301, 46–56.
Sotoft, L. F., Christensen, K. V., Andresen, R., Norddahl, B. 2012. Full scale plant with mem-
brane based concentration of blackcurrant juice on the basis of laboratory and pilot
scale tests. Chemical Engineering and Processing 54, 12–21.
Souza, A. L. R., Pagani, M. M., Dornier, M., Gomes, F. S., Tonon, R. V., Cabral, L. M.
C. 2013. Concentration of camu-camu juice by the coupling of reverse osmosis and
osmotic evaporation processes. Journal of Food Engineering 119, 7–12.
Tan, S., Li, L., Xiao, Z., Wu, Y., Zhang, Z. 2005. Pervaporation of alcoholic beverages—
The coupling effects between ethanol and aroma compounds. Journal of Membrane
Science 264, 8.
Thanedgunbaworn, R., Jiraratananon, R., Nguyen, M. H. 2007. Mass and heat transfer analy-
sis in fructose concentration by osmotic distillation process using hollow fibre module.
Vaillant, F., Jeanton, E., Dornier, M., O’Brien, G. M., Reynes, M., Decloux, M. 2001.
Concentration of passion fruit juice on an industrial pilot scale using osmotic evapora-
tion. Journal of Food Engineering 47, 195–202.
Vera, E., Sandeaux, J., Persin, F., Pourcelly, G., Dornier, M., Ruales, J. 2009. Deacidification
of passion fruit juice by electrodialysis with bipolar membrane after different pretreat-
ments. Journal of Food Engineering 90, 67–73.
Vatai, Gy. 2007. Processing of Agricultural Raw Materials and Foods by Complex
Membrane Separation Processes (in Hungarian). Doctoral thesis, Hungarian Academy
of Sciences, Budapest.
Vincze, I., Banyai-Stefanovits, E., Vatai, G. y. 2007. Concentration of sea buckthorn
(Hippophae rhamnoides L.) juice with membrane separation. Separation and
Purification Technology 57, 455–460.
Vincze, I., Stefanovits-Bányai, E., Vatai, G. y. 2006. Using nanofiltration and reverse osmosis
for the concentration of seabuckthorn (Hippophae rhamnoides L.) juice. Desalination
200, 528–530.
Zambra, C., Romero, J., Pino, L., Saavedra, A., Sanchez, J. 2015. Concentration of cranberry
juice by osmotic distillation process. Journal of Food Engineering 144, 58–65.
Warczok, J., Ferrando, M., López, F., Güell, C. 2004. Concentration of apple and pear juices
by nanofiltration at low pressures. Journal of Food Engineering 63, 63–70.
7 Membrane Processes
for Sugar and Starch
Processing
Frank Lipnizki
CONTENTS
7.1 Introduction................................................................................................... 242
7.2 Membrane Processes in the Cane and Beet Sugar Industry.......................... 243
7.2.1 Cane Sugar Production...................................................................... 243
7.2.1.1 Purification of Raw Sugar Cane Juice................................244
7.2.1.2 Concentration of Clarified Cane Juice................................246
7.2.1.3 Molasses Treatment............................................................246
7.2.1.4 Decolorization of Remelted Raw Sugar..............................246
7.2.2 Beet Sugar Production....................................................................... 247
7.2.2.1 Recycling of Sugar Beet Press Water and Isolation of
Pectin from Beet Pulp.........................................................248
7.2.2.2 Purification of Raw Beet Juice............................................ 249
7.2.2.3 Demineralization of Beet Sugar Juice................................ 250
7.2.2.4 Concentration of Clarified Thin Juice................................ 251
7.2.3 Common Applications in Beet and Cane Sugar Production............. 252
7.2.3.1 Recycling of Ion Exchange Resin Regeneration Waste...... 252
7.2.3.2 Evaporator Condensate Polishing....................................... 252
7.2.3.3 Sweet Water Concentration................................................. 252
7.3 Starch and Starch-Based Sweetener Industry................................................ 252
7.3.1 Corn/Maize Starch Processing.......................................................... 253
7.3.1.1 Steeping Water Handling.................................................... 254
7.3.1.2 Gluten Concentration.......................................................... 255
7.3.1.3 Starch Washing................................................................... 255
7.3.2 Wheat Starch Processing................................................................... 255
7.3.2.1 Treatment of Wheat Starch Effluents.................................. 257
7.3.3 Potato Starch Processing................................................................... 257
7.3.3.1 Concentration of Proteins from Potato Fruit Water............ 258
7.3.4 Starch-Based Sweetener.................................................................... 258
7.3.4.1 Sweetener Demudding........................................................ 261
7.3.4.2 Product Demineralization and Polishing............................ 262
241
7.3.4.3 Evaporator Condensate Polishing....................................... 262

7.3.4.4 Sweet Water Concentration................................................. 262
7.4 Outlook.......................................................................................................... 262
References...............................................................................................................264
7.1 INTRODUCTION
Sugars and starches belong to the category of carbohydrates, which are important
energy sources for organisms and nonessential nutrients in the human diet. Sugars
are mono- or disaccharides that can be immediately transformed to energy by organ-
isms. Starches, on the other hand, are polysaccharides, a space-efficient storage of
energy for organisms. Before transforming polysaccharides into energy for organ-
isms, they have to be therefore converted into mono/disaccharides, which can be
achieved by different metabolisms. Hence, both starches and sugars play an impor-
tant role in human nutrition and consequently the starch and sugar processing indus-
try is a key segment of the food industry. The introduction of membrane technology
into the sugar and starch industry can be related to the invention of the phase inver-
sion membrane by Sidney and Sourirajan in the 1960s [1]. This invention started the
rapid growth of the membrane market and the large-scale introduction of membranes
to the food industry in general and subsequently to the starch and sugar industry.
The success of membranes in the food industry, including the starch and sugar
industry, is related to the advantages offered by membrane technology. Some of the
key advantages are (1) the gentle treatment of heat-sensitive products at low/moder-
ate temperatures compared to other technologies requiring higher temperatures; (2)
unique separation mechanisms based on, for example, sieving, solution diffusion,
or ion exchange mechanism for the concentration, fractionation, desalination, and
purification of products; (3) simple plant layout and extension due to the compact and
modular design of the units; and (4) low energy consumption compared to alternative
processes, for example, evaporators. Based on its advantages, membrane technology
is often recognized as the best available technology (BAT) and therefore considered
as a key technology for process intensification in the food industry.
The key disadvantage and challenge of membrane processes is membrane foul-
ing. In the sugar and starch industry, the presence of fouling components such as
starches, proteins, pectins, or polyphenols can significantly reduce the productivity
and further impact the separation properties of the membrane process. The main
impact of fouling can be reduced by regular cleaning intervals, for example, one
cleaning interval per 24 hours or by selecting appropriate pretreatment methods such
as prefiltration, decantation, or carbonation. Further, research is now focused on the
development of improved and/or functionalized membranes to reduce or even avoid
fouling and thus minimize the need for cleaning and pretreatment.
Another limitation of membrane technology in the sugar and starch industry is
the maximum degree of concentration that can be reached with reserve osmosis, the
state-of-the-art technology to concentrate sugars. The osmotic pressure of a 25° Brix
sugar solution is about 40 bar and approaches the limits of the conventional plant
and modules designs, that is, spiral wound modules, while conventional evaporation
technologies can concentrate sugars up to 75° Brix. One approach to overcome this
Membrane Processes for Sugar and Starch Processing 243
limitation is the combination of reverse osmosis and membrane distillation/osmotic

distillation. However, further developments in the area of membrane distillation/
osmotic distillation and optimization of the process integration are required.
In the following, an overview of successful and potential applications of mem-
brane processes in the sugar and starch industry will be given. The first section of
this chapter is on membrane applications in the sugar industry, covering applications
in both the cane and beet sugar processing industry. The second section discusses
the applications of membranes in the starch industry, focusing first on membrane
applications in the corn, wheat, and potato starch processing and then on the pro-
duction of starch-based sweeteners. The final section of this chapter will provide a
brief outlook on future developments of membrane technology in sugar and starch
processing. It should be noted that the sections of this chapter are self-contained and
can be read independently of each other. Thus, the reader is encouraged to move
directly to the section of interest.
7.2 MEMBRANE PROCESSES IN THE CANE AND

BEET SUGAR INDUSTRY
Cane and beet sugar are produced in over 130 countries worldwide at an annual
production rate of approximately 140 million tons, of which 65%–70% is related
to cane sugar. Sugar production is one of the most labor-intensive and energy-con-
suming industry segment in the food industry. The initial research on membranes
in the sugar industry was started by R.F. Madsen from De Danske Sukkerfabrikker
(DDS—The Danish Sugar Factories, later Danisco, and now Nordic Sugar) in the
beginning of the 1970s. Since then, a lot of work to develop membrane applications
in the sugar industry has been undertaken, which led to the implementation of mem-
brane technology for some applications in the sugar industry. However, there are still
many challenges, such as the implementation of membranes for the concentration
of thin juice or for the purification of beet juice and concentration of the thin juice.
The content of this section combines and updates an early review by Trägårdh and
Gekas [2] on the membrane industry with a more recent review by Lipnizki et al. [3].
In the first part of this section, the developments of membrane processes in
cane sugar production are highlighted, while the second part focuses on beet sugar
production.
7.2.1 Cane Sugar Production

A general overview of traditional cane sugar production with the main production
steps is given in Figure 7.1.
The production of cane sugar starts with the delivery of bundles of cut sugar cane
to the cane sugar mill. Within 24 hours after delivery, the cane is chopped and shred
using rotating knifes and hammer mills. This pretreatment of the sugar cane is fol-
lowed by the extraction of the cane sugar juice. This is achieved either by roller mills
in a countercurrent process using hot freshwater that is pumped through the chain of
multiple roller mills or by continuous diffusion. The resulting dark green cane juice
is then purified by clarification by using heat and lime as the clarifying agent to settle
Cane delivery
Cane
milling
Juice concentration Raw sugar
Clarifier by evaporation crystallization
Freshwater
Lime
Raw juice
Liming
Drum filter
Condensate
Mud removal Raw sugar transportation
Sugar mill
Sugar refinery Decolorization
by ion exchange
Crystallization
Raw sugar
remelt
Refined sugar Sweet water

from regeneration
FIGURE 7.1 Traditional cane sugar production.
the solids and obtain a clear juice. In order to produce sugar for direct consumption,
sulfitation and/or carbonation are used as alternatives to clarification. The cane juice
is subsequently concentrated to 60–75° Brix in multistage evaporators and is referred
to as syrup/raw syrup. In the final steps, the syrup is boiled and crystallized in sev-
eral steps, resulting in a white sugar and a remaining fraction of sugar syrup/molas-
ses. It should be noted that it is quite common in the cane sugar industry to separate
cane sugar production between two factories: sugar mills and sugar refineries. In the
sugar mill, the cane juice is extracted and then either concentrated to produce raw
syrup/syrup or concentrated and crystallized to produce raw sugar. The raw syrup/
sugar is then transferred to the sugar refinery for final purification, decolorization,
and crystallization. The following section covers membrane applications in both the
sugar mill and refinery.
7.2.1.1 Purification of Raw Sugar Cane Juice

For raw sugar cane juice purification, ultrafiltration has been proposed as an alter-
native to conventional liming. The key advantages of ultrafiltration over liming are
lower energy consumption and higher purity achieved by the combined removal of
color and macromolecules, such as fat, starch, and dextrans, from the raw cane juice.
The use of ultrafiltration for the clarification of cane sugar juice was initially pat-
ented by Madsen in 1971 [4] and its feasibility was confirmed by early results on a
pilot scale as reported by Nielsen et al. [5] using a plate-and-frame module equipped
with polymeric membranes. The first full-scale membrane installation for the clarifi-
cation of cane juice was done in 1994 as part of the New Applexion Process (NAP), a
new process concept for the production of very low color cane sugar using inorganic
tubular ceramic membranes [6]. The membrane installation was operated for four
seasons until 1998 after which a membrane change became necessary [7]. The NAP
process can be divided into two steps and starts with limed juice from an initial clari-
fier and thus replaces carbonation and/or sulfitation commonly used in white sugar
production. In the first step, ultrafiltration is used to remove high-molecular-weight
components such as starch, dextran, wax, gums, etc. from the cane juice followed by
juice softening using ion exchange to remove calcium and magnesium salts from the
ultrafiltered cane juice in a second step. An alternative concept to the NAP process
is the SAT process [8] (see Figure 7.2).
In the SAT process, the cane juice is preclarified before the ultrafiltration process
with tubular ceramic membranes. The underflow is sent to a vacuum filter and then
mixed with ultrafiltration retentate. The combined stream is passed to a second clari-
fier. The overflow from this second clarifier can be added to either the ultrafiltration
permeate before evaporation directly or to the feed of the ultrafiltration unit. The
underflow of the second clarifier is sent back in front of the vacuum filter. Apart
from tubular inorganic ceramic membranes, tubular stainless-steel microfiltration
membranes have also been installed for the purification of preclarified cane juice [9].
Apart from tubular inorganic membranes, tubular polymeric membranes have also
been tested for the purification of raw juice. In pilot trials, it has been demonstrated
that tubular polymeric membranes can be applied for the purification of clarified
cane juice and cane juice clarifier underflow [10].
Despite the success of membranes in tubular configuration, the final aim is to
apply polymeric membranes in spiral wound configuration for the clarification of
Crystallization
1st clarifier Tubular MF/UF unit
Permeate
Processing Retentate
Feed
aids
2nd clarifier Refined white
1st underflow sugar
Rotary vacuum
filter
Suspended
matter 2nd underflow
FIGURE 7.2 SAT process.

cane juice due to their lower operating costs, higher packing density, and ease of
membrane replacement. The successful use of spiral wound ultrafiltration modules
for the purification of clarified cane juice was demonstrated on a pilot scale during
the season 1997/1998 [11] and on commercial scale during the season 1998/1999
[12]. In order to increase the sugar recovery to more than 99%, the retentate from
spiral wound was further concentrated and diafiltrated using tubular carbon mem-
branes. The general applicability of spiral wound ultrafiltration modules was further
confirmed in other trials [13–17].
7.2.1.2 Concentration of Clarified Cane Juice

For the concentration of the clarified cane juice, nanofiltration/reverse osmosis
(NF/RO) have been considered as a preconcentration step before evaporation. While
conventional evaporation technology typically concentrates the clarified caner juice
to 65–70° Brix, nanofiltration/reverse osmosis is typically limited to 25–35° Brix due
to the high osmotic pressure at these sugar concentrations. Combining nanofiltration/
reverse osmosis and evaporation can reduce the thermal load of evaporation by 49%
and thus could lead to more environmental-friendly sugar production [18]. Owing
to the ongoing optimization in the heat/steam utilization in existing sugar factories,
this approach is mainly limited to new sugar factories. Additionally, if evaporation is
required, reverse osmosis can be used as a condensate polisher (see Section 7.2.3.2).
Recently, membrane distillation has also been considered for the concentration of
cane juice. Compared to reverse osmosis/nanofiltration, membrane distillation is not
restricted by osmotic pressure. In a first laboratory-scale test, it was demonstrated
that it is feasible to concentrate clarified sugar cane juice (20° Brix) by membrane
distillation [19]. However, further investigations and scale-up are required.
7.2.1.3 Molasses Treatment

In both sugar cane mills and refineries, molasses are a by-product of the crystalliza-
tion process and is sold at a low price as cattle feed and for alcohol production [2].
The typical composition of cane molasses is 55% sucrose, 10% ash, 5%–10% organic
nonsucrose components, and 18%–25% water. The ash and nonsucrose components
inhibit the crystallization process and result in high concentrations of noncrystal-
lized sucrose in cane molasses. Using ultrafiltration with polymeric or ceramic mem-
branes can concentrate high-molecular-weight components and ash and thus separate
these components from sucrose [5,20]. Since the presence of high-molecular-weight
components tends to complicate sugar production in different ways, it is aimed to
remove at an early stage, which reduces the need for ultrafiltration. Alternatively, if
the molasses have no or low concentrations of high-molecular-weight components,
electrodialysis can be considered for the treatment of molasses. Using electrodialy-
sis with nonfouling ion exchange membranes can separate diluted molasses into a
concentrated potassium stream, which can be utilized as a fertilizer and an ion-free
sucrose stream for crystallization [21].
7.2.1.4 Decolorization of Remelted Raw Sugar

In case the raw cane juice or syrup has not been satisfactorily purified in the cane
sugar mill, microfiltration and ultrafiltration have been proposed as an alternative
Remelted
Tubular MF/UF unit
raw sugar
Flocculation/coagulation Pre-decolorization
Recovery of displacement water Recovery of brine from
from ion exchange regeneration of ion exchange
Recovered Recovered
water brine
NF/RO unit RO unit
Concentrated Concentrated
sugar color
Crystallization
Decolorization
by ion exchange
FIGURE 7.3 Decolorization of raw sugar remelt with membrane technology, including
recovery displacement water and brine.
and/or in addition to the conventional ion exchange for decolorization and purifica-
tion. The successful application of microfiltration and ultrafiltration is related to the
pretreatment of raw sugar. Flocculation and coagulation have been tested as pretreat-
ment before microfiltration and ultrafiltration to support the removal of color and
turbidity in the raw sugar (see Figure 7.3). Both polymeric [5,22] and inorganic mem-
branes have been applied [22–25] and the first commercial unit for this application
was reported to have been installed at a European factory in 1997 using inorganic
membranes for a capacity of 100 tons/day of raw sugar [26]. As a posttreatment and
to remove remaining inorganic matters from the remelted raw sugar, electrodialysis
has been proposed [23].
Further, if ion exchange is part of the decolorization concept, nanofiltration is
an interesting alternative to recycle the ion exchange resin regeneration waste (see
Section 7.2.3.1), and for the treatment of the displacement water before regeneration,
reverse osmosis can be applied (see Section 7.2.3.3).
7.2.2 Beet Sugar Production

The production of beet sugar is similar to the cane sugar process and an overview of
the key production steps is given in Figure 7.4.
The beet sugar production process starts with washing and slicing of the sugar
beets into cossettes, which are very thin V-shaped beet slices. This is then followed
by the extraction of the beet sugar by extraction. Using hot water extraction, the
raw beet juice is extracted from the beet cossettes, leaving behind a nutrient-rich
pulp with very low sugar content, which is typically used as cattle feed. In order
to remove proteins, pectins, inorganic salts, and coloring substances from the raw
juice liming followed by carbonation and demineralization is applied. In the sub-
sequent step, the purified thin juice is concentrated by multistage evaporation from
a sugar concentrate of 14–16° Brix to 70–75° Brix. The resulting thick juice is then
boiled and crystallized separating the white sugar and the molasses. The different
applications of membrane processes in the beet sugar production are introduced
in the following.
Sugar beet delivery
Pulp
Lime
press
kiln
Freshwater Carbonation
Beet
pulp
Beet washing
CO2
Thin juice
Beet slicing
filtration
Press water Lime
Sugar beet
milk
cossettes Raw juice
Ion exchange
Evaporation Liming
thin juice demineralization
Crystallization thin juice concentration
Thin
Concentrated
juice
thin juice
Thick juice
filtration
Sweet water
Condensate from regeneration
Cooling and drying

White drum
sugar Storage
tank Packaging
Centrifugation
FIGURE 7.4 Traditional beet sugar production.
7.2.2.1 Recycling of Sugar Beet Press Water and

Isolation of Pectin from Beet Pulp
The recycling of press water and isolation of pectin from beet pulp are two
approaches to improve the efficiency of the conventional sugar extraction by diffu-
sion (see Figure 7.5).
For 10 tons of sugar beets resulting in 1 ton of sugar, typically, 6 tons of water is
required for the pressing of the extracted pulps from the diffusion tower. The result-
ing press water is a diluted stream with 1%–3% total solids of which 60%–80% are
sugar, while the remaining total solids consist of salts, colloids, and other suspended
impurities. Recycling the press water directly to the diffusion tower as convention-
ally done can influence the productivity since the presence of sugar and other impu-
rities can have a negative impact on the sugar extraction efficiency. Therefore, it
has been suggested to polish the press water with RO [27]. Thus, the RO permeate
with the polished press water could be recycled to the diffusion tower, while the RO
Diffusion tower Pulp

Pretreatment
press
Press water
Freshwater
Diafiltration
water
Beet
pulp UF unit
Pectin
isolated
pH adjustment
prefiltration
To dryer
Sugar beet RO unit
cossettes Press water (recovered)
Raw juice Low-grade sugar

crystallization
FIGURE 7.5 Integration of sugar beet press water and pulp recycling by membrane
technology.
retentate stream could be further utilized in low-grade sugar crystallization. The

concept was tested on a pilot scale at two Italian sugar factories and its general
applicability was shown. However, it was difficult to maintain high fluxes in the RO
unit despite extensive pretreatment of the RO feed consisting of liming, carbonation,
sedimentation, alkalization, phosphatization, and filtration.
The beet pulp after the pressing contains pectins, hemicelluloses, celluloses, and
smaller amounts of proteins, lignins, phenolics, fats, and ash. Pectin is used in the
food industry as a thickener, fat replacer, or fat mimic. Hence, isolating the pectin
from the beet pulp would lead to a valuable by-product. The concept was proven on
a laboratory scale using sugar beet pulp extract, which was extracted, pH adjusted,
and prefiltered before ultrafiltration with diafiltration [28]. However, upscaling and
further optimization are required to establish this process.
7.2.2.2 Purification of Raw Beet Juice

Similar to the clarification of cane sugar juice, the use of ultrafiltration for the
purification and clarification of beet juice was initially patented in 1971 by
Madsen [4]. The concept was to replace classical lime purification partially or
fully and with micro/ultrafiltration, separating the beet juice into a retentate
stream containing most of the impurities and permeate stream of purified thin
juice. The first successful test of the general concept was conducted in the cam-
paigns of 1979–1981 using plate-and-frame modules and polymeric membranes
[5]. In recent years, the focus was on the polymeric spiral wound and tubular
modules for the purification of the clarified juice on pilot and commercial scales
[10,29]. The tubular membranes were tested either directly on clarified juice or
after a preconcentration with spiral wound modules. Apart from using polymeric
membranes, the inorganic—ceramic and metallic—tubular membranes were
Lime kiln
1 2 Pretreatment
Carbonation Clarifier
Pretreatment
Clarifier
Raw juice
overflow
MF/UF unit
Drum filter
CO2 Tubular MF/UF unit
Purified
raw juice
Lime
MF/UF unit Suspended
milk Purified
Raw matter
raw juice
juice
Liming or partial liming
FIGURE 7.6 Concepts for the integration of membrane technology in the purification of
sugar beet raw juice.
applied for this application on pilot and commercial scales [30,31]. An important
factor to implement micro- and ultrafiltration successfully for beet juice purifica-
tion is the pretreatment of the juice. Independent of the membrane material and
module, the selection of the correct pretreatment can lead to significantly higher
fluxes compared to processing raw juice directly [32]. The potential pretreatment
technologies are mesh screens, settling, preliming, and carbonation or combi-
nations of the technologies. Different approaches are shown in Figure 7.6. An
example for an overall concept to treat raw juice is the A.B.C process by Honiron
Engineering (USA) [33]. This concept combines continuous screening (“A”) with
micro/ultrafiltration followed by an optional softening and alkaline adjustment
before evaporation (“B”) and adsorption (“C”). In the initial screening step, the
diffuser juice is prefiltered with a 150-μm screen, heated to 80°C, and then fur-
ther screened with a rotary filter. In the subsequent step, the final clarification
of raw juice is carried out by micro/ultrafiltration, separating the raw juice into
a retentate stream containing the impurities, which is blended with molasses for
Brix adjustment or evaporated to produce animal feed, and a purified permeate
stream. Before concentration by evaporation, an optional softening with a weak
cationic ion exchange resin and an alkaline adjustment might be applied. In this
concept, further, an adsorption step follows the evaporation to remove colorants
and viscosity precursor components.
7.2.2.3 Demineralization of Beet Sugar Juice

In the beet sugar industry, the beet sugar juice is conventionally demineralized by
ion exchange before concentration by evaporation. Alternatively, electrodialysis can
be applied for the complete or partial demineralization of the beet sugar juice. The
first successful integration of electrodialysis in the European sugar industry was
started in 1996 [31]. In this case, the target was to debottleneck the ion exchange and
thus double the plant capacity without increasing the ion exchange. Electrodialysis
was therefore installed in front of the ion exchange as partial demineralization of
the 12–24° Brix juice by 55% with a sugar loss of less than 0.5% of sugar produc-
tion. Since electrodialysis became more and more accepted in the sugar industry, it
is now possible to demineralize beet sugar juice up to 30° Brix by up to 80% using
electrodialysis [34]. Additionally, if ion exchange is part of the demineralization con-

cept, nanofiltration can be applied for the recycling of the ion exchange resin regen-
eration waste (see Section 7.2.3.1) and reverse osmosis can be used for the treatment
of the displacement water before regeneration (see Section 7.2.3.3).
7.2.2.4 Concentration of Clarified Thin Juice

The concentration of clarified thin juice by evaporation is the most energy-consum-
ing step in the beet sugar industry and requires about 50% of the total energy in the
production. Therefore, this step was one of the first potential applications for mem-
branes to be considered. The first trials using RO with cellulose acetate membranes
for the concentration of thin juice were carried out in the beginning of the 1970s [5].
Owing to the limited temperature stability of cellulose acetate, these tests had to be
conducted at 25–30°C and resulted in commercially unviable fluxes. After the intro-
duction of the thin-film reverse osmosis membranes in the beginning of the 1980s,
it became feasible to operate up to 80°C and thus concentrate the thin juice at its
normal temperature. Despite higher fluxes, the performance of RO was still limited
by the osmotic pressure to a water reduction of 20%, and further concentration by
evaporation was required. More recently, different approaches with nanofiltration
membranes were tested for fouling and thus long-term performance of the mem-
branes appeared to be a problem with these membranes [30,35].
The work on the concentration of thin juice by reverse osmosis/nanofiltration is
still under investigation and the focus is on the optimization of the integration of
reverse osmosis/nanofiltration and evaporation [36]. Further, reverse osmosis/nano-
filtration might be an interesting option to be used as a capacity booster in existing
installations without increasing the steam requirement.
Since evaporation is an essential part of the thin juice concentration, reverse
osmosis can be applied to polish the evaporator condensate by, for example, concen-
trating the chemical oxygen demand (COD) in the evaporator carryover; for details,
see Section 7.2.3.2. An overview of the potential of membrane applications related
to thin juice concentration is further given in Figure 7.7.
NF/RO unit
Thin Permeate
juice 99% water
Evaporator
Preconcentrated Concentrated
thin juice thin juice
Condensate
Condensate RO unit Permeate
recovered
water
Retentate
concentrated COD
FIGURE 7.7 Overview of potential membrane applications in thin juice concentration.

7.2.3 Common Applications in Beet and Cane Sugar Production

7.2.3.1 Recycling of Ion Exchange Resin Regeneration Waste
In the sugar industry, ion exchange resins are used for the decolorization and demin-
eralization of cane and beet sugar juice. The regeneration of ion exchange resins
is commonly achieved by passing an alkaline brine solution through the columns,
which desorbs the retained impurities. The resulting waste streams have a high salin-
ity combined with a high COD. Spiral wound and tubular nanofiltration membranes
have been found to be suitable to regenerate the alkaline brine solution by concen-
trating the impurities and recovering most of the salts in the permeate [20,26,37].
Thus, the salt and water consumption for the regeneration of the ion exchange can be
reduced significantly.
7.2.3.2 Evaporator Condensate Polishing

The condensate from the evaporators in both the beet and sugar industry can contain
a high COD/biological oxygen demand (BOD). Reverse osmosis can reduce these
levels by up to 90%, resulting in a concentrated COD/BOD stream and a polished
permeate stream. Depending on the composition of the evaporator condensate, this
recovery of the COD/BOD might be enhanced if the feed to the reverse osmosis unit
is pH-adjusted and thus the present acids are converted to salt.
7.2.3.3 Sweet Water Concentration

Sweet waters—water containing sugars—are also present in both the cane and beet
sugar industry. These sweet waters can result from different sources such as the
displacement water from ion exchange units or flushing water from storage tanks.
Depending on the source, the sugar load of these streams might vary from a few ppm
to several Brix. The challenge of treating these streams is that a sugar solution of
1° Brix accounts for a COD of 5000 mg/L. By treating these sweet waters by reverse
osmosis, it is often possible to reuse the concentrated sugar in the retentate as well
as the purified water permeate in the factory. The limiting factor for concentrating
sugars is the osmotic pressure, which is already 40 bar for 25° Brix, while on the
permeate site, COD levels below 100 mg/L can be achieved.
7.3 STARCH AND STARCH-BASED SWEETENER INDUSTRY

Every year, approximately 60 million tons of starches are produced worldwide, with
the United States as the major starch-producing country with a market share of 40%.
In the food industry, starches and its derivatives are either directly used as food
additives, for example, as thickener for soups, or further transformed to starch-based
sweeteners such as glucose and dextrose, which are used as a sugar replacement.
Further, owing to its gluing and viscosity-increasing characteristics, starches and
its derivatives are also used in other industries such as the paper, textile, and oil
industry. The main starch source is corn/maize, which accounts for 85% of the starch
production worldwide followed by other sources such as wheat, potato, tapioca, taro,
and rice.
The first three subsections of this section are devoted to the production of starch
from its three main sources: corn, wheat, and potatoes, while the final sections focus
on the most important starch derivative—starch-based sweetener.
7.3.1 Corn/Maize Starch Processing

The corn wet milling process is a well-defined and well-established process for the
production of corn starch by separating the corn into its four key components: starch,
germ, fibers, and protein. In the initial step of the corn wet milling process, the corn
arriving at the starch plant will be inspected and cleaned to remove dust, chaff, and
cob (see Figure 7.8). In the subsequent steeping step, the corn is soaked for around
50 h in warm water with 0.1% sulfur dioxide in large steeping tanks. During this
step, the weak acid steeping water swells and softens the corn by losing the gluten
bonds and releasing the starch. The resulting steeping water is evaporated to con-
centrate its proteins and then either used as corn steep liquor—a nutrient used, for
example, in the bioethanol and pharmaceutical industry—or mixed with the spent
germ and hulls and then dried as corn gluten feed, which is used in animal feed.
The steeped corn is coarsely milled, resulting in water slurry containing the
grinded corn. This slurry is then sent to cyclones separating the germ from the
slurry. The recovered germ is further washed, dewatered, and final pressed to extract
the corn oil from the germ, while the resulting press cake from the extraction can
also be utilized as animal feed. After cyclones, the remaining slurry is milled very
finely to release starch and gluten from the fibers in the kernel. This is followed by
two sieving steps. In the first step, screens remove the fibers from the starch and the
gluten and the collected fibers are washed and passed over a second screen to remove
any residual starch and gluten. The recovered fibers are mixed with the concentrated
Corn steeping Steeping water

Steep
liquor
Germ
Degermination washing Steeping water
concentration
Germ
Fiber press
Stone Gravity bar Refiner milling
catcher screen Fibers
Gluten thickener
Gluten dewatering
Stones
Gluten
Coarse
grinding Fiber
screens
Degritting Starch washing

Starch
Washwater
Primary separator
FIGURE 7.8 Corn wet milling process.

steeping proteins as animal feeds, while the remaining starch–gluten suspension is

processed further in the starch separators. In these centrifugal separators, the gluten
is separated from the starch. The gluten stream from the separators is concentrated
with a gluten thickener separator and vacuum belt filters and dried to form corn
gluten meal, which is used in animal feed. The starch slurry is further purified by
diluting several times and washing in hydrocyclones. The resulting starch milk has
a purity typically greater than 99.5% and is either dried and sold as unmodified
starches, chemically or mechanically modified into specialty starch or converted to
corn syrups and dextrose.
Most of the membrane applications in corn wet milling are related to the reduc-
tion of water consumption.
7.3.1.1 Steeping Water Handling

The first potential membrane applications in the wet milling process are related to
the steeping water. Typically, 0.7–0.8 m3 of steeping water is produced per ton of corn
[38], a diluted composition of proteins, amino acids, lactic acid, and minerals plus
sugars and ethanol. Conventionally, steeping water is concentrated by evaporation
from 6%–12% TS to over 50% TS. Reverse osmosis combined with evaporation in a
hybrid process was investigated as an alternative to evaporation only [39]. Removing
57% of the water by reverse osmosis followed by evaporation for further concentra-
tion can result in significant reduction in electrical and thermal energy compared to
an evaporator with mechanical vapor recompression [40]. Another approach was the
use of a cascade of centrifugation, ultrafiltration, and reverse osmosis. In the first
step, the steeping water was passed through a centrifuge and the overflow from the
centrifuge was further polished by ultrafiltration. In the final step, the ultrafiltration
permeate was concentrated in a reverse osmosis unit. The overall water recovery
was around 80% at a quality acceptable for discharge from the plant [41]. Despite
these studies, the fluxes obtained in the membrane processes were low and impacted
by fouling. Further, the replacement of evaporators can be only partially achieved
or requires a cascade of processes. Additionally, the rejections of some of the low-
molecular-weight components in the steeping water such as ethanol or amino acids
even by reverse osmosis are low. In relation to the steeping water evaporators, the
use of reverse osmosis as an evaporator condensate polisher has been investigated.
The evaporator condensate from the steeping water evaporators typically contains
1500 mg/L COD, a level too high for direct recycling and therefore commonly sent
to sewage treatment. Alternatively, owing to the low osmotic pressure of the con-
densate, RO could be applied recovering up to 98% of the evaporator condensate at
COD level of around 100 mg/L [42]. An alternative use of the steeping water is as a
nutrient in the pharmaceutical and bioethanol industry. To reduce the microbiologi-
cal activity of the steeping water microfiltration can be used as an alternative to cen-
trifugation and pasteurization before usage. Investigations related to the use of steep
water in the bioethanol industry suggested that both investment and operating costs
were lower compared to heat pasteurization and centrifugation. Further, the treat-
ment with microfiltration reduced fouling in subsequent fermenters, beer still, and
steeping water evaporators. Additionally, it was possible to recover insoluble proteins
and starch, which could be added to the corn gluten feed [43].
7.3.1.2 Gluten Concentration

In gluten processing, dry matter—nutrients/proteins—can be lost in the overflow of
the gluten thickener separator and filtrate of the vacuum belt filters. Alternatively,
tubular stainless-steel microfiltration membranes were tested as an alternative to
separators and vacuum belt filters. Using microfiltration as an alternative to a gluten
thickener separator for the concentration of the light gluten, it was possible to achieve
similar concentrate/underflow and permeate/overflow compositions. By replacing
the vacuum belt filter with microfiltration for the concentration of the heavy gluten,
the compositions of the concentrate and permeate/filtrate stream were similar but the
concentration of the dry matter in the gluten cake of the belt filter was higher. It was
further noted that microfiltration removed more ash and inorganic matter from the
concentrate, which might increase the value of the gluten. However, further valida-
tion is required [44].
7.3.1.3 Starch Washing

The overflow from the first stage of the starch-washing hydrocyclones, the so-called
light middlings, are diluted suspensions consisting mainly of proteins and some
starch. In the conventional process, this stream flows countercurrent from the wash-
ing to the front of the process, where it is concentrated as light steeping water. In
order to reduce freshwater consumption and reduce the volume of steeping water,
reverse osmosis has been installed to separate the light middlings. Reverse osmosis
separates the light middlings into a permeate stream, which is recycled as partial
freshwater replacement in the washing stage and retentate stream is used in the front
end of the process. Hence, the overall process reduces the light steeping water vol-
ume by 50% and the freshwater consumption by 30%, allowing a nine-stage cyclone
washing to run as efficiently as a 15-stage cyclone washing [45,46].
7.3.2 Wheat Starch Processing

The traditional processes to produce wheat starch and vital gluten as by-products are
the Martin and Batter process. The Martin or “dough ball” process was originally
invented by the Italian chemist Beccari in 1745 and further developed by Martin in
1853 in France [47]. The key feature of the Martin process is the separation of the
wheat starch and vital gluten by washing of the stiff dough. The modern Martin pro-
cess starts with the mixing of wheat flour with water at a ratio of approximately 1:0.6
to produce stiff dough. The dough is allowed to briefly rest so that flour particles and
gluten can hydrate and thus a continuous matrix of long intermeshed gluten strands
can be formed. The developed dough is then kneaded with water in trough, result-
ing in the segregation of gluten particles from the starch suspension. This gluten–
starch mixture is then transferred inside the gluten washer, a long rotating reel with
40-mesh-plate screens. The screens retain the gluten and allow the starch milk to
pass. Water is sprayed onto and through the screens to wash out the starch and purify
the gluten. To extract the remaining starch, the gluten are transferred to a mixer and
kneaded with excess water. Finally, the gluten is dewatered, shredded, and flash-
dried to produce dry gluten powder. The starch suspension is screened/fine-screened
to remove the remaining starch gluten and bran. The clarified starch suspension is
then refined with a nozzle centrifuge with the addition of washwater to remove the
B-starch with pentosanes and solubles. The concentrated A-starch fraction from
the nozzles is further purified and concentrated by multistage hydrocyclones with
countercurrent washing. The resulting starch milk containing the B-starch from the
center of the separator is dewatered with a peeler centrifuge or a vacuum drum filter
before flash drying. The initial disadvantages of the Martin process was the high
water consumption of around 10–15 m3 of water per ton of wheat flour for washing.
In the modern Martin process, this amount has been reduced to 5–7 m3 of water per
ton of wheat flour by recycling of process water and the increased separation effi-
ciency of starch and gluten.
The Batter process was developed in 1944 in Canada/USA [47]. The key feature
of the Batter process is separation of the wheat starch and vital gluten using a thin
flour batter. In the initial step of the process, a batter is prepared by mixing wheat
flour and water at a ratio of 1:0.7–1.8. The batter is allowed to rest for the gluten to
hydrate and to start agglomeration. The addition of water supported by mixing with a
cutting pump results in a curd-like suspension of gluten strands. The starch is washed
from the gluten curds and separated from the starch suspension by gyrating screens,
retaining the gluten and allowing the starch suspension to pass. The final purification
and concentration of the starch in the batter process is similar to the Martin process.
A more recent method for wheat starch process is the Alfa Laval/Raisio process,
which was first installed in 1976 in Finland. The process starts with the production of
flowable batter, mixing wheat flavor and water at a ratio of 1:1.2–2.0, which is mixed
at high shear in a pin mill to form a uniform mixture. Using a two-phase decanter
centrifuge, this mixture is then separated into an A-starch fraction and a protein-rich
fraction containing gluten, B-starch, solubles, and pentosanes. The A-starch frac-
tion is purified by screens to remove fibers, centrifugation, and hydrocyclones. The
protein-rich phase is then allowed to mature, resulting in the aggregation of the glu-
ten. This is then followed by addition of water and mixing in a pin mill before the
separation of the gluten fraction from the B-starch and solubles and pentosans with
vibrating screens. The gluten fraction is handled in the conventional way, while the
B-starch and solubles/pentosanes are separated by centrifuge.
Another alternative is the so-called hydrocyclone process developed in the 1970s
in the Netherlands using hydrocyclones instead of a two-phase decanter. This pro-
cess starts with the preparation of dough based on a wheat flour and water ratio of
1:0.6–0.7 by shear mixing. The dough is separated by hydrocyclones into an A-starch
fraction and a protein-rich fraction containing gluten, B-starch, pentosanes, and sol-
ubles. The A-starch and protein-rich fraction are separated and purified similar to
the Alfa Laval/Raisio process but without the maturing process of the protein-rich
fraction.
The latest process is the high-pressure disintegration (HD) process, which was
originally developed for potato starch and in the 1980s modified for wheat starch
[47]. In the initial step, wheat flour and water are mixed at a ratio of 1:0.9–1.0 and
pumped under high pressure and shear through a homogenizer valve. The resulting
mixture is then separated in a three-phase decanter, resulting in an A-starch fraction,
gluten and B-starch fraction, and a fraction consisting of solubles and pentosanes. The
A-starch fraction is then purified using screens, centrifugation, and hydrocyclones.
The gluten and B-starch fraction is aggregated before the separation of the gluten
from the B-starch with the addition of water using rotary screens and gluten washer.
The soluble fraction containing pentosanes and solubles is then screened to remove
the fine gluten before concentration of the pentosanes by evaporation.
7.3.2.1 Treatment of Wheat Starch Effluents

Most of the work on membrane processes in wheat starch production is related to
wheat starch effluents. Depending on the process used, 1–3 m3 of effluent is produced
per ton of wheat flavor. These effluents consist of diluted soluble with a high COD.
Initial studies based on the Martin and Batter process demonstrated that UF com-
bined with RO or RO alone can be used to separate these effluents into a protein-rich
stream, which can be spray-dried and used as a gluten substitute or animal feed, while
the final permeate can be recycled into the process. However, the overall economics
of the concept was uncertain and highly dependent on membrane life and fluxes [48–
50]. Related studies improved membrane fluxes by pretreating the feed with enzymes
[51,52]. Despite flux improvements, the overall economic feasibility of the process
remained uncertain and was strongly dependent on the membrane life cycle, the pro-
tein rejection, and the hemicellulase concentration [51]. An alternative approach to
treat wheat starch process water is the use of anaerobic digester in combination with
ultrafiltration. Connecting a pilot ultrafiltration unit to an anaerobic fluidized digester
treating different wastewaters from cereal production, including water from the pro-
cessing of wheat flour with ultrafiltration, it was found that COD, BOD, and total solid
(TS) can be reduced by 99% [53]. The permeate from the ultrafiltration unit was dis-
charged and the retentate was returned to the digester. The COD loading was 8.2 kg/
(m3 day) and the methane yield from the biogas production was 0.29 m3 per kg COD
or 68% of the total gas production. The applicability of the combination anaerobic
digestion with ultrafiltration to treat wheat starch effluents is also confirmed by the
full-scale results at Tenstar Products, Ashford, UK [54]. The digester is designed for
a capacity of 2000 m3 and handles a wastewater COD load of 5250 kg/day. The COD
destruction rate is 78%, resulting in a gas production of 2150 m3/day. The two tubular
ultrafiltration lines connected to the digester have membrane area of 144 m2 each and
produce together 7 m3 permeate per hour. The ultrafiltration lines are running 24 h
per day with one caustic cleaning cycle per month. The membrane life cycle is 3 years.
7.3.3 Potato Starch Processing

The potato starch production starts with the delivery of the potatoes to the factory,
sampling, and storage. The potatoes are then washed to remove sand stones and foli-
age. The potatoes are then disintegrated using, for example, rasper—rotating drums
fitted with rasping blades—resulting in a mixture of mainly starch granulates, fibers,
and potato fruit water. In the next stages of the process, these three components are
separated and purified. One approach is to remove the fruit water from the fibers and
starch using a decanter. The fibers are extracted from the starch using sieves under
the addition of washing water. After extraction the starch slurry is classified using
a disk stack centrifuge, separating larger starch granulates from the smaller starch
granulates and remaining fibers.
The classified starch slurry in the concentrate of the centrifuge is then refined
using countercurrent hydrocyclones with washing water to remove soluble proteins
from the starch and then dried. The overflow from the centrifuge containing the
small granulates and fibers is extracted a second time using additional smaller mesh
sieves. The fibers recovered are added to the fiber line, while the starch is further
refined and also dried.
7.3.3.1 Concentration of Proteins from Potato Fruit Water

One of the key challenges in the potato starch industry is the potato fruit water. The
potato fruit accounts for approximately 75% of raw material and contains approxi-
mately 1.5%–2% proteins, amino acids, sugar, salts, and some residual starch.
Traditionally, the fruit water is used as fertilizer and sprayed on fields. One of the
early approaches to concentrate proteins was by the use of ultrafiltration [55,56].
Using tubular ultrafiltration modules, it was possible to increase the amount of total
solids from approximately 6.5% to 18% and to remove most of the salts from the
potato fruit water concentrate. However, the fouling and foaming tendency of the
potato fruit water was identified as a potential problem with ultrafiltration [57].
Alternatively, reverse osmosis showed higher protein yields and an overall reduced
energy consumption for the protein concentration [58]; further, the COD reduction in
the permeate has been improved, which allowed the recycling of water, for example,
as potato washwater. The advantages of using tubular reverse osmosis for the con-
centration of potato fruit water were highlighted in pilot plant operations combined
with an economical evaluation at Emsland Stärke in Germany. The combination
of the concentration of the proteins followed by coagulation, separation, and dry-
ing of the proteins and evaporation of the remaining fruit water after separation by
evaporation was found to be the most economical solution [57]. A modification of
this process was later presented, treating the condensate from the evaporator by a
biological treatment and polishing the filtrate by a second RO unit for reuse as puri-
fied water in the starch refining. However, this modified process was associated with
high investment and maintenance costs [59]. While previous approaches involved the
coagulation and drying of the proteins, resulting in protein with a low functionality,
which are typically used in animals, the focus is most recently on the recovery of
native proteins, which can be used in the food, pharmaceutical, and cosmetic indus-
try. Using tubular ultrafiltration combined with diafiltration, it is possible to recover
proteins with high functional and organoleptic properties. The key to the success was
the pretreatment of the potato fruit water, removing fibers plus air, which caused in
previous approaches foaming problems [60].
7.3.4 Starch-Based Sweetener
The most important starch derivatives are starch-based sweeteners, which are pro-
duced by acid and/or enzymatic hydrolysis of the starch carbohydrates. These sweet-
eners are nutritive sweeteners, which are used as a low-cost replacement of sucrose
extracted from sugar cane and beets. The two key groups of starch-based sweeteners
are glucose/dextrose syrup and high-fructose syrups (HFSs). The concept of starch
hydrolysis for the production of starch-based sweeteners can be dated nearly 3000
years ago [61]. The commercial development of starch-based sweeteners is however

closely related to breakthrough in enzyme technology. The initial step in producing
nutritive sweeteners was the development of glucoamylase—an enzyme converting
starch into glucose syrup—in the 1940s/1950s. The next milestone in the starch-
based sweetener production was the discovery of glucose isomerase, which converts
dextrose to its isomer, fructose, and this led to the general commercialization of
high-fructose corn syrup (HFCS) in the beginning of the 1970s. The isomerization
process typically produces syrup with 42% fructose (42-HFCS). The introduction of
industrial-scale chromatographic separation in the 1980s was used to increase the
fructose concentration to 90%. This 90-HFCS is often blended with 42-HFCS to
55-HFCS, which can be further processed to produce crystalline fructose. In order
to mimic the flavor and mouth feel of beet and cane sugar, a blend of 55% fructose
and 45% dextrose is commonly used, since dextrose is less sweet than sucrose, while
fructose is sweeter than sucrose.
Today, the annual production of starch-based sweeteners is about 17 million tons
worldwide. Most of the glucose/dextrose syrups are based on corn starch with the
largest production in the United States. The worldwide production of HFSs is about
16 million tons per year of which over 90% is related to HFCSs—HFSs derived from
corn. About 60% of the HFCS market is related to 55-HFCS followed by about 30%
of 42-HFCS. The demand of HFCS is related to the production in which it is used as
an ingredient. Over 90% of 55-HFCS is used in the beverage and soft-drink industry,
which also accounts for 45% of the 42-HFCS usage. Other key markets for 42-HFCS
are food manufacturers (22%), cereal and bakery producers (13%), and the dairy
industry (7%). Owing to its importance, the focus is on the production of HFCS, cov-
ering directly the production of corn/dextrose syrup, 42-HFCS, and 55/90-HFCS.
The initial steps in the refinery process are liquefaction, saccharification, and
mud removal to convert the starch into corn/dextrose syrup (see Figure 7.9).
In the liquefaction step, the starch, suspended in water is liquefied by either
enzyme–enzyme liquefaction or acid-enzyme liquefaction, to reach a liquefaction
product with 10–20 dextrose equivalent (DE), a measure for the degree of starch
hydrolysis. It should be noted that a complete conversion of starch into dextrose
equals a DE of 100. For the enzyme–enzyme liquefaction, the pH of the natural
starch slurry is increased by the addition of a dilute base, for example, caustic soda.
To activate the first enzyme, calcium chloride is added. The starch slurry is then
heated via a steam jet and released into a primary liquefaction reactor with a few
minutes residence time. After flash cooling and addition of the second enzyme, the
slurry is fed into a second liquefaction reactor for a residence time of about 2 hours.
In the alternative acid-enzyme, adding a dilute acid, for example, hydrochloride,
decreases the pH of the natural starch slurry. Heating via a jet stream and release
into a primary liquefaction reactor with a few minutes residence time leads to an
initial breakdown of the starch by heat and shear. Following flash cooling and pH
adjustment, the slurry is fed into the second liquefaction reactor with an enzyme for
further conversion.
For the saccharification step, the pH is reduced by the addition of an acid, that
is, hydrochloric acid. In this step, the complete conversion of starch into dextrose
is achieved under the addition of enzymes, amyloglucosidase and pullanase. The
Flash
pH adjustment cooling
(enzyme addition) Saccharification
Enzyme addition
Starch pH adjustment Rotary vacuum filter (RVF)
Steam jet Mud removal
Dextrose
1st liquefaction
2nd liquefaction syrup
reactor
reactor pH adjustment
Enzyme activator Protein and fat
Deoxygenation pH adjustment
Dextrose
Filtration decolorization by
carbon adsorption
Isomerization
Dextrose concentration
by evaporation
Dextrose demineralization
pH adjustment Filtration by ion exchange
Final 42-HFCS
Fructose demineralization
by ion exchange concentration
by evaporation
Fructose 42-HFCS
decolorization
by carbon Filtration
adsorption
Fructose concentration
by evaporation Fructose/42-HFCS
Final concentration Final demineralization for 55/90-HFCS
of 55-HFCS by of 55-HFCS by production
42-HFCS
MF/UF evaporation ion exchange
55-HFCS 90-HFCS
55-HFCS polishing Final Chromatographic
55-HFCS
cartridge separation
filtration Blending
FIGURE 7.9 Starch-based sweetener production.
saccharification takes place in a series of continuous stirred tanks with a residence

time of about 2 days. In order to separate the mud fraction consisting mainly of
proteins and fats from the corn/dextrose syrup, commonly a centrifuge and/or a
rotary vacuum filter (RVFs) is used. At this stage, the corn/dextrose syrup can be
processed further by decolorization, deionization, concentration, etc. and sold as
syrup or maltodextrin or further converted to 42-HFCS. In the dextrose refining step,
the corn/dextrose syrup is prepared for the isomerization of 42-HFCS. The syrup is
passed through a carbon treatment to remove soluble proteins and color. The syrup
is therefore heated, adjusted to a highly acidic pH, and then passed through columns
typically packed with granulated carbon. Alternatively, powdered carbon is added to
the syrup in a stirred vessel. In order to remove the carbon from the process, stream
leaf filters are used. In the next step, the decolorized syrup is passed through ion
exchange to remove ionic matters, resulting from the starch and chemical additives
such as acids and bases, from the syrup. This removal is commonly achieved with
a two-pass cation–anion exchanger. Before isomerization, the syrup is concentrated
about 1.5 times by evaporation, deoxygenated and adjusted to neutral/slightly basic
pH. Furthermore, magnesium is added as an enzyme activator. Deoxygenation and
magnesium addition is achieved by either special chemicals acting as oxygen scaven-
ger and magnesium provider or addition of magnesium sulfate followed by a vacuum
flash deaerator. The isomerization process itself takes place in packed-bed reactors
with immobilized glucose isomerase converting dextrose to 42% fructose. Carbon
treatment and ion exchange purify the fructose similar to the dextrose. The result-
ing stream is then concentrated by evaporation to provide a stream, which is either
used for the production of 55/90-HFCS or passed through cartridge filters and a
final evaporation step to produce 42-HFCS. Additionally, an ion exchange step might
be added before filtration in the 42-HFCS production to increase the purity of the
product. In the final stage, the 42-HFCS is concentrated by chromatographic separa-
tion beyond the equilibrium point of the isomerase reaction. The concentration of
90% fructose is achieved in a multistage moving-bed chromatographic system with
a calcium ion exchange resin, which has strong affinity to fructose. The resulting
90-HFCS is then directly purified by passing through a final ion exchange stage to
remove ionic contents and impurities, a cartridge filter, and finally concentrated by
evaporation or blended with 42-HFCS to obtain 55-HFCS after final purification.
7.3.4.1 Sweetener Demudding

Conventionally, RVFs with diatomaceous earth (kieselguhr) coating are used for the
removal of the so-called mud phase consisting mainly of proteins, fats, and enzymes
after the liquefaction and saccharification step. The use of these RVFs is commonly
associated with high investment and operating costs, for example, high costs for kie-
selguhr and for the disposal of kieselguhr combined with sugar losses in the kiesel-
guhr. Furthermore, the RVFs introduce a high complexity to the process combined
with safety issues for the operators. Alternatively, the use of ultrafiltration has been
proposed for concentrating the mud fraction and purification of the sweeteners. This
approach removes the need for filter aid and removes more color and turbidity from
the sweetener, thus reducing the need for downstream processing [62,63]. The dex-
trose yield of this process using open-channel modules—plate-and-frame modules
or tubular modules—is typically between 93% and 97%, which can be increased by
the use of diafiltration to 99%. Alternatively, microfiltration/ultrafiltration in spi-
ral wound configuration can be used in combination with high-speed separators or
decanters. In this approach, the high-speed separator/decanter would remove most
of the mud fraction, while the subsequential membrane unit removes mainly color
and haze. A concept for such a synergy process combining a two-phase decanter and
ultrafiltration is shown in Figure 7.10.
Saccharification
Mud removal with decanter

Liquefied
starch
Syrup purification by
ultrafiltration Syrup
DE 40–95
Mud fraction:
Proteins
fats
enzymes
Proteins, fats, and enzymes
FIGURE 7.10 Sweetener demudding.

In the future, purification and saccharification might be carried out simultane-

ously in the enzymatic membrane reactor with an ultrafiltration membrane rejecting
enzymes and recovering the sweetener in the permeate [64].
7.3.4.2 Product Demineralization and Polishing

To remove minerals and ionic matter, conventional ion exchange resins are used to
purify the dextrose syrups. Alternatively, electrodialysis [65] and nanofiltration have
been proposed for this step. However, since high purities are required in particular
for the enzymatic conversion of glucose to fructose, a final ion exchange polishing
step might still be required [66].
In case very high purities of the syrups are required, for example, pyrogen-free
sweeteners, an additional polishing step can be placed after the ion exchange and
evaporation step. Conventionally, cartridge filters are applied for this step. Alternative
cross-flow ultrafiltration with ceramic tubular membranes or polymeric membranes
in plate-and-frame and/or spiral wound modules has been applied.
7.3.4.3 Evaporator Condensate Polishing

Similar to the sugar industry (see Section 7.2.3.2), evaporator condensate is pro-
duced in the starch and starch-based sweetener industry. Owing to carryover, the
evaporator condensate stream might be high in COD/BOD. Using reverse osmosis,
the evaporator condensate can be separated into a concentrate stream containing
most of the COD/BOD and a purified permeate stream with significantly reduced
concentrations of COD/BOD for recycling/reuse. As the pretreatment before reverse
osmosis, the evaporator condensate should be prefiltered to remove particles, such as
resin fine and pH adjusted.
7.3.4.4 Sweet Water Concentration

In the production of starch-based sweeteners, sweet waters, diluted sweetener
streams, are generated, for example, from the washing/rinsing of ion exchange, chro-
matographic, and carbon columns as well as from storage tanks and truck tanks
(Figure 7.11). The sweet water typically contains between 1% and 10% sweeteners
depending on their source. The sweeteners in the sweet water often result in high
COD/BOD levels of the streams. Reverse osmosis can be used to concentrate the
sweetener for potential reuse in the process or animal food additive and to generate
a permeate stream that can be either recycled, for example, as flushing water, or eas-
ily handled in the wastewater treatment. Using conventional spiral wound modules
suitable for up to 80 bar, sweetener concentrations of up to 50% can be achieved,
whereas the concentrations and the fluxes depend on the osmotic pressure of the
sweetener. Owing to the low initial concentration and the high final concentrations,
the use of reverse osmosis is an attractive alternative to conventional evaporation.
7.4 OUTLOOK
The growth of membrane processes in the sugar and starch industry will be stimu-
lated by the general acceptance of membrane technology and the growth of the
membrane market. The development of new applications for the sugar and starch
Adsorption/ion exchange/chromatographic
Storage tanks columns Tank truck
Storage tank
Column Tank truck
washwater
wash/rinse water washwater
Sweet water
1%–10% sweetener Reverse osmosis
Purified water for
recycling
Concentrated sweetener
up to 50% for recycling
FIGURE 7.11 Sweet water concentration.
industry for the established membrane processes such as microfiltration, ultrafiltra-

tion, nanofiltration, and reverse osmosis will not only be supported by environmen-
tal targets such as reduction in water consumption and CO2 emission but also by
an increasing demand for improved production efficiency. One of the approaches to
increase production efficiency is the research on continuous membrane reactors in
the production of starch-based sweeteners to reduce processing time and enzyme
utilization combined with the improved product quality to reduce downstream
processing [66]. This approach is still under development but progress in fouling
membranes, energy-efficient module designs combined with improvement in pre-
treatment should support its large-scale industrialization in the short/medium term.
Additional exploration of the potentials of emerging membrane processes such as
electrodialysis, pervaporation/vapor permeation, and membrane contactors in the
sugar and starch industry might inspire further growth of membrane technology
in these industries. An additional key driver for the establishment and strengthen-
ing of membrane technology in the sugar and starch industry is integrated process
solution, for example, synergies and hybrid process including membrane systems.
Apart from providing economic benefits, the development in this area will support
the understanding and awareness of membranes in the sugar and starch industry—
factors that are key to the long establishment and growth of membrane technologies
in these industries.
One of the newest market trends in the sugar and starch industry is biorefineries,
which are integrated factories for the simultaneous production of food, biochemicals,
and biofuels with optimal utilization of the feedstock. Approaches to integrate the
production of sugars and starch with the production of bioethanol are investigated
and already partly established in the industry. This work was recently extended and
now focuses now on the integrated production of biochemicals and biopolymers.
Furthermore, the utilization of sugar and starch by-products, such as bagasse or corn
fibers, is under investigation. Membrane processes can contribute to all of these new
concepts as highly selective and low-energy separation processes.
In conclusion, membrane processes have been established in the sugar and starch
industry, and future growth will be supported by current R&D and new market
trends.
REFERENCES
1. S. Loeb and S. Sourirajan 1962. Seawater demineralization by means of a semiper-
meable membrane. In: Advances in Chemistry ACS Series No. 38, R. Gould (Ed.),
Washington DC: American Chemical Society, pp. 117–132.
2. G. Trägårdh and V. Gekas 1988. Membrane technology in the sugar industry.
Desalination, 69, 9–17.
3. F. Lipnizki, M. Carter, and G. Trägårdh 2006. Applications of membrane processes in
the beet and cane sugar industry. Sugar Industry/Zuckerindustrie, 131, 29–38.
4. R.F. Madsen 1971. Process for the purification and clarification of sugar juice. British
Patent No. 1,361,674.
5. W.K. Nielsen, S. Kristensen, and R.F. Madsen 1982. Prospects and possibilities in
application of membrane filtration systems within beet and cane sugar industry. Sugar
Technology Reviews, 9, 59–117.
6. R.J. Kwok 1996. Production of super VLC raw sugar in Hawaii. Experience with the
new NAP ultrafiltration/softening process. International Sugar Journal, 98, 490–496.
7. X. Lancrencon 2004. Membrane cross flow filtration for the production of refined sugar
at a mill and in a refinery. International Sugar Journal, 105, 390–393.
8. C.C. Chou 2002. White and refined sugar production from cane sugar factories. In:
First Biennial World Conference on Recent Developments in Sugar Technologies,
Delray Beach, Florida, USA, 16–17 May, 2002.
9. S. Wittwer 2004. Scepter® Stainless Steel Membranes by Graver Technologies, In:
Practical Membrane Technology Short Course, Las Vegas, USA, 11–12 July, 2004.
10. T.J. Tyndall 1999. Recent developments in sugar clarification with tubular polymeric
membranes. In: Proceedings of the Symposium on Advanced Technology for Raw
Sugar and Cane and Beet Sugar Refined Sugar Production, New Orleans, USA, 8–10
September, 1999.
11. M. Saska, J. McArdle, and A. Eringis 1999. Filtration of clarified cane juice using spiral
polymeric membrane configuration, Indian Sugar, April, 7–13.
12. J. McArdle, A. Eringis, and B. Eaton 1999. Filtration of clarified cane juice using spiral
polymeric membrane configuration. In: Proceedings of the Symposium on Advanced
Technology for Raw Sugar and Cane and Beet Sugar Refined Sugar Production, New
Orleans, USA, 8–10 September, 1999.
13. R.J. Steindl and C.D. Doyle 1999. Applications and benefits of membrane filtration for
the Australian sugar industry. In: Proceedings of the Australian Society of Sugar Cane
Technologists, 21, 406–411.
14. T. Martoyo, M. Hino, H. Nagase, and A. Bachtiar 2000. Pilot test on ultrafiltration
of cane raw juice at the Indonesian plantation white Kedawoeng sugar factory. Sugar
Industry/Zuckerindustrie, 125, 787–792.
15. A.M. Ghosh, M. Balakrishnan, M. Dua, and J.J. Bhagat 2000. Ultrafiltration of sug-
arcane juice with spiral wound modules: On-site pilot trials. Journal of Membrane
Science, 174, 205–216.
16. A.M. Ghosh and M. Balakrishnan 2003. Pilot demonstration of sugarcane juice ultra-
filtration in an Indian sugar factory. Journal of Food Engineering, 58, 143–150.
17. R.J. Steindl and D.W. Rackemann 2010. Membrane filtration of clarified juice. In:
Proceedings of the 27th International Society of Sugar Cane Technologists Congress,
Veracruz, Mexico, 7–11 March, 2010.
18. S. Gul and M. Harasek 2009. Combined membrane-evaporation process (CMEP) for
thin sugar juice concentration. In: IMeTI Workshop on “Membrane Applications in
AgroFood”, Cetraro, Italy, 18–20 October, 2009, pp. 53–56.
19. S. Nene, S. Kaur, K. Sumod, B. Joshi, and K.S.M.S. Raghavarao (2002). Membrane
distillation for the concentration of raw cane-sugar syrup and membrane clarified sug-
arcane juice. Desalination, 147, 157–160.
20. S. Cartier, M.A. Théoleyre, and M. Decloux 1996. Combination of flocculation and
crossflow filtration for removing colored impurities in raw cane sugar solutions. In:
Conference on Sugar Processing Research, New Orleans, Louisiana, April 14–17, 1996.
21. R.N. Smith and R.E. Lacey 1982. Electromembrane processes for the food industry.
In: Scientific Conference Papers, Corn Refiners Assoc., Inc., Washington, USA,
pp. 91–118.
22. J.R. Wilson and R.W. Percival 1990. Ultrafiltration: A new alternative for the man-
agement of regenerant waste streams. In: Proceedings of the 1990 Sugar Processing
Research Conference, Townsville, Australia, pp. 116–125.
23. S.K. Thampy, P.K. Narayanan, G.S. Trivedi, D.K. Gohil, and V.R. Indusekhar 1994.
Demineralisation of sugar cane juice by electrodialysis. In: Proceeding of Twelfth
Conference IMS, Bhavnagar, India.
24. M. Decloux and L. Tatoud 2000. Importance of the control mode in ultrafiltration: Case
of raw cane sugar remelt. Journal of Food Engineering, 44, 119–126.
25. M. Hamachi, B.B. Gupta, and R. Ben Aim 2003. Ultrafiltration: A means for decolor-
ization of cane sugar solution. Separation and Purification Technology, 30, 229–239.
26. S. Wadley, C.J. Brouckaert, L.A.D. Baddock, and C.A. Buckley 1995. Modelling of
nanofiltration applied to the recovery of salt from waste brine at a sugar decolourisation
plant. Journal of Membrane Science, 102, 163–175.
27. M. Bogliolo, A. Bottino, G. Capannelli, M. De Petro, A. Servida, G. Pezzi, and
G. Vallini 1996. Clean water recycle in sugar extraction process: Performance analysis
of reverse osmosis in the treatment of press water. Desalination, 108, 261–271.
28. D. Hatziantoniou and J.A. Howell 2002. Influence of the properties and characteris-
tics of sugar-beet pulp extract on its fouling and rejection behaviour during membrane
filtration. Desalination, 148, 67–72.
29. L. Attridge, A. Eringis, and I. Jaferey 2001. Ultrafiltration of beet diffusion juice using
spiral and tubular polymeric membranes. In: ASSBT 2001, 31st General Meeting,
Vancouver, 28 February–3 March, 2001.
30. A. Hinkova, Z. Bubník, P. Kadlec, and J. Pridal 2002. Potentials of separation mem-
branes in the sugar industry. Separation and Purification Technology, 26, 101–110.
31. F. Lutin, M. Bailly, and D. Barb 2002. Process improvements with innovative technolo-
gies in the starch and sugar industries. Desalination, 148, 121–124.
32. G. Schrevel 2002. Separation of macromolecules in beet sugar processing. Sugar
Industry/Zuckerindustrie, 127, 768–769.
33. C.C. Willet 1997. The A.B.C. process for the production of refined sugar from beets,
International Sugar Journal, 99, 48–50.
34. F. Lutin 2000. Electrodialysis in the sugar industry as a purification technology. In:
SPRI Conference, Porto, Portugal, April 9–12, 2000.
35. P.J.W. Koekoek, J. Van Nispen, and D.P. Vermeulen 1998. Nanofiltration of thin juice
for improvement of juice purification. Sugar Industry/Zuckerindustrie, 123, 122–127.
36. S. Gul, A. Friedl, and M. Harasek 2009. Reverse osmosis as a pre-concentration tech-
nology in the sugar industry. In: Euromembrane 2009 Abstracts, Montpellier, France,
September 6–10, pp. 356–357.
37. S. Cartier, M.A. Theoleyre, and M. Decloux 1997. Treatment of sugar decolorizing
resin regeneration waste using nanofiltration, Desalination, 113, 7–17.
38. J.B. May 1987. Wet milling: Process and production. In: Corn Chemistry and
Technology by S.A. Watson and P.E. Ramstad (Eds.), American Association of Cereal
Chemists, St. Paul, MN, pp. 377–397.
39. R.J. Ray, J.K. Gienger, and S. Retzlaff 1986. Membrane-based hybrid processes for
energy-efficient waste-water treatment. Journal of Membrane Science, 28, 87–106.
40. J.K. Gienger and R.J. Ray 1988. Membrane-based hybrid processes. AIChE Symposium
Series, 84, 168–177.
41. Y.V. Wu 1988. Reverse osmosis and ultrafiltration of corn light steepwater solubles.
Cereal Chemistry, 65, 105–109.
42. N. Singh and M. Cheryan 1997. Membrane technology in corn wet milling. Cereal
Foods World, 42, 520–525.
43. K.D. Rane and M. Cheryan 2001. Membrane filtration of corn steep water. Cereal
Chemistry, 78, 400–404.
44. C.I. Thompson, K.D. Rausch, R.L. Belyea, and M.E. Tumbleson 2006. Microfiltration
of gluten processing streams from corn wet milling. Bioresources Technology, 97,
348–354.
45. A. Cicuttini, W.A. Kollacks, and C.J.N. Rekers 1983. Reverse osmosis saves energy and
water in corn wet milling. Starch/Stärke, 35, 149–154.
46. W.A. Kollacks and C.J.N. Rekers 1988. Five years experience with application of
reverse osmosis on light middlings in a wet mill. Starch/Stärke, 40, 88–94.
47. A. Sayaslan 2004. Wet-milling of wheat flour: Industrial processes and small-scale test
methods. Lebensmittel-Wissenschaft und-Technologie, 37, 499–515.
48. A.G. Fane and C.J. Fell 1977. Recovery of soluble protein from wheat starch factory
effluent. AIChE Symposium Series, 73, 198–205.
49. F. Meuser and H.-D. Smolnik 1976. Möglichkeiten des Einsatzes der Ultrafiltration und
der reversiblen Osmose zur Gewinnung und Aufarbeitung löslicher lnhaltsstoffe aus
Prozesswassern der Stärkeindustrie. Stärke/Starch, 28, 271–278.
50. F. Meuser and H.-D. Smolnik 1976. Zur Problematik der Ultrafiltration von
Weizenstärke-Prozesswasser. Stärke/Starch, 28, 421–425.
51. J.L. Harris 1985. Protein recovery from wheat starch factory effluent by ultrafiltration:
An economic appraisal. Food Technology Australia, 37, 564–567.
52. J.L. Harris and M. Dobos 1989. Enhanced ultrafiltration flux rates by enzymatic hydro-
lysis in protein recovery from wheat starch effluent. Journal of Membrane Science, 41,
87–102.
53. P.M. Sutton 1986. Innovative biological systems for anaerobic treatment of grain and
food processing wastewaters. Starch/Stärke, 38, 314–318.
54. G.J. Butcher 1989. Experiences with anaerobic digestion of wheat starch processing
waste. International Biodeterioration, 25, 71–77.
55. G. Eriksson and B. Sivik 1976. Ultrafiltration of potato process water—Influence of
processing variables. Potato Research, 19, 279–287.
56. B.J. Oosten 1976. Ultrafiltration of potato juice results in high yield of protein. Starch/
Stärke, 28, 135–137.
57. H. Rüffer, U. Kremser, and M. Seekamp 1997. Experiences with a reverse osmosis pilot
plant for the concentration of potato fruit water in the potato starch industry. Starch/
Stärke, 49, 354–359.
58. F. Meuser and F. Köhler 1981. Einsatz der Membranfiltrationstechnik zur

Prozesswasseraufbereitung in der Kartoffel- und Weizenstärkeindustrie. Chemie,
Mikrobiologie, Technologie der Lebensmittel, 7, 51.
59. W. Bergthaller, W. Witt, and H.-P. Goldau 1999. Potato starch technology. Starch/
Stärke, 51, 235–242.
60. H.J. Zwijnenberg, A.J.B. Kemperman, M.E. Boerrigter, M. Lotz, J.F. Dijksterhuis, P.E.
Poulsen, and G.-H. Koops 2002. Native protein recovery from potato fruit juice by
ultrafiltration. Desalination, 144, 331–334.
61. L.-T. Chang 1992. Scientific briefs. Starch/Stärke, 44, 117.
62. X. Lancrenon, M.A. Theoleyre, and G. Kientz 1994. Mineral membrane filtration for
the corn refining industry. International Sugar Journal, 96, 365–367.
63. R.B. Amar-Rekik, S. Bejar, and R. Ellouz 1994. Clarification of glucose syrups using
mineral membranes. International Sugar Journal, 96, 434–436, 467–471.
64. K.A. Sims and M. Cheryan 1992. Continuous saccharification of corn starch in a mem-
brane reactor. Part II: Membrane performance and reactor stability. Starch/Stärke, 44,
345–348.
65. R.N. Smith and R.E. Lacey 1992. Electromembrane processes for the food industry. In:
Scientific Conference Papers, Corn Refiners Assoc., Inc., Washington, DC, pp. 91–118.
66. N. Singh and M. Cheryan 1998. Membrane technology in corn refining and bio-prod-
ucts processing. Starch/Stärke, 50, 16–23.
8 Vegetable Oil
Production
Emulsification
Andras Koris
CONTENTS
8.1 Role of Membrane Filtration in Vegetable Oil Purification.......................... 270
8.1.1 Miscella Membrane Degumming...................................................... 272
8.1.2 Dry Degumming by Membrane Filtration........................................ 274
8.1.2.1 Advices for Practical Design of Dry Membrane
Degumming........................................................................ 276
8.1.3 Biodiesel Production Using Ultrafiltration Membrane
Separation Technology...................................................................... 276
8.2 Membrane Emulsification and Encapsulation in Food Industry................... 281
8.2.1 Specifications of Membrane Emulsification Operation..................... 283
8.2.1.1 Direct or Cross-Flow Membrane Emulsification................284
8.2.1.2 Premix Membrane Emulsification...................................... 285
8.2.1.3 Materials of Emulsification Membranes............................. 285
8.2.1.4 Sizing of the Cross-Flow Membrane Emulsification
Process Parameters............................................................. 286
8.2.1.5 Ideas for O/W and W/O Emulsion Production by
Membrane Technique......................................................... 288
8.2.2 Possibilities in Food Nanotechnology............................................... 290
8.2.2.1 Simple Nanoemulsions....................................................... 291
8.2.2.2 Nanostructured Multiple Emulsions................................... 291
8.2.2.3 Nanostructured Multilayer Emulsions................................ 291
8.2.3 Microencapsulation........................................................................... 292
References............................................................................................................... 295
The utilization of vegetable oil is almost of the same age as that of humanity. Earlier,
the need for such oil was increased with the demand in application fields, techno-
logical development, and population growth. In the last decade, the demand for veg-
etable oil has catapulted due to a combination of factors. The first is the increased
consumption of edible oils, particularly in emerging countries such as China and
India due to, among other things, population growth, improving living standards,
and changing diets. The second is the development of the biofuels industry (and
more specifically biodiesel) around the world, particularly in the European Union,
269
the United States, Brazil, Argentina, China, and India, and price increases due to
various factors such as increase in oil prices, low stock worldwide, drought, and
speculation. The last factor is changing weather patterns that leads to a rise in the
demand of vegetable oil, which can have major geographical impacts and can be,
potentially, quite large.
There are two major consumers of vegetable oils: the food sector, which rep-
resents over 80%; and industrial sector, including biodiesel. The main driver for
expansion is still the growing demand for edible oils for the food market, although
another important part of this demand comes from the biodiesel sector. The veg-
etable oil market is bound for major changes, and will face substantial challenges
and opportunities. Improving living standards in emerging economies, population
growth coupled with changing diets, and the expansion of the biodiesel industry are
new trends that will have a major impact in the future development of this sector
(Rosillo-Calle et al., 2009).
In the vegetable oil industry, as well as in other industries, energy efficiency and
environmental-friendly processes are important factors for a company to be success-
ful in the market. Membrane techniques are possible alternative “green” methods for
conventional liquid separation processes. Generally, membrane separation processes
are a possible solution for the following problems:
• High energy consumption during the processes of liquids, for example,

mixing or concentration by thermal evaporation
• Decrease of essential and healthy substances in the liquid product, which is
a typical phenomenon of high-temperature processes
• Production of a large amount nonreusable and nondischargeable wastewater
8.1 ROLE OF MEMBRANE FILTRATION IN VEGETABLE

OIL PURIFICATION
The application of membrane separation techniques in the edible oil industry started
in the late 1970s with wastewater treatment ultrafiltration-reverse osmosis (UF-RO),
miscella microfiltration, protein purification (UF-RO), and nitrogen production
(Gupta, 1977; Köseoglu, 1995). In general, it was assumed that membrane filtra-
tion is energy efficient and the loss of oil is decreased compared to conventional
separation processes. In the 1990s, researchers expressed that the advances of mem-
brane filtration could be utilized in other steps of vegetable oil production. Snape and
Nakajima (1996) stated that membrane separation is a potential alternative method
for commercial phospholipid separation, wax and acid removal, deodorization distil-
late separation, solvent recovery, and bleaching. After a decade of intensive research
and optimization, the industrial application of membrane filtration for vegetable oil
purification found its way into the field of degumming, dewaxing, deacidifying, gen-
eral clarification, and used cooking oil reclamation. The membrane filtration method
is used both in edible oil and biodiesel production.
In Figure 8.1, the efficiency of membrane filtration is demonstrated; conven-
tional water degumming and membrane degumming are compared using flow-
charts. It can be seen that membrane degumming needs only a prefiltration of
Vegetable Oil Production 271
Conventional degumming process
Stream Water
Degummed oil
Crude Further
oil refining
Pump Heat Mixer Coagulator Centrifuge
exchange
Moisture + gum + oil
Gum + oil Membrane degumming process

Press oil
Pump 1 Pump 2 Further

refining
Degummed oil
Sludge
Prefilter Membrane filtration
FIGURE 8.1 Flowchart of conventional water and membrane degumming.
the media and one pump to accomplish the purification, while water degumming
requires a pump, heating, mixing, a coagulator, and a disk-stack centrifuge. An
additional advantage of membrane filtration in the processing line is that not only
the gum is removed but other impurities as well, so the charge on the following
purification steps is also decreased. Furthermore, the membrane filtration process
is environment friendly due to its low chemical demand. The increasing demand
of consumers for healthier food is another advantage for membrane purification
since the operating conditions are material friendly so as to preserve the bioactive
compounds in the final product.
The degumming process is important where phosphatides and phospholipids
exist in the crude oil. Typically, sunflower seeds, and also rapeseeds, carry such
materials in high content (100–300 ppm phosphorus content). The phosphatides and
phospholipids form the so-called gum in the crude oil. Recently, these substances
have been totally removed by the degumming process (<10 ppm) although some of
these materials, for example, lecithin (phosphatidylcholine), have health benefits or
are valuable, and they are also important for the typical odor and taste of several
oils. The reason for this is that gums reduce the efficiency of other refining steps,
for example, bleaching, and they increase the turbidity and decrease the shelf-life of
the final product. The presence of gums is an unwanted phenomenon, especially in
the case of cooking oils because they are less stable than triglycerides at high tem-
perature. The recovery of lecithin is also difficult when the hydrophilic part of the
phosphatide is connected to water molecules, so it is in a hydrated state.
“Membrane degumming” is the term used for the membrane technology that
removes gums from both miscella and crude oil. Most of the cooking oils are
recovered by hexane extraction in food industry; the degumming of the organic sol-
vent–oil mixture, the miscella, is called “miscella membrane degumming.” In the
case of pressed oil membrane filtration, the technology is called “dry membrane
degumming” since no solvents are present in the process, and the oil is dry. The past
and present states of the miscella and dry degumming are detailed in the following
sections.
8.1.1 Miscella Membrane Degumming

From oily seeds, such as sunflower seeds or rapeseeds, the main part of the oil con-
tent is obtained by hexane extraction. The final hexane–oil mixture of this process,
the miscella, is a stable oil-in-hexane emulsion; the oil does not flow freely on the
surface. This property is favorable for the application of membrane technology.
During miscella membrane degumming, the liquid is conducted to a micro- or an
ultrafilter to retain the gum content and other impurities of the crude vegetable oil.
The first patent on miscella membrane degumming was announced by Sen Gupta
in 1977 (U.S. Patent 4,062,882). He stated that the size of the micelles is 20 kDa or
larger, whose size spectra is greatly retained by ultrafiltration (Figure 8.2). This tech-
nique is also widely known as “micelle-enhanced ultrafiltration” (MEUF) and it was
followed by many other researchers. Iwama (1989) and Kim et al. (2002) separated
soybean oil from hexane. The membranes were fabricated from polyimide with phase
inversion with 20 kDa molecular weight cut-off (MWCO). The researchers could
reach a volumetric concentration factor (VCF) of 10 with 90% phospholipid reten-
tion. Lin et al. (1997) applied commercial hexane-resistant polymeric (1 kDa) and
polyamide (15 kDa MWCO) membrane for cottonseed miscella membrane filtration.
The phospholipid retention was 99% and 95%, respectively. Pagliero et al. (2005)
investigated the gum separation of asymmetric polyvinylidene-difluorite (PVDF)
membranes. In the case of sunflower seed and soybean miscella filtration, the phos-
phorus separation was varied between 95% and 99%. Many researchers dealt with a
different membrane material or with a combination of different methods in parallel
(De et al., 1998; Wu and Lee, 1999; Garcia et al., 2006; Hafidi et al., 2005) in order
Oil Hexane
droplet
Phosphatides
FIGURE 8.2 An ideal micelle in organic solvent.

to remove gums and other impurities from the miscella. Others investigated different
industrial parameters (Ebert and Cuperus, 1999; Subramanian et al., 2001). It must
be emphasized that in most of the cases, cross-flow membrane filtration was applied.
The efficiency of miscella membrane degumming can meet industrial standards
according to recent publications as well. Saravan et al. (2006) filtered rice bran oil
and water-degummed oil–hexane miscella on a nonporous polymeric flat-sheet
membrane with a silicone active layer. In the case of rice bran oil, the phosphorus
rejections were between 95% and 98%, and it was between 66% and 85% in case of
soybean, which was already degummed partially, so mainly nonhydratable phospha-
tides were retained. A tubular ceramic membrane with 15 kDa MWCO was applied
on crude soybean oil–hexane miscella to remove phospholipids (Marenchino et al.,
2006). The researchers could reach 30 L/m2.h permeate flux and gum rejection was
above 95% at 30°C and transmembrane pressure (TMP) of 2 bar. Polyethersulfone
membranes with 4 and 9 kDa of MWCO were studied from the aspect of phospho-
lipid removal from sunflower seed oil miscella by Garcia et al. (2006). The rejection
of phospholipids was between 95% and 97%. The membrane with the 9 kDa MWCO
showed higher miscella flux, lower oil retention, and higher free fatty acid rejection
compared to the 4 kDa MWCO, and the experiments were carried out up to 3.2 VCF.
de Souza et al. (2008) degummed corn oil–hexane miscella using a ceramic
membrane with the setup introduced in Figure 8.3. The aim of their study was to
investigate the degumming (removal of phospholipids) of crude oil–hexane miscella,
VD Valve
Retentate
Thermometer T Warm water
M Manometer
Feed tank
Hot water
Membrane
V3
Permeate
Balance Rotameter
V1 Control panel with
Back flux frequency inverter
V2 for the pump
M
Pump
FIGURE 8.3 Experimental miscella membrane degummer. (From de Souza, M. P. et al.:

J. Food Eng., 2008;86(4):557–64.)
260
I II III
240 Exp A
220 Exp B
200 Exp C
180
Permeate flux (kg/m2.h)
160
140
120
100
80
60
40
20
0
0 5 10 15 20 25 30 35 40 45 50
Time (min)
FIGURE 8.4 Permeate flux versus time when the feed is concentrated. (From de Souza, M. P.
et al.: J. Food Eng., 2008;86(4):557–64.)
using an alumina multichannel ceramic membrane with an average pore diameter

of 50 nm. The influence of TMP (0.5 and 1.5 bar), tangential velocity (v), (1.4 and
2.4 m/s) and percentage of corn oil on the miscella (25% and 35% w/w), in terms of
the permeate flux and removal of phospholipids, was investigated.
A phospholipid removal of between 65% and 93.5% was achieved, resulting in a
minimum phosphorus content in the permeate of 23 mg/kg and a reduction in color
and waxes, besides the conservation of tocopherols and tocotrienols in the crude oil. A
raised TMP and a greater percentage of oil in the miscella had a positive effect on the
retention of phosphorus, while the tangential velocity had a negative influence. Under
the best operational conditions used, the permeate flux reached 120 kg/h−1 m2 at 40°C.
The concentration experiment is shown in Figure 8.4 from the aspect of permeate flux.
In 2008, Ribeiro et al. (2008) published their results of a miscella membrane
degumming pilot-plant-scale apparatus optimization. With the setup used by the
researchers, it was possible to reduce greatly the phosphorus content of soybean oil–
hexane miscella (from 800 mg/kg to 2 mg/kg with a flux of 40 L/m2.h).
8.1.2 Dry Degumming by Membrane Filtration

Nowadays, the purification of pressed crude oils (without any solvents) by membrane
filtration is an alternative green technology to conventional refining. The removal of
pollutants from the feed is more complex than miscella membrane degumming due
to the high viscosity of crude oil, 20–70 cP, when the viscosity of the hexane–oil
miscella varies between 0.5 and 5 cP (at 25°C). The number of publications in the
field of dry membrane degumming is significantly lower compared to that of mis-
cella membrane filtration; however, sunflower, rapeseed, and coconut kernel oils are
produced in large quantities by pressing.
The pioneers of membrane dry degumming were Zhang et al. (1996) and
Subramanian et al. (1997, 1998). Zhang and his research team applied self-fabri-
cated polyimide membranes while Subramanian with his colleagues used flat-sheet
membranes with silicone active layer (10, 20, 30 nm pore size). Crude soybean and
rapeseed oils were the experimental materials in the dead-end ultrafiltration process
with a phosphorus removal of 93% and 96%. Later, Subramanian et al. (1999) tried
hydrophobic and hydrophilic polytetrafluoroethylene (PTFE) and PVDF membranes
as well but they could reach 99% of gum retention only with the optimization of the
silicone active layer membrane process.
The main disadvantage of dry membrane degumming with polymeric mem-
branes was the unsatisfactory permeate flux besides irreversible fouling. Practically,
it means the membrane pores and surface are plugged and covered by the accumu-
lation of nondissolved solid (NDS) particles and thus not only impurities but also
triglycerides are retained. In such cases, mild cleaning methods are not efficient;
usually, organic solvents, acids/bases, and high-temperature wash with detergents
have to be applied, but the use of these liquids is limited due to the low resistance of
polymeric membranes against them.
For example, a significant increase in productivity was observed when research-
ers applied cross-flow setup and organic solvent conditioning (ethanol and propa-
nol) on polymeric membranes in order to change the hydrophobicity (Koris and
Vatai, 2002), but the shelf-life of the membranes was still too short (several experi-
ments). The rapid development of inorganic ceramic membranes gave a boost to
pressed oil purification. Alicieo et al. (2002) tried polysuphon (PS) hollow fiber
and ceramic tube membranes in the filtration of crude soybean oil. The titania-
based ceramic membrane provided an excellent 99% phosphorus retention. In
2006, Koris and Marki (2006) published good results with sunflower seed oil as
well. They used 20-nm pore size ceramic tube membranes with zirconia active
layer to obtain 98% gum retention with a satisfactory level of permeate flux. The
ceramic filters also provided good stability in these experiments, so it was able to
increase the shelf-life up to years. Another important remark on crude oil mem-
brane filtration is that prefiltration cannot be omitted; the presence of fine seed and
peel particles and other solid impurities in the feed can drastically increase mem-
brane fouling and the frequency of washing. It is also important to note that most
of the publications mention not only the decrease of phosphorus content in the
permeate but a (at least partial) simultaneous removal of free fatty acids, saponifi-
able materials, chlorophyll, and waxes.
Liu et al. (2012) studied the removal of phospholipids from Jatropha oil through
a conventional degumming process combined with ultrafiltration membrane separa-
tion in a small-scale batch system. The optimum operating condition was determined
to be 65°C, with 4 wt% acid solution added, and a centrifugation speed of 1600 rpm.
After the degumming process, the phospholipid content of Jatropha oil was reduced
from 1200 to 60 ppm. This was further reduced to less than 20 ppm by subjecting
the oil to ultrafiltration membrane separation. The authors found that the entire pro-
cess not only decreased the phospholipid content of the oil but also improved its fuel
properties, especially its kinematic viscosity and carbon residue. The kinematic vis-
cosity was decreased from 30.02 cSt (mm2/s) to 27.20 cSt, while the carbon residue
was decreased from 7.8% to 4.0%. Aside from the phospholipid content, the other
two properties mentioned above were also considered to be important in the use of
pure plant oil as a fuel in diesel engines.
The performance of polypropylene hollow fiber ultrafiltration membrane during
NDS removal from palm kernel oil was investigated by Purwasasmita et al. (2013).
The polypropylene hydrophobic hollow fiber membrane in dead-end configuration
has been used for palm kernel oil NDS removal. The researchers found that tem-
perature and transmembrane pressure have a proportional effect on permeate flux. In
contrast, they have an inverse effect on the rejection of NDS. During the experiment,
permeate fluxes and rejections of NDS varied from 3.4 to 8.7 L/m2 . h and from 51%
to 94%, respectively. The best operating conditions suggested are a feed temperature
of 30°C and a TMP of 1 bar, which produced the highest NDS rejection.
8.1.2.1 Advices for Practical Design of Dry Membrane Degumming

In the design of a membrane application or a process, the most important process
parameters are the productivity and the separation quality. In case of edible oil mem-
brane filtration, the productivity is often expressed in permeate flux whose parameter
is mainly controlled by the pore size of the membrane, but the TMP, axial velocity,
and process temperature have a significant effect on the flux as well. The gum reten-
tion of the process depends highly on the pore size, but to reach industrially accept-
able permeate quality, fine-tuning of other process parameters such as TMP, axial
velocity, and temperature is also necessary. So it is possible to select the appropri-
ate membrane and estimate the necessary membrane area next to pumping power
requirement. Figure 8.5 shows how the sunflower seed oil flux depends on the pore
size, pressure, and axial velocity in case of a ceramic (ZrO2) membrane.
To give some guidance on proper pore size choice for optimal gum separation, a
comparable diagram is introduced in Figure 8.6. The amount of gum is expressed
in total phosphorus content and the shown membranes are ceramic ones again. The
continuous lines in Figure 8.6 represent an idea for retention since no data are avail-
able between the dots, which are measured points. Another important point in the
design is the process time. From this aspect, vegetable oil filtration behaves as a
classical concentration with the use of membranes; the initial flux decreases as a
function of process time or volumetric concentration factor due to concentration–
polarization phenomena and fouling (Figure 8.7).
8.1.3 Biodiesel Production Using Ultrafiltration Membrane

Separation Technology
The discovery of the potential of vegetable oil to serve as fuel was made by one of
the most famous scientist of the nineteenth century named “Rudolf Diesel.” Diesel
stated in 1912 that “the use of vegetable oils for engine fuels may seem insignificant
20
18 2.8 m/s, 100 nm

16
1.4 m/s, 100 nm
14
2.8 m/s, 20 nm
Flux (L/m2.h)
12
10
6
4
2
0
0 1 2 3 4 5 6
TMP (bar)
FIGURE 8.5 Sunflower oil flux as a function of pore size and pressure at 50°C.
100
90
Phosphorus retention (%)

80
70
60
50
40
100 90 80 70 60 50 40 30 20 10
Pore size (nm)
FIGURE 8.6 Total phosphorus retentions of ceramic membranes at 50°C.
today. But such oils may become in course of time as important as petroleum and the
coal tar products of the present time” (Agarwal, 2007).
The use of vegetable oils as an alternative renewable fuel competing with petro-
leum was proposed in the beginning of the 1980s (Demirbas, 2003). The most com-
monly used biodiesel production method is transesterification, where an animal
fat or vegetable oil is reacted with an alcohol (usually methanol) to form fatty acid
methyl esters (FAME) and glycerol (Van Gerpen, 2005). After completion of the
reaction, the transesterification product is a multicomponent mixture containing
mainly FAME, methanol, glycerol, water, and salts. The purity of biodiesel is an
important issue, and affects the cost of the final product. A key measure of bio-
diesel quality is the level of free glycerol in the biodiesel. In order to remove glyc-
erol from FAME or biodiesel, there are many downstream processing treatments.
5
Flux (L/m2·h)
2
0 1 2 3 4 5 6
Time (h)
FIGURE 8.7 Flux behavior of ceramic membranes during concentration (pore size = 20 nm,
TMP = 4 bar, t = 50°C, velocity = 4.4 m/s).
Some problems with conventional purification steps are the production of significant
amounts of waste (e.g., wastewater) or toxic materials (e.g., residual methanol and
catalyst). Karaosmanoglu et al. (1996) noted that for conventional production pro-
cesses, for each liter of biodiesel, 10 L of waste water are produced.
At present, membrane separation technologies are new to biodiesel purification
processes. However, recent work has shown the efficiency of using membrane tech-
nology in the production of biodiesel. The membrane refining technique can be used
for the purification of crude biodiesel and also in the purification of FAME.
He et al. (2006) compared conventional biodiesel-refining techniques and hollow
fiber membranes such as polyacrylonitrile and polysulfone. The authors noted that
the membrane-refining technique overcomes the formation of emulsion of water and
esters, decreases purification losses in comparison to conventional techniques, and
provides biodiesel purity of 99 wt.% (He et al., 2006).
Using the ceramic membrane separator only for the purification of crude palm
biodiesel, Wang et al. (2009) found that the residual soap and glycerol could be lower
than the EN14538 specifications after being reduced at a TMP of 0.15 MPa and a
temperature of 60°C. Furthermore, the group at the University of Ottawa invented a
new technology for biodiesel production using membrane reactor (Dubé et al., 2007;
Tremblay et al., 2008, Figure 8.8). Their results illustrate the advantages in using a
membrane reactor to produce biodiesel, where products are continuously removed
from the reactor in a different phase than the lipid reactant.
Other researchers have employed membrane technology in the purification of
FAME. Othman et al. (2010) investigated eight different types of commercial poly-
meric solvent-resistant nanofiltration (SRNF) membranes for separating the methyl
esters-rich effluent (biodiesel) from the mixture of homogeneous catalyst, free glyc-
erol, and excess methanol after the transesterification process at various separation
pressures and constant temperature. The separation of FAME from the permeate
TT
Drain Permeate
collection
Hot water tank
in
Back pressure
Heat controller
Membrane
exchanger tube
Hot water
out
Feed pump
Circulating pump
Drain
FIGURE 8.8 Schematic diagram of membrane reactor. (From Dubé, M. A., Tremblay, A.
Y., Liu, J.: Biores. Tech., 2007;93:639–47.)
stream also makes the recycled methanol (MeOH) phase back to the membrane
reactor, thus lowering the overall alcohol-to-oil molar ratio to 10:1 (Cao et al., 2008).
Saleh (2011), from his literature survey, found that there were almost no reports
on the direct removal of glycerol from untreated biodiesel using a membrane sepa-
ration system. Certainly, none of the reported uses of such a system resulted in the
achievement of American Society for Testing and Materials (ASTM) and European
Norms (EN) levels for free glycerol in FAME. Nonetheless, it is likely that mem-
brane technology can be successfully used to separate glycerol droplets from FAME
while avoiding costly and environmentally deleterious water washing, adsorption, or
ion-exchange methods (Saleh, 2011).
Another new alternative technology, generally applied for extracting water-sol-
uble components from organic liquids, can be applied to biodiesel. In this technol-
ogy, hydrophobic porous membranes can be used to prevent bulk mixing of the two
phases and facilitate contact and mass transfer of species between the two phases.
One of the novel reactors is enabled to separate the reaction products (FAME/glyc-
erol in methanol) from the original vegetable oil feed. Owing to the immiscibil-
ity of lipid feedstock and alcohol, lipids form droplets (diameter of 20–1800 μm),
which are excluded from passing through the membrane pores (diameter of
1.4 μm). The microporous inorganic membrane selectively permeates FAAE, alco-
hol, and glycerol while retaining the emulsified oil droplets. As a result, no lipids
(Triradylglycerolipids [TG], Diradylglycerolipids [DG], Monoradylglycerolipids
[MG]) are found in the permeate stream, which implies that high conversions
typically necessary in conventional biodiesel processes are not required here. The
free and total glycerine contents of the biodiesel easily meet international standards
for purity (Sdrula, 2010).
A new innovative fatty acid and glycerol production technology was introduced
by Chakraborty and his colleagues in 2012. Their submerged membrane bioreactor
(SMBR) is an energy-efficient method to continuously convert residual oil stream
into fatty acid. SMBR systems have mostly been used to treat industrial wastewater,
domestic wastewater, and specific municipal wastewater, where stringent discharge
standards were required in order to make it usable. In the early 1990s, membrane
bioreactor (MBR) installations were mostly constructed in external configuration, in
which the membrane module share outside the bioreactor and biomass is recirculated
through a filtration loop. After the mid-1990s, with the development of SMBR sys-
tem, MBR applications in municipal wastewater extended widely. The applications
in SMBR is till today only for wastewater treatment while for other possible applica-
tion such as recovery or production of value-added component, in biotechnological
applications, in food processing, etc., it is yet to be explored. The enzymatic biphasic
processes are of increasing use in the production, transformation, and valorization of
different biomass-based raw materials. Important applications have been developed
in the field of food, drinks, fine chemicals synthesis, pharmaceutical-grade products,
energy, and cosmetics, or even for clean and green environmental purposes. Most of
the time, the reactions and separation are carried out in a classical side stream enzy-
matic membrane bioreactor (EMBR). The conventional side stream EMBR could
be used as a continuous process in which enzymes are separated from end products
with the help of a selective membrane layer. In two-phase bioconversions, the mem-
brane acts as a support for the interface between two distinct liquid phases. The
membrane not only separates the phases but also provides interfacial contact area
and, together with the enzyme, acts as an interfacial catalyst.
In the work of Chakraborty et al. (2012), the concept of the two separate phase
membrane bioreactor has been explored using enzyme-loaded membranes in the
submerged configuration for the treatment of waste biomass for the recovery of fatty
acids and glycerol (Figures 8.9 and 8.10). The hydrolysis of triglycerides into fatty
Pump
SMBR
Gas Aqueous phase
cylinder
Organic phase Microporous membrane with lipase
FIGURE 8.9 Schematic view of SMBR by Chakraborty et al. (2012).

Fatty acids Glycerol
Membrane wall Lipase Pore

Triglyceride
FIGURE 8.10 Production scheme of fatty acids in membrane micropores with an immobi-
lized enzyme.
acids and glycerol has been used as a model reaction to study and optimize the sub-
merged enzyme-loaded membrane performances. Chakraborty et al. (2012) focused
on the study of the enzyme immobilization within the submerged membrane mod-
ule, evaluation of the performance of the submerged enzyme-loaded membrane as a
function of physical, chemical, and fluid dynamics conditions. For this investigation,
commercial virgin olive oil was used. Once the operation of the reactor was studied,
the system was tested for the hydrolysis of triglycerides present in fried vegetable oil.
It has also been observed that the productivity of the reactor using fried cooking veg-
etable oil is 82 ± 2% compared to the one obtained with virgin olive oil. The fact that
lower productivity was due to the oil composition could be confirmed by the fact that
by using the virgin olive oil again, the reactor performance was the one originally
obtained with this pure substrate source, that is, enzyme catalytic activity was not
damaged by the raw material of waste fried cooking oils. An experimental optimiza-
tion of operating parameters has been carried out as well. With the response surface
methodology (RSM) analysis, the submerged enzyme-loaded membrane showed
maximum performance at TMP 82.9 kPa, pH 7.4, temperature 35.18°C with an axial
velocity of 0.069 m/s, and organic stirring 89.92 rad/s, which is quite comparable
with the experimental data. Virgin olive oil has been used for optimization studies
and results have been applied for the hydrolysis of glycerides present in fried oils.
Results confirmed that the SBMR can work efficiently with waste oils, producing
and simultaneously separating glycerides hydrolysis reaction products.
8.2 MEMBRANE EMULSIFICATION AND

ENCAPSULATION IN FOOD INDUSTRY
Emulsions play an important role in the food industry. For example, several salad
dressings, cream liqueurs, and artificial dairy products are often made through the
emulsification of the immiscible oil in the aqueous phase (oil-in-water, or O/W emul-
sion, Figure 8.11). Others like margarine and low-fat spreads are water-in-oil (W/O)
emulsions in general.
50 µm
FIGURE 8.11 Structure of a fine homogeneous O/W emulsion by ME.
Food emulsions can be classified depending on their end-uses as well. At first,

some of the emulsions are already final products to their nature, for example, coffee
creamers and cream liqueurs; these liquids are simple emulsions with great stability.
Second, other emulsions are ingredients that are components of a more structured
product, such as yogurts and other gel systems. Finally, emulsions can assist in creat-
ing new matrixes, for example, ice creams or whipped products (Charcosset, 2009).
Emulsification technologies are usually applied to prepare uniform droplets, which
are later turned into solid spheres or capsules as well. The common techniques are
shown in Figure 8.12. Membrane emulsification (ME) is a relatively novel technique
introduced by Nakashima and Shimizu in the late 1980s (Nakashima et al., 1991). In
this process, the dispersed phase is forced through the pores of a microporous layer
(membrane) directly into the continuous phase. Emulsified droplets are formed and
detached at the end of the pores. The advantages of ME over conventional emulsifica-
tion processes are that it enables to obtain very fine emulsions of controlled droplet
sizes and narrow droplet size distributions; successful emulsification can be carried
out with much less consumption of emulsifier and energy, and because of the lowered
shear stress effect, ME allows the use of shear-sensitive ingredients, such as starch and
proteins (Vladisavljevic et al., 2000). The method of ME has already been applied in
some areas of food, chemical, electronic, and medical industry (Kandori et al., 1992;
Katoh et al., 1996; Nakashima, 2000). For ME, several types of membranes, ceramic,
polymeric, and glass, are mainly tested. The Shirasu porous glass (SPG) membrane
was developed by Nakashima and Shimizu (Nakashima and Shimizu, 1986) in Japan
for mechanical emulsification. This type of membrane has uniform pores and narrow
pore size distribution compared to, for example, ceramic membranes. The SPG mem-
branes are also available in a wide range of pore sizes.
In the publications of other researchers, to ensure good quality (low droplet
size and their small span in the emulsion), relatively high axial cross-flow velocity
(0.5–1.4 m/s) is suggested for continuous phase and transmembrane pressure:critical
Rotor-stator (-rotor) devices High-pressure homogenizer
Ultrasound emulsification Membrane emulsification
Continuous phase
Droplet phase
FIGURE 8.12 Collection of recently used emulsification techniques. (From http://www.lvt.

uni-karlsruhe.de/english/1087.php.)
pressure ratio of approximately 1.1:1.2 for disperse phase (Vladisavljevic and

Schubert, 2002; Vladisavljevic et al., 2004). The problems with these setups are the
increased shear stress near the membrane surface, the higher energy usage of the
recirculation pump, and low performance (low disperse phase flux). There are many
publications about the understanding of the effect of operating parameters for a bet-
ter ME (Yasuno et al., 2002; Giorno et al., 2005; Dragosavac et al., 2008; Egidi et al.,
2008). One of the innovative methods to improve the process is the application of
vibrating membrane (Zhu and Barrow, 2005; Kelder et al., 2007). According to these
research studies, ME could be enhanced by mechanically exciting the membrane,
thereby enabling the formation of smaller droplets of a narrower size distribution,
combined with higher specific production rate. However, it seems not easy to control
this kind of combined method and, also, there is no information about the costs. The
application of turbulence promotion to intensify the ME process to an industrial level
is a superb solution and a definite answer for skeptics. With appropriate fine-tuning
of static turbulence promotion, the driving force of the process could be increased up
to 14.4 with no unwanted change in the structure of the emulsion, besides low wall
shear stress (0.6 Pa) on the product (Koris et al., 2011).
8.2.1 Specifications of Membrane Emulsification Operation

Compared with conventional turbulence-based methods such as homogenization
and rotor-stator systems, less energy is needed in ME to access the same range in
droplet size. The technique makes it attractive for industry for its simplicity, poten-
tially lower energy requirements, less need for surfactants, and a narrow droplet size
distribution. The system is applicable to both the oil–water (O/W) and water–oil
(W/O) emulsions production (Joscelyne Simon, 1999) . Even in a highly concentrated
dispersion phase, a stable emulsion can be obtained (Katoh et al., 1996). Also, the
production of multiple emulsions can be realized by ME.
Through a careful choice of different parameters of the membrane, relative to the
nominal pore size, 2–10 times the diameter of emulsion droplets is obtained. The
effects of the operating parameters are relatively well known, particularly in the
quality factors. The pore size and pore distribution of the membrane have a direct
impact as is reflected in the results, but the interfacial tension and shear forces acting
along the wall are also important factors.
ME technologies can be divided into two categories: direct/cross-flow and premixed
emulsification.
8.2.1.1 Direct or Cross-Flow Membrane Emulsification

During emulsification, dispersed phase particles under certain conditions pass through
the membrane pores and droplets are formed at the edge of the pore. In the case of
cross-flow mode, since the surface is parallel to the progressive flow of the continu-
ous phase, droplets detach from the pore ends mainly due to the helping force (Figure
8.13). This phenomenon could help in size adjustment and emulsion quality. At stirred
cell or direct emulsification, the shear force is intensified with a stirrer for the same
reasons (Gijsbertsen-Abrahamse, 2003). Ideally, droplet size can be controlled mainly
by selecting the membrane, the flow rate, and the TMP. The additional advantages of
cross-flow ME are the simple design and ease of extensibility (Akmal, 2010). A small-
sized commercial membrane emulsificator is introduced in Figure 8.14.
Mixer (n)
Cross-flow
Dispersed phase (p1)
Droplets
Continuous
Continuous phase (p0)
phase (v, p0)
Droplets
Membrane Membrane
Dispersed phase (p1)
Stirred cell
FIGURE 8.13 A visual comparison of cross-flow and direct (or stirred cell) membrane
emulsification techniques.
N2 gas
Dispersed phase: 30 mL
Continuous phase: 150 mL
SPG membrane: 40 mL
Line: SUS heating line
Stirrer: 0 ~ 600 rpm
FIGURE 8.14 Commercial membrane emulsifier IMK-40M1 by MCTech Co. Ltd. (From
http://www.mctplus.co.kr/en/3-1.htm.)
8.2.1.2 Premix Membrane Emulsification

In premix ME, the rough premixed emulsion is forced through the membrane to
reduce the size of the dispersed phase droplets. Comparing cross-flow emulsification
with premix emulsification, the high concentration of dispersed phase fraction can
be produced with premix, although in this case, the droplets do not form as a mono-
disperse system, such as in a cross-flow emulsification case, because the dispersed
phase particles are of different sizes. In fact, the premix emulsification is a modified
form of the classic emulsification method, such as high-pressure homogenization.
The process begins with a rough preemulsion, which is further refined by passing it
through the capillaries of a microporous membrane. In most cases, the continuous
phase of the preemulsion wets the membrane and the emulsion droplets are split
smaller. In some cases, the dispersed phase wetted the membrane and phase inver-
sion occurs, which may result in a very large volume of disperse phase fractions. It
should be noted that only certain materials can be produced by phase inversion.
The energy costs of premixed emulsification are relatively low, since there is no need
for transverse flow. The energy requirement of this process can be one order of magni-
tude lower than for cross-flow emulsification in case of highly concentrated products.
However, in general, it is not possible to produce the desired emulsion in an early stage
of operation; additional homogenization and repeated cycles are required. This opera-
tion is generally known as repeated or multistage premixed emulsification; better yield
and droplet size distribution can be achieved with it, but only with an increase in total
energy intake. The disadvantage of premixed emulsification is the fouling of the mem-
brane, which depends on the components of the product (Akmal, 2010).
8.2.1.3 Materials of Emulsification Membranes

The most commonly used membranes in the production of oil-in-water emulsions are
the hydrophilic SPG membranes, ceramic aluminum oxide- and zirconium oxide-
coated membranes, and macroporous silica glass plates. Further experiments were
carried out of silicon nitride microfilters as well. For water-in-oil emulsion preparation,
mainly PTFE membranes, hydrophobic SPG, and micromanufactured metal and silicon
nitride membranes are used. In general, the tubular membranes are often used in cross-
flow mode, while in stirred cell setup, the membrane shape is a circular flat-sheet.
8.2.1.4 Sizing of the Cross-Flow Membrane Emulsification

Process Parameters
Scientists and engineers, who are dealing with such novel applications as ME, are
often faced with the lack of sizing calculations. In this regard, help is extended to
make an impact for the important process parameters. One of the most important
process parameters is the dispersed phase flux (JD), which refers to the amount of
emulsified fluid. It allows the determination of the necessary membrane area. The
dispersed phase flux, JD, is related to the TMP according to Darcy’s law:
K ⋅ TMP
Jd =
µ⋅L
where K is the membrane permeability, L the membrane thickness, and μ the dis-
persed phase viscosity.
In cases where the membrane may be assumed to have uniform cylindrical pores
of radius r, the permeability K is given by the Hagen–Poiseuille equation:
nr 2
K=
8π
To ensure high productivity and good product quality, the determination of the
driving force (DF) of the process could also be necessary. The DF is expressed as the
ratio of TMP and critical pressure (CP) according to the following formula:
TMP
DF =
CP
The TMP is an important parameter in the product quality, but its adjustment
differs from the classical setting of TMP at membrane filtration because it is slightly
affected by the continuous phase velocity (Figure 8.15):
( Pc,in + Pc,out )
TMP = Pd −
2
The CP is equivalent to the minimum pressure required to obtain dispersed phase

permeation that is the capillary pressure, Pcap:
4 γ owcosθ
Pcap
dp

τ − profile Pd
Pc,in v Pc,out
R
Pd
L
FIGURE 8.15 Schematic profile of the tube membrane with the indication of pressures,
geometrical parameters, and the shear profile.
The critical pressure depends on the O/W interfacial tension (γow), the contact
angle (θ) of the dispersed phase against the membrane surface wetted with the con-
tinuous phase, and the average membrane pore diameter (dp). The shear stress (τ)
near the lumen side membrane surface is calculated from
λ ⋅ ρ ⋅ v2
τ = k⋅ [ Pa ]
2
where λ is the friction factor (in laminar case, λ = 16/Re), ρ is the density of the
continuous phase (kg/m3), and v is the axial cross-flow velocity (m/s). Constant k
is a geometry-dependent correction coefficient for the system with noncylindrical
inserts (Koris et al., 2011). This process parameter is important in case of processing
shear-sensitive materials.
Process parameters can be estimated on an empirical way as well in order to
ensure accurate apparatus design. For example, the following equation was devel-
oped to estimate the performance of an SPG membrane producing soybean oil-in-
water emulsion based on experimental data (R2 = 0.9):
 L 
J d  2  = 2.2 ⋅ DF + 180 ⋅ τ − 31
 m ⋅h

where Jd is the probable dispersed phase flux, DF is the applied driving force, and τ
is the shear stress above the membrane surface where oil droplets are formed.
Next to productivity, the average droplet size of the emulsion is an important
qualitative indicator. Here, the size is expressed in Sauter diameter (D[3,2]), and it is
defined as the diameter of a sphere that has the same volume/surface area ratio as a
particle of interest, whose value refers to a reliable size measurement method. The
following formula can help in the prediction of droplet size as a function of driving
force (R2 = 0.85):
D[3, 2](µm ) = 1.45 ⋅ DF − 0.6 ⋅ DF 2 + 10.8

The introduced equations were developed for 3.1 micron pore-sized membrane
and for room temperature. The applicability spectrum is from 1.1 to 14.4 driving
forces and from 0.05 to 0.6 Pa shear stresses.
8.2.1.5 Ideas for O/W and W/O Emulsion Production

by Membrane Technique
Astaxanthin is a naturally occurring fat-soluble dye, which has a very strong antioxi-
dant effect. Astaxanthin can be found in some algae, yeast, salmon, trout, shrimp,
lobster, and in some bird feathers (e.g., flamingo). Other carotenoids are converted
in the body to vitamin A, which is dangerous since vitamin A is toxic in excessive
quantities while astaxanthin is not and it can be consumed in unlimited quantities.
The astaxanthin bioavailability depends on the physical appearance; crystalline
form is the worst. When astaxanthin is dissolved in an O/W emulsion’s dispersed
oil phase, the bioavailability is much better. A way to further improve its absorp-
tion is to produce O/W emulsions supersaturated with astaxanthin. This carotenoid-
enriched water-dispersed O/W emulsion can be used in many foodstuffs, such as
orange juice and various dairy products. By the addition of antioxidants, such as
tocopherol, an O/W emulsion can be prepared in which 3-week storage period does
not occur in the degradation of carotenoids. However, it remains important that the
carotenoid-enriched emulsions cannot stand light and oxygen because it results in a
strong decay of carotenoids. Ribeiro and his colleagues applied a membrane method
in the production of the premixed emulsion, which was repeated several times in
order to develop the appropriate product. Preemulsion was madefrom palm oil with
dissolved astaxanthin and the mixture was dispersed in water. The oil droplets were
stabilized by a combination of two emulsifiers. The preemulsions were transferred to
the membrane between 5 and 15 bar pressure; the emulsion was concentrated from
10 to 40 mass% (Ribeiro et al., 2005).
Recently, the calorie reduction in butter and margarine has become a strategic
issue in the food industry because of the growing market demand for healthy foods.
In 1996, Katoh and colleagues started to work out a membrane technology for the
production of low-fat (25 mass%) spread. It has been shown that if the applied hydro-
philic membrane was pretreated with immersion in the oil phase, the dispersed phase
flux increased with two orders of magnitude. Furthermore, the researchers assumed
that ME is an appropriate method to produce W/O emulsions on an industrial scale
(Katoh et al., 1996).
Low-fat spread preparation method studied by Katoh and colleagues may be of
great interest for today’s health-conscious society. As health-conscious consumers
look toward healthy, enjoyable delicacies, the demand for low-fat products increases.
This product has light, creamy texture because the fine dispersed oil droplets can
ensure a similar taste compared to traditional products with higher fat content.
Because both the oil and water phases are found in the product, it can be easily
enriched with water- and oil-soluble vitamins as well. Thanks to the low fat and
reduced calorie content, obesity and heart and vascular disease risks may diminish.
The hydrolysis of water-insoluble esters needs to be carried out in multiphase
organic/aqueous systems, in which, in general, a phase transfer catalyst is able to
work at the interface. Biocatalysts such as lipases can be activated by interfacial
Pump
Membrane module
Pump
Dispersed phase
Continuous phase
FIGURE 8.16 Representation of the experimental apparatus used to distribute lipase

at the interface of the oil–water emulsion. (From Giorno L. et al.: J. Membr. Sci., 5 June
2008;317(1–2):19–25.)
phenomena and in addition selectively distinguish between enantiomers, thus being

able to carry out kinetic resolution of racemic esters. The preparation of stable and
uniform multiphase reaction systems and the uniform distribution of biocatalysts at
the O/W interface in mild operating conditions are among the main technological
problems in developing these reactors. In the work of Giorno et al. (2008), ME tech-
nique was used to distribute lipase from Candida rugosa at the interface of stable
oil-in-water emulsions (Figure 8.16). The enzyme itself was used as a surfactant.
SPG membranes having a nominal pore diameter of 0.1 μm were used to prepare
emulsions. Stable emulsions with more than 90% of droplets of 1.6 (±0.40) μm were
obtained.
Lipase showed 100% enantioselectivity converting 90% of (S)-isomer in less
than 24 h with a catalytic activity of 6.55 × 10−3 (±5.33 × 10−4) mmol/h gram raw
powder. This performance was achieved thanks to the enzyme’s optimal distribu-
tion at the interface of stable, uniform, and small droplets obtained by applying
a shear stress much lower than the traditional emulsification processes. The suit-
ability of ME to optimize the distribution of the lipase at the oil–water interface of
heterogeneous bioorganic reaction systems has been demonstrated. The mild opera-
tive conditions in terms of shear stress of this technique allowed emulsions to be
obtained with droplets stabilized by the lipase itself without the need for additional
emulsifier. Thanks to the low shear stress and enzyme optimal spatial arrangement
at the stable and constant oil–water interface, lipase showed very high enantiose-
lectivity (100%) at high conversion degree (up to 90% of the (S)-naproxen ester)
(Giorno et al., 2008).
8.2.2 Possibilities in Food Nanotechnology

Nanotechnology is a relatively recent trend in scientific research and industrial appli-
cations aspects, although its development emerged in the 1980s. Nanotechnology
deals with the characterization, fabrication, and manipulation of biological and non-
biological structures smaller than 100 nm. Structures on this scale have been shown
to have unique and novel functional properties. Consequently, interest and activities in
this research area have greatly increased over the past few years (Weiss et al., 2006).
According to the National Nanotechnology Initiative (2006), “Nanotechnology is
the understanding and control of matter at dimensions of roughly 1 to 100 nanome-
ters, where unique phenomena enable novel applications. Encompassing nanoscale
science, engineering and technology, nanotechnology involves imaging, measuring,
modeling, and manipulating matter at this length scale.”
Nanotechnology has the potential to impact many fields of the food sector. Food
security, disease treatment delivery methods, new tools for molecular and cellular
biology, new materials for pathogen detection, and protection of the environment are
examples of the important links of nanotechnology to the science and engineering of
food systems. Examples of nanotechnology as a tool for achieving further advance-
ments in the food industry are as follows (Weiss et al., 2006):
• Increased security of manufacturing, processing, and shipping of food

products through sensors for pathogen and contaminant detection
• Devices to maintain historical environmental records of a particular prod-
uct and tracking of individual shipments
• Systems that provide integration of sensing, localization, reporting, and
remote control of food products (smart/intelligent systems) and that can
increase efficacy and security of food processing and transportation
• Encapsulation and delivery systems that carry, protect, and deliver func-
tional food ingredients to their specific site of action
Many nanotechnological research focus on the development of applications in

biosciences and engineering. Strategies to apply nanoscience to the food industry
are quite different from these more traditional applications of nanotechnology. Food
processing is a multitechnological manufacturing industry involving a wide vari-
ety of raw materials, high biosafety requirements, and well-regulated technological
processes. Four major areas in food production may benefit from nanotechnology:
development of new functional materials, microscale and nanoscale processing,
product development, and methods and instrumentation design for improved food
safety and biosecurity (Weiss et al., 2006).
The influence of the material properties of foods at the nanoscale level on their
bioavailability and nutritional value has been highlighted (Blundell and Thurlby,
1987; Aguilera, 2005). In addition, the relationship between the morphology of
food materials and their bulk physicochemical properties has been investigated
(Losche, 1997), for example, biopolymers in solutions, gels, and films (Chinnan
and Park, 1995; Janaswamy and Chandrasekaran, 2005). Functional nanostructures
can incorporate individual biological molecules, which is useful in the development
of biosensors that can use natural sugars or proteins as target-recognition groups

(Charych et al., 1996).
In summary, there are a large number of potential applications of nanotechnology
within the food industry; however, many of these may be difficult to adopt com-
mercially because the commercial emulsification methods are either too expensive
or too impractical to implement on an industrial scale. Membrane techniques are
widely known as energy-efficient and cost-effective methods, so the operation costs
can be cut with their application. The subsequent sections focus on a limited num-
ber of nanotechnology applications that may have commercial potential in the near
future. Most likely, the limited application of nanotechnology to the food industry
will change as nanofabrication technologies become more cost-effective. Weiss et al.
(2006) in their work classify three groups of food nanoemulsion; simple nanoemul-
sions, nanostructure multiple emulsions, and nanostructured multilayer emulsions.
8.2.2.1 Simple Nanoemulsions

In modern literature, such emulsions are often referred to as “nanoemulsions.”
Nanoemulsions have been produced and studied for many years, so a large body
of literature dealing with their preparation, characterization, and utilization exists
(McClements, 2004). Functional food components can be incorporated within the
droplets, the interfacial region, or the continuous phase. Encapsulating functional
components within the droplets often enables a slowdown of chemical degradation
processes by engineering the properties of the interfacial layer surrounding them
(McClements and Decker, 2000). While it is difficult to engineer the interfaces to be
completely impermeable to compounds in the bulk phase that may interact with the
encapsulated compounds, the rate of permeation can often be significantly reduced,
thus increasing the kinetic stability of the bioactives.
8.2.2.2 Nanostructured Multiple Emulsions

The use of multiple emulsions can create delivery systems with novel encapsulation
and delivery properties. The most common examples of this are oil-in-water-in-oil
(O/W/O) and water-in-oil-in-water (W/O/W) emulsions (Garti and Benichou, 2001,
2004). For example, a nanostructured W1OW2 emulsion would consist of nanometer-
sized water droplets or reverse micelles (W1) contained within larger oil droplets
(O) that are dispersed within an aqueous continuous phase (W2). Functional food
components could be encapsulated within the inner water phase, the oil phase, or the
outer water phase, thereby making it possible to develop a single delivery system that
contains multiple functional components. This technology could be used to separate
two aqueous phase components that might adversely react with each other if they
were present in the same aqueous phase. Alternatively, it could be used to protect and
release an aqueous phase component trapped within the inner water droplets (W1) to
a specific site such as the mouth, stomach, or small intestine.
8.2.2.3 Nanostructured Multilayer Emulsions

Recent studies have shown that the use of multilayer emulsions can create novel deliv-
ery systems. These systems typically consist of oil droplets (the core) surrounded by
nanometer-thick layers (the shell) comprising different polyelectrolytes. These layers
are formed using a layer-by-layer (LbL) electrostatic deposition method that involves
sequential adsorption of polyelectrolytes onto the surfaces of oppositely charged col-
loidal particles. An ionic emulsifier that rapidly adsorbs to the surface of lipid droplets
during homogenization is used to produce a primary emulsion containing small drop-
lets; then an oppositely charged polyelectrolyte is added to the system, which adsorbs
to the droplet surfaces and produces a secondary emulsion containing droplets coated
with a two-layer interface. This procedure can be repeated to form oil droplets coated
by interfaces containing three or more layers. Under certain circumstances, emul-
sions containing oil droplets surrounded by multilayer interfaces have been found
to have better stability against environmental stresses than conventional oil-in-water
emulsions with single-layer interfaces (Gu et al., 2005; Mun et al., 2005; Guzey and
McClements, 2006). In addition, it is possible to develop smart delivery systems by
engineering the properties of the nanostructured shell around the droplets.
A functional component trapped within the core of a multilayer emulsion delivery
system could be released in response to a specific environmental trigger by designing
the response of the shell to the environment as in the following examples:
1.
Complete shell dissociation: Weakening electrostatic interactions can cause
shells to completely dissociate under specific solution conditions (pH, ionic
strength). For instance, changing the pH can cause one or more of the poly-
electrolytes to lose its charge, or increasing the ionic strength can weaken
the electrostatic attraction of a polyelectrolyte to the next layer, thereby pro-
moting desorption.
2.
Modulation of shell porosity: The thickness and porosity of shells can
change with exposure to pH and ionic strength. This determines the rate at
which functional components trapped inside the core will diffuse into the
surrounding medium. By selecting the appropriate polyelectrolytes to use
and the assembly conditions, one could design systems to release, under
specific environmental triggers, functional components smaller than some
particular dimension.
In principle, one could vary the release of 1 or more encapsulated materials using
either of these release mechanisms, either individually or in combination (simultane-
ously or sequentially).
8.2.3 Microencapsulation
Microencapsulation is a procedure for the closure of solid, liquid, and gaseous
materials. The microcapsules are regular shapes of a diameter of 0.5–2000 μm,
which are made of one or more polymers, permeable coating systems (Figure 8.17)
(Mathiowitz, 1999). The ME operations can be used to shape such microcapsules.
The beneficial properties of microencapsulation include the following: increased
shelf life can simply be prolonged; loss, bad taste of agents, and odor can be masked
from incompatible substances and/or materials separation; and relatively few aids
are necessary for their manufacture.
The advantageous features of microencapsulation include enhanced durability,
simply prolonged release of active compounds, masking of unpleasant taste and odor
Wall Matrix
Core
Reservoirs
FIGURE 8.17 Typical forms of an ideal capsule.
materials, separation of incompatible substances and excipients, and relatively low

auxiliary material requirement for the production (Rácz and Selmeczi, 2001). The
scheme of possible application of ME in the encapsulation process of shear-sensitive
biomaterials is introduced in Figure 8.18.
Microencapsulation is widely used in the food, cosmetic, agricultural, and phar-
maceutical industries as well. Flavoring agents were processed as capsules already in
the 1930s; vitamin encapsulation started in the 1940s, whose main aim is to protect
and reinforce the stability of the compounds. Microencapsulation could be applied
to produce vitamin-containing food enriched with various trace elements as well
(Wilson and Shah, 2007). The closed functional ingredients can include, for example,
processing aids (leavening agents and enzymes), preservatives (acids and salts), vita-
mins, minerals, flavorings (natural and synthetic), and spices. Microencapsulation
prevents (or minimizes) the evaporation of the flavorings during preparation, trans-
port, storage, and cooking.
To produce capsules in the food industry, some kind of biopolymer is used in
the microencapsulation procedure, which can be made from sugar, starch, rubber,
proteins, plastics, dextrin, or alginate (Figure 8.19). The use of liposomes as biopoly-
mer recently started to gain ground (Taylor et al., 2005). Liposomes are spherical
particles composed of phospholipids, which contain both hydrophilic and lipophilic
Dispersed phase
+ active
Cooling,
compound
filtration, and
drying
Fine,
homogeneous
Membrane
emulsion Micro or
emulsifier
nanocapsules
Continuous Evaporation
phase of continuous
phase
FIGURE 8.18 Membrane emulsification to assist the encapsulation process.

40 μm
FIGURE 8.19 Hollow microspheres (microcapsules). (From http://www.life.kyutech.ac.jp.)
elements. Because of the effectiveness in the use of liposome in pharmaceutical and

medical applications, food scientists have begun to use liposomes as carriers for
specific functional components. Functional components such as proteins, enzymes,
vitamins, and flavoring substances are being used in many food processes (Figure
8.20). With microencapsulation, food ingredients are stabilized against degradation
but the defense against pathogens can also be made more efficient.
10 μm
FIGURE 8.20 Protection of probiotic bacteria in gelatin-maltodextrin microcapsules.

(Image courtesy of Antonela Borza, Food Science Program, Department of Process
Engineering and Applied Science, Dalhousie University.)
REFERENCES
Agarwal, A. K.: Biofuels (alcohols and biodiesel) applications as fuels for internal combus-
tion engines. Prog. Energy Combust. Sci., 2007;33:233–71.
Aguilera, J. M.: Why food microstructure? J. Food Eng., 2005;67(1–2):3–11.
Akmal, N., Karin, S., Remko, B.: Premix emulsification: A review. Wageningen University,
Food Process Engineering Group, Bomenweg 2, 6703 HD Wageningen, 2010.
Alicieo, T. V. R., Mendes, E. S., Pereira, N. C., Lima, O. C. M.: Membrane ultrafiltration of
crude soybean oil. Desalination, 2002;148:99–102.
Blundell, J. E., Thurlby, P. L.: Experimental manipulations of eating-advances in animal
models for studying anorectic agents. Pharmacol. Ther., 1987;34(3):349–401.
Cao, P., Dube, M. A., Tremblay, A. Y.: Methanol recycling in the production of biodiesel in a
membrane reactor. Fuel, 2008;87:825–33.
Chakraborty, S., Drioli, E., Giorno, L.: Development of a two separate phase submerged bio-
catalytic membrane reactor for the production of fatty acids and glycerol from residual
vegetable oil streams. Biomass Bioenergy, In press, 2012;46:574–83.
Charcosset, C.: Preparation of emulsions and particles by membrane emulsification for the
food processing industry. J. Food Eng., 2009;92(3):241–9.
Charych, D., Cheng, Q., Reichert, A., Kuziemko, G., Stroh, N., Nagy, J., Spevak, W., Stevens,
R. A.: “Litmus test” for molecular recognition using artificial membranes. Chem. Biol.,
1996;3:113.
Chinnan, M. S., Park, H. J.: Effect of plasticizer level and temperature on water vapor trans-
mission of cellulose-based edible films. J. Food Process. Eng., 1995;18(4):417–29.
De, B. K., Das, R., Dutta, B. K., Bhattacharyya, D. K.: Membrane degumming and dewaxing
of rice bran oil and its refining. Fett/Lipid, 1998;100(9):s416–21.
de Souza, M. P., Cunha Petrus, J. C., Guaraldo Goncalves, L. A., Viotto L. A.: Degumming of
corn oil/hexane miscella using a ceramic membrane. J. Food Eng., 2008;86(4):557–64.
Demirbas A.: Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical
alcohol transesterifications and other methods: A survey. Energy Convers. Manage.,
2003;44:2093–109.
Dragosavac, M. M., Sovilj, M. N., Kosvintsev, S. R., Holdich, R. G., Vladisavljević, G. T.:
Controlled production of oil-in-water emulsions containing unrefined pumpkin seed
oil using stirred cell membrane emulsification. J. Membr. Sci., 2008;322(1):178–88.
Dubé, M. A., Tremblay, A. Y., Liu, J.: Biodiesel production using a membrane reactor. Biores.
Tech., 2007;93:639–47.
Ebert, K., Cuperus, F. P.: Solvent resistant ultrafiltration membranes in edible oil processing.
Membr. Technol., 1999;107:5–8.
Egidi, E., Gasparini, G., Holdich, R. G., Vladisavljević, G. T., Kosvintsev S. R.: Membrane
emulsification using membranes of regular pore spacing: Droplet size and uniformity
in the presence of surface shear. J. Membr. Sci., 2008;323(2):414–20.
García, A., Álvarez, S., Riera, F., Álvarez, R., Coca, J.: Sunflower oil miscella degumming
with polyethersulfone membranes: Effect of process conditions and MWCO on fluxes
and rejections. J. Food Eng., 2006;74(4):516–22.
Garti, N., Benichou, A.: Double emulsions for controlled-release applications: Progress and
trends. In: Sjoblom J, editor. Encyclopedic Handbook of Emulsion Technology. New
York: Marcel Dekker, 2001;377–407.
Garti, N., Benichou, A.: Recent developments in double emulsions for food applications.
In: Friberg, S., Larsson, K., Sjoblom, J., editors. Food Emulsions, 4th ed. New York:
Marcel Dekker. 2004;353–412.
Gijsbertsen-Abrahamse, A. J.: Membrane emulsification: Process principles. Thesis,
Wageningen University, The Netherlands, with Dutch summary, 2003. ISBN
90-5808-845-6.
Giorno, L., Mazzei, R., Oriolo, M., De Luca, G., Davoli, M., Drioli, E.: Effects of organic sol-
vents on ultrafiltration polyamide membranes for the preparation of oil-in-water emul-
sions. J. Colloid Interface Sci., 2005;287:612–23.
Giorno, L., Piacentini, E., Mazzei, R., Drioli, E.: Membrane emulsification as a novel method
to distribute phase-transfer biocatalysts at the oil/water interface in bioorganic reac-
tions. J. Membr. Sci., 2008;317(1–2):19–25.
Gu, Y. S., Decker, A. E., McClements, D. J.: Production and characterization of oil-in-water
emulsions containing droplets stabilized by multilayer membranes consisting of beta-
lactoglobulin, iota-carrageenan and gelatin. Langmuir, 2005;21:5752–60.
Gupta, A. K. S.: Process for refining crude glyceride oils by membrane filtration, U.S. Patent
4062882, 1977.
Guzey, D., McClements, D. J.: Formation, stability and properties of multilayer emul-
sions for application in the food industry. Adv. Colloid Interface Sci., 2006;128–130:
227–48.
Hafidi, A., Pioch, D., Ajana, H.: Membrane-based simultaneous degumming and deacidifica-
tion of vegetable oils. Innov. Food Sci. Emerg. Technol., 2005;6:203–12.
He, H. Y., Guo, X., Zhu, S. L.: Comparison of membrane extraction with traditional extrac-
tion methods for biodiesel production. JAOCS, 2006;83:457–60.
Iwama, A.: New process for purifying soybean oil by membrane separation and an economi-
cal evaluation of the process. J. Am. Oil Chem. Soc., 1989;64:1258.
Janaswamy, S., Chandrasekaran, R.: Cation-induced polymorphism in iotacarrageenan.
Carbohydr. Polym., 2005;60(4):499–505.
Joscelyne, S. M., Trägårdh, G.: Membrane emulsification—A literature review. Food
Engineering, Lund University, Box 124, 22100, 1999.
Kandori, K., Kishi, K., Ishikawa, T.: Preparation of uniform silica hydrogel particles by SPG
filter emulsification method. Colloids Surface, 1992;62:259–62.
Karaosmanoglu, F., Cıgızoglu, K. B., Melek, T., Ertekin, S.: Investigation of the refining step
of biodiesel production. Energy Fuels, 1996;10:890–5.
Katoh, R., Asano, Y., Furuya, A., Sotoyama, K., Tomita, M.: Preparation of food emulsions
using a membrane emulsification system. J. Membr. Sci., 1996;113:131–5.
Kelder, J. D. H., Janssen, J. J. M., Boom, R. M.: Membrane emulsification with vibrating
membranes: A numerical study. J. Membr. Sci., 2007;304(1–2):50–9.
Kim, I. C., Kim, J. H., Lee, K. H., Tak, T. M.: Phospholipids separation (degumming)
from crude vegetable oil by polyimide ultrafiltration membrane. J. Membr. Sci.,
2002;5284:1–11.
Koris, A., Marki, E.: Ceramic ultrafiltration membranes for non-solvent vegetable oil degum-
ming (phospholipid removal). Desalination, 2006;200(1–3):537–9. (ISSN 0011-9164).
Koris, A., Piacentini, E., Vatai, G., Bekassy-Molnar, E., Drioli, E., Giorno, L.: Investigation
on the effects of a mechanical shear-stress modification method during cross-flow
membrane emulsification. J. Membr. Sci., 2011;371(1–2):28–36.
Koris, A., Vatai, Gy.: Dry degumming of vegetable oils by membrane filtration. Desalination,
2002;148(1–3):149–53 (ISSN 0011-9164).
Köseoglu, S. S.: Current status membrane technology in the edible oil industry. In Proceedings
of World Conference and Exhibition on Oilseed and Edible Oils Processing, Istanbul,
Turkey, October 8–10, 1996.
Lin, L., Ree, K. C., Köseoglu, S. S.: Bench-scale membrane degumming of crude vegetable
oil: Process optimization. JOMSC, 1997;134:101–8.
Liu, K.-T., Gao, S., Chung, T.-W., Huang, C.-m., Lin, Y.-S.: Effect of process conditions on
the removal of phospholipids from Jatropha curcas oil during the degumming process.
Chem. Eng. Res. Design, 2012;90(9):1381–6.
Losche, M.: Protein monolayers at interfaces. Curr. Opin. Solid State Mater. Sci.,
1997;2(5):546–56.
Marenchino, R., Pagliero, C., Mattea, M.: Vegetable oil degumming using inorganic mem-
branes. Desalination, 2006;200(1–3):562–4.
Mathiowitz, E., Kretz, M. R., Brannon-Peppas, L.: Microencapsulation. In Encyclopedia of
Controlled Drug Delivery. New York: John Wiley and Sons Inc., 1999;2:493–546.
McClements, D. J.: Food Emulsions: Principles, Practice and Techniques, 2nd edn. Boca
Raton, FL: CRC Press, 2004.
McClements, D. J., Decker, E. A.: Lipid oxidation in oil-in-water emulsions: Impact of molec-
ular environment on chemical reactions in heterogeneous food systems. J. Food Sci.,
2000;65(8):1270–82.
Mun, S., Decker, E. A., McClements, D. J.: Influence of droplet characteristics on the for-
mation of oil-in-water emulsions stabilized by surfactant-chitosan layers. Langmuir,
2005;21:6228–34.
Nakashima, T., Shimizu, M.: Porous glass from calcium alumino boro-silicate glass.
Ceramics, 1986;21:408.
Nakashima, T., Shimizu, M., Kukizaki, M.: Membrane Emulsification, Operation Manual,
Industrial Research Institute of Miyazaki Prefecture, Miyazaki, Japan, 1991.
Nakashima, T., Shimizu, M., Kukizaki, M.: Particle control of emulsion by membrane emul-
sification and its application. Adv. Drug Deliv. Rev., 2000;45:47–56.
National Nanotechnology Initiative. 2006. Available from: http://www.nano.gov/nanotech-
101/what/definition., Accessed August 1, 2012.
Othman, R., Mohammad, A. W., Ismail, M., Salimon, J.: Application of polymeric sol-
vent resistant nanofiltration membranes for biodiesel production. J. Membr. Sci.,
2010;348:287–97.
Pagliero, C., Mattea, M., Ochoa, N., Marchese, J.: Fouling of polymeric membranes during
degumming of crude sunflower and soybean oil. JOFE, 2007;78(1):194–7.
Purwasasmita, M., Juwono, P. B., Karlina, A. M., Khoiruddin, Wenten, I. G.: Non-dissolved solids
removal during palm kernel oil ultrafiltration. Reaktor, Oktober 2013;14(4):Hal. 284–90.
Rácz, I., Selmeczi, B.: A molekuláris és mikrokapszulázás művelete. In: Vincze, J. (szerk.),
Gyógyszer-technológia 2 Művelettan-eljárástan. Medicina Könyvkiadó Rt, Budapest,
2001;120–7.
Ribeiro, A. P. B., Bei, N., Guaraldo Goncalves, L. A., Cunha Petrus, J. C., Viotto, L. A.: The
optimisation of soybean oil degumming on a pilot plant scale using a ceramic mem-
brane. J. Food Eng., 2008;87(4):514–21.
Ribeiro, H. S., Rico, L. G., Badolato, G. G., Schubert, H.: Production of o/w emulsions
containing astaxanthin by repeated premix membrane emulsification. J. Food Sci.,
2005;70(2):117–23.
Rosillo-Calle, F., Pelkmans, L., Walter, A.: A global overview of vegetable oils, with refer-
ence to biodiesel. A report for the IEA Bioenergy Task 40, June 2009 (http://www.
bioenergytrade.org/downloads/vegetableoilstudyfinaljune18.pdf.).
Saleh, J.: A membrane separation process for biodiesel purification. A thesis submitted to the
Faculty of Graduate and Postdoctoral Studies in partial fulfillment of the requirements
for the degree of Doctor of Philosophy in Environmental Engineering Ottawa Carleton
Institute of Environmental Engineering (OCIENE), 2011.
Saravanan, M., Bhosle, B. M., Subramanian, R.: Processing hexane-oil miscella using a non-
porous polymeric composite membrane. J. Food Eng., 2006;74(4):529–35.
Sdrula, N.: A study using classical or membrane separation in the biodiesel process.
Desalination, 2010;250(3):1070–2.
Snape, J. B., Nakajima, M.: Processing of agricultural fats and oils using membrane technol-
ogy. J. Food Eng., 1996;30:1–41.
Subramanian, R., Ichikawa, S., Nakajima, M., Kimura, T., Maekawa, T.: Characterization
of phospholipid reverse micelles in relation to membrane processing of vegetable oils.
European Journal of Lipid Science and Technology, 2001;103(7):93–7.
Subramanian, R., Nakajima, M.: Membrane degumming of crude soybean and rapeseed oils.
JAOCS, 1997;74(8):971–5.
Subramanian, R., Nakajima, M., Kawakatsu, T.: Processing of vegetable oils using polymeric
composite membranes. J. Food Eng., 1998;38:41–56.
Subramanian, R., Nakajima, M., Yasui, A., Nabetani, H., Kimura, T., Maekawa, T.: Evaluation
of surfactant-aided degumming of vegetable oils by membrane technology. JAOCS,
1999;76(10).
Taylor, T. M., Davidson, P. M., Bruce, B. D. et al.: Liposomal nanocapsules in food science
and agriculture. Crit. Rev. Food Sci. Nutr., 2005;45:587–605.
Tremblay, A. Y., Cao, P., Dubé, M. A.: Biodiesel production using ultralow catalyst concentra-
tions. Energy Fuels, 2008;22:2748–55.
Van Gerpen, J.: Biodiesel processing and production. Fuel. Process. Technol.,
2005;86:1097–107.
Vladisavljevic, G. T., Brösel, S., Schubert, H.: Preparation of water-in-oil emulsions using
microporous polypropylene hollow fibres: Conditions for producing small uniform
droplets. Chem. Papers, 2000;54(6a):383–8.
Vladisavljevic, G. T., Lambrich, U., Nakajima, M., Schubert, H.: Production of O/W emul-
sions using SPG membranes, ceramic α-aluminium oxide membranes, microfluid-
izer and a silicon microchannel plate—A comparative study. Colloids Surfaces A:
Physicochem. Eng. Aspects, 2004;232(2–3):199–207.
Vladisavljevic, G. T., Schubert, H.: Preparation and analysis of oil-in-water emulsions with
a narrow droplet size distribution using Shirasu-porous-glass (SPG) membranes.
Desalination, 2002;144(1–3):167–72.
Wang, Y., Xingguo, Y., Liu, Y., Ou, S., Yan, Y., Tang, S.: Refining of biodiesel by ceramic
membrane separation. Fuel. Process. Technol., 2009;90:422–7.
Weiss, J., Takhisto, P., McClements, D. J.: Functional materials in food nanotechnology. JFS
R: Concise Rev/Hypotheses Food Sci., 2006;71(9):R107–16.
Wilson, N, Shah, N. P.: Microencapsulation of vitamins. ASEAN Food J., 2007;14:1–14.
Wu, J. C., Lee, E.: Ultrafiltration of soybean/hexane extract by porous membrane. JOMSC,
1999;154:251–9.
Yasuno, M., Nakajima, M., Iwamoto, S., Maruyama, T., Sugiura, S., Kobayashi, I., Shono,
A., Satoh, K.: Visualization and characterization of SPG membrane emulsification.
J. Membr. Sci., 2002;210(1):29–37.
Zhang, S. Q., Kutowy, O., Kumar, A.: Application of ultrafiltration membranes in refining
of crude vegetable oils. In Proceedings of the 8th Annual Meeting of North American
Membrane Society, Ottawa, Canada, 1996; p. 95.
Zhu, J., Barrow, D.: Analysis of droplet size during crossflow membrane emulsification using
stationary and vibrating micromachined silicon nitride membranes. J. Membr. Sci.,
2005;261(1–2):136–44.
9 Food Applications of
Membrane Bioreactors
Lidietta Giorno, R. Mazzei,
Emma Piacentini, and Enrico Drioli
CONTENTS
9.1 Introduction................................................................................................... 299
9.2 General Aspects of Membrane Bioreactors................................................... 301
9.2.1 Membrane Bioreactors with Biocatalyst Compartmentalized
Upstream or Downstream the Membrane......................................... 305
9.2.2 Biocatalytic Membrane Reactors with Biocatalysts Immobilized
at the Membrane Level......................................................................309
9.2.2.1 Immobilization Techniques................................................ 311
9.3 Membrane Bioreactors Applications in Food................................................ 312
9.3.1 Membrane Bioreactors in Milk and Whey Processing...................... 312
9.3.1.1 Lactose Hydrolysis.............................................................. 314
9.3.1.2 Lactic Acid Production....................................................... 315
9.3.1.3 Protein Hydrolysis............................................................... 317
9.3.1.4 Hydrolysis of Milk Fat........................................................ 320
9.3.2 Membrane Bioreactors in Fruit Juices Processing............................ 321
9.3.3 Membrane Bioreactors Using Plant as Material Source for
Biotransformation.............................................................................. 326
9.3.4 Plant Raw Material Used as Source.................................................. 329
9.3.4.1 Starch Hydrolysis................................................................ 329
9.3.4.2 Oil Processing..................................................................... 331
9.3.5 Membrane Bioreactors in Alcoholic Beverages Processing.............. 335
9.3.6 Membrane Bioreactors for Wastes Coming from Food
Processing Industry........................................................................... 343
9.3.6.1 Valorization of Waste by Membrane Bioreactor.................344
9.3.7 Membrane Bioreactors in Integrated Membrane Operations............348
9.4 Conclusions.................................................................................................... 350
References............................................................................................................... 350
9.1 INTRODUCTION
Membrane bioreactors (MBRs) are considered key technologies to implement
knowledge-based sustainable growth. On the basis of changes observed in the past
decades, analysts predict for the coming years a significant growth of the world
299
population combined with a tendency to live in megacities, with more than 8 million
people. For example, in the second half of the last century, the world population dou-
bled with less than 20% of it living in megacities. By 2050, it is expected that about
90% of the more than 10 billion people will live in megacities. Changes in lifestyle
and consumption will have important implications for production, processing, retail
sectors, and environment. Where and how goods are produced, processed, packaged,
preserved, distributed, prepared, and disposed of will affect areas such as energy
consumption and waste generation. Analysis of waste generation from various pro-
duction sectors surprisingly evidences that the production of high-quality goods,
such as drugs and food, produces more kilograms of wastes per kilogram of product
compared to fine chemistry and oil refinery. This clearly indicates that advanced
technologies will have to be increasingly introduced and they will play a major role
in promoting a passage from resource-intensive to knowledge-intensive production
approach in these industrial sectors. The holistic approach and life cycle assessment
indicate that not only are precise production systems needed in order to prevent
wastes, but a radical change in the production lines and strategies is also needed in
order to make wastes valuable and marketable products. In fact, it is quite clear that
optimization of existing solution to treat wastes and limit demand of source materi-
als will only promote incremental progresses. To achieve breakthrough progresses,
ground-breaking solutions are needed in which the rational production of appropri-
ate “wastes” that can become valuable coproducts is crucial. This is the scenario that
shifts the attention toward bio-derived chemical and energy feedstock. Although the
controversy of whether bio-derived feedstock is more convenient than oil-derived
feedstock from an environmental point of view still remains, there is no doubt that
the limited resources impose the use of renewable bio-derived resources and their
precise processing is crucial in making them sustainable.
Selective and precise processes are needed to implement this strategy. Biocatalysts,
such as enzymes, are much more precise than chemical catalysts traditionally used in
industrial production. They have specific interactions with reagents (or substrates) and
can show high reaction rate in mild reaction conditions with high reaction specificity
and stereospecificity. Enzymes can even distinguish between enantiomers; in fact, in
nature, molecular recognition is based on chiral interactions. Selective molecular and
ion transport through membranes and precise transformation of molecules promote
the extraordinary efficiency of the “cell factory” in living organisms. Transferring
this approach to industrial production is the current challenge. The development of
bio-mimicking reaction systems such as MBRs is certainly among the most suitable
approach to promote breakthrough advances in sustainable industrial production.
Similar to biomembrane systems, which need to combine various components,
properties, functions, and processes to comply with the overall aim of providing
metabolites while removing catabolites to keep the cell alive (Figure 9.1), the bio-
mimicking membrane reactors are composed of biocatalysts that perform the selec-
tive bioconversion and artificial nanostructured membranes that regulate the selective
transport between compartments (Figure 9.2) on the basis of suitable mechanisms
and driving forces.
Biological membranes are very selective, self-regulating, self-repairing, and self-
cleaning; however, they do not have enough mechanical or chemical strength to be
Food Applications of Membrane Bioreactors 301
FIGURE 9.1 Biomembrane systems.
(a) a a
(b)
b C C b
d d
c c
b b
d d
c c
FIGURE 9.2 Biocatalysts that perform the selective bioconversion and artificial nanostruc-
tured membranes that regulate the selective transport between compartments. (a) Biocatalysts
have specific interactions with reagents (or substrates). (b) A perm selective barrier that regu-
lates transport between two phases.
applied for intensive production. On the other hand, while artificial membranes hold
enough strength, they are far from possessing the selectivity and self-healing and
cleaning properties of biomembranes.
New fabrication methods to prepare nanostructured biohybrid membranes with
well-controlled architecture and functions are needed to fully exploit the potentiali-
ties of this technology.
In this chapter, the current development of membrane bioreactors and their appli-
cation in food will be discussed.
9.2 GENERAL ASPECTS OF MEMBRANE BIOREACTORS

MBRs or biochemical membrane reactors are systems in which a chemical con-
version promoted by a catalyst of biological origin is implemented by a membrane
(a) Side-stream module Submerged or immersed module
Membrane
Membrane
Reaction tank Separated

Separated
products Reaction tank products
Biocatalyst Substrate Product
(b) Side-stream module Submerged or immersed module

Biocatalytic
membrane
Biocatalytic
membrane
Separated Separated
Reaction tank Reaction tank
products products
FIGURE 9.3 (a) Bioreactor combined with a membrane separation unit, where the mem-
brane works as a permselective barrier. (b) Bioreactor with a membrane acting as a catalytic
and separation unit (it supports the biocatalyst and works as a permselective barrier).
operation. The bioconversion can occur in a vessel that is combined with a mem-
brane module or it can take place at the membrane level itself (Figure 9.3).
Therefore, the membrane can either compartmentalize the biocatalyst in a circuit
of the membrane module (lumen or shell) or support the biocatalyst in its micro- or
nanostructured matrix. The latter type of systems, that is, where the membrane con-
tributes directly to the bioconversion, is also called biocatalytic membrane reactors
(BMRs) to indicate that the membrane itself has catalytic properties. The membrane
module can be placed externally to the reaction mixture (side-stream configuration)
or it can be immersed within the tank containing the reaction mixture (submerged
configuration). The latter configuration is common in wastewater treatment; how-
ever, it is being explored also for the production of valuable components. In particu-
lar, the submerged BMR can be of great interest in food processing and production.
Besides the membrane module configuration and place where the reaction takes
place, the crucial role of a membrane in a biochemical membrane reactor is to pro-
mote and control the mass transport of reaction components between the phases
adjacent to it. Therefore, it can remove reaction products from the reaction environ-
ment, so as to shift the bioconversion toward the product formation, on the basis of
Le Chatelier’s principle, thus improving reaction conversion; it can supply reagents
Membrane
Reagent tank Reaction tank
FIGURE 9.4 Membrane bioreactor where the membrane supplies reagents to the biocatalyst.
to the biocatalyst, so that overcoming inhibition phenomena due to high substrate

concentration, from which biocatalysts usually suffer, or contaminants present in the
stream to process (Figure 9.4).
The rational supply of one or more reagents and/or the removal of products or
intermediates not only permit the fine control of reaction performance, but it can also
permit to obtain stable intermediate reaction products by sequestrating them from
subsequent conversion in multistep reactions. This is not possible in traditional batch
reactors where all reaction components are kept in the same reaction vessel.
In addition to promoting the selective transport through it, the membrane can
also control the contact between phases adjacent to its nanostructured matrix while
implementing a bioconversion. The two phases can be kept separated (as, e.g., in a
membrane-based solvent extraction process) or they can be finely dispersed into each
other (as in a membrane emulsification [ME] process).
MBRs and BMRs can work in a single liquid phase (aqueous or organic), hetero-
geneous liquid phases (organic/water), as well as in multiphase (liquid/gas) systems.
The types of biocatalysts used in MBRs, the properties of the reaction compo-
nents, and the application strongly influence the overall MBR structure and configu-
ration. Table 9.1 summarizes the most common cases.
Strictly speaking, here, compartmentalization and immobilization are not used
synonymously. In fact, while the term “immobilization” of a biocatalyst on/in a
membrane does include a compartmentalization of the biocatalyst in a microenvi-
ronment, compartmentalization of a biocatalyst in a circuit of the membrane does
not imply that the biocatalyst is immobilized. In the latter case, unless it is immobi-
lized on a carrier, the biocatalyst can be free in suspension flushing along one circuit
of the membrane.
When the biocatalyst is an enzyme, the reactor system is also called enzyme
membrane reactor, to indicate that the membrane works just as a permselective bar-
rier, or enzymatic membrane reactor, to indicate that the membrane also embeds the
enzyme and implements the enzyme-catalyzed reaction in addition to promoting the
selective mass transfer through its matrix.
The most common MBRs on the basis of biocatalyst compartmentalization/
immobilization and membrane separation processes will be discussed in the follow-
ing sections.
TABLE 9.1
Most Common Biocatalysts and Role of the Membrane in the Membrane
Bioreactor
Common Properties of Reaction
Biocatalyst Status Membrane Role Components
Enzymes Compartmentalized Enzyme recycle, Enzymes need cofactors,
product separation, substrates are large
and/or reagent polymers, reaction
supply mixture is very viscous
Immobilized on Support for the The size of the substrate
membrane surface catalyst is too big to enter the
membrane matrix,
products can pass
through the membrane
Immobilized within Support for the The size of the substrate
the membrane catalyst, reagent and product is suitable
matrix supply, product to be transported
separation through the membrane
Bacterial cells Compartmentalized Cell recycle, Cells operate the
products and/or transformation of
purified interest during the
components growing phase of the
separation and/or fermentation
reagent supply
Immobilized Support for the Cells can operate the
catalyst, reagent transformation of
supply, product interest during a phase
separation different from the
growing one
Fungi Compartmentalized Biocatalyst recycle, Biocatalyst grows in the
and/or attached on components bulk phase and/or it
the membrane separation needs to attach on a
surface surface to form a
biofilm
Yeast
Virus Biocatalyst growth
Algae/microalgae
Mammalian cells Compartmentalized Cell recycle, Cells, such as blood,
metabolites supply, etc., need to be
catabolites removal maintained alive in
bulk phase
Attached Support for cell Cells anchorage
growth, dependent, such as
metabolites supply, hepatocytes, etc., need
catabolites removal to adhere to the surface
for the differentiation
and biotransformation
9.2.1 Membrane Bioreactors with Biocatalyst Compartmentalized

Upstream or Downstream the Membrane
In these types of reactor systems, the membrane works as a permselective barrier
combined to the bioreactor. This configuration is suitable for reactions carried out
by biocatalyst that are not deactivated by shearing stress and/or that need interaction
with other components, such as coenzymes, cofactors, etc.; by cells in the grow-
ing phase of a fermentation process, by cells or aggregates that are too big to be
entrapped within a membrane. A reaction in which the substrate has a larger size
compared to the microporous membrane matrix, the product size is increased after
formation (i.e., by crystallization), or the reaction mixture is very complex and vis-
cous, is also best performed in MBRs where the membrane works as a separation
unit. In general, all those cases in which the mass transport of reagents or products
through the membrane matrix to the immobilized enzyme would limit the reactor
efficiency have to be performed with this configuration.
The most common mechanisms by which the membrane retains the biocatalyst
within the bulk reaction phase are molecular exclusion and electrostatic repulsion
(Figure 9.5).
Figure 9.6 depicts the schematic representation of a cell-recycle MBR in which
a continuous fermentation is carried out. The most common membrane operation
combined to it is a microfiltration or an ultrafiltration unit to retain and recycle back
the cells and large molecules while permeating water and small molecules (including
(a)
Substrate
Product
Enzyme
Complexed
Porous membrane enzyme
(b) Negatively
charged cofactor
-
- -
-
- - -
- -
- - -
- - -
- - Product
- - -
- -
- - -
- - -
- - - -
- -
-
-
Negatively charged membrane
FIGURE 9.5 Membrane separation mechanisms: (a) molecular sieving and (b) electrostatic
repulsion.
Bleed
Cell
recycle
pH Filter
MF/UF NF
Permeate
T
Feed
Fermentor
FIGURE 9.6 Continuous membrane fermentor apparatus with ultrafiltration cell-recycle

system.
product). Most often, the product is in a diluted form and in the presence of other
small components, so that further downstream processing to concentrate and purify
it is necessary. However, its very clear solution can be easily treated.
For example, nanofiltration can be applied to separate and concentrate the product
and recycle back to the fermentor water and other components.
The general behavior of the increased performance of a continuous fermentation
compared to a batch fermentation for a Lactobacillus producing lactic acid from
glucose is illustrated in Figure 9.7.
Another important reaction in which the selective membrane barrier is extremely
useful in implementing the reaction on a productive scale is the cofactor-dependent
9
8
7
6
O.D. (660 nm)
5
Continuous
4
3 Batch
2
1
0
0 2 5 8 10 14 18 20 22 23 30 35 40 42 45
Time (h)
FIGURE 9.7 Behavior of a continuous fermentation performance compared to a batch

fermentation.
TABLE 9.2
Some Reactions of Interest Catalyzed by NAD(P)H Dependent Enzymes
Enzyme Reaction Catalyzed
Glucose dehydrogenase from Gluconobacter β-d-Glucose + NAD(P)+ ⇄
suboxydans d-gluconolactose + NAD(P)H
Lactate dehydrogenase Lactic acid + NAD + ⇄ pyruvic acid + NADH
Malate dehydrogenase Malic acid + NAD+ ⇄ oxaloacetic acid + NADH
Leucine dehydrogenase Pyruvic acid + NH3+ + NADH + H+ ⇄
l-alanine + NAD+
Glyceraldehyde-3-phosphate dehydrogenase Glyceraldehyde-3-phosphate + HPO4= + NAD+
⇄ 1,3-bisphosphoglycerate + NADH + H+
Horse liver alcohol dehydrogenase 3-Methylpentane-1,5-diol + NAD+ ⇄
(−)-(3S)-3-methylvalerolactone + NADH
Alcohol dehydrogenase Limonoate A-ring lactone + NADH+ ⇄
17-dehydrolimonoate A-ring lactone + NADH
5-α-Reductase Androsterone + NADPH ⇄
dihydrotestosterone + NADP+
Methane monooxygenase from Methylococcus CH4 + O2 + NAD(P)H + H+ →
capsulatus and Methylosinus trichosporium CH3OH + H2O + NAD(P)+
enzyme-catalyzed reaction. In this case, a charged membrane is used to retain within

the reaction bulk-phase cofactors, such as NAD(P)/NAD(P)H. Table 9.2 summarizes
some of the reactions that need cofactors.
The major challenges in such types of reactions are the regeneration and the
retention of the cofactor in the reaction medium and the separation of the reaction
product. An example of a reaction using the NAD+ cofactor and the conjugated reac-
tion to regenerate the reduced NADH is illustrated in Figure 9.8.
The reaction illustrates the production of l-alanine from l-lactate. Figure 9.9 also
reports the NAD+/NADH structure, which illustrates the overall negative charge of
the molecule due to the presence of phosphorus groups. A negatively charged mem-
brane can be used to retain both oxidized (NAD+) and reduced (NADH) form of the
cofactor in the bulk solution. An alternative method to retain the NAD cofactor is to
enlarge its size by linking it to a soluble polymer, such as polyethylene glycol (PEG).
LDH
-Lactate Pyruvate
NAD+ NADH + H+
-Alanine NH+4
AlaDH
FIGURE 9.8 Conjugated reactions for regeneration of coenzyme during l-Alanine produc-
tion from l-Lactate.
0.12
0.1
Concentration (mol/L)
0.08
0.06
0.04 STR
MSTR
0.02
0
0 50 100 150 200 250
Time (min)
FIGURE 9.9 Reaction rate in traditional and charged membrane reactor. (Drioli, E.,
Giorno, L. 1999. Biocatalytic Membrane Reactors: Application in Biotechnology and the
Pharmaceutical Industry, Taylor & Francis Publisher, London, UK. Permission requested to
Taylor & Francis.)
However, experiments evidenced that in some cases, the reaction performance

with derivatized NAD is lower than with native NAD (Table 9.3).
On the other hand, the use of a charged membrane reactor permits to achieve the
same performance compared to a stirred-tank reactor (STR), which maintains the
cofactor in the reaction mixture. The advantage of the charged membrane reactor
is that it can promote the separation of the reaction product from the other reaction
component.
The cases discussed earlier examined the role of the membrane as a permselective
barrier to remove the reaction product. However, as earlier mentioned, the membrane
can also work as a permselective barrier to supply reagents to the biotransformation
TABLE 9.3
Enzymes Activity with Derivatized Cofactor
Enzyme Activity with Coenzyme References
l-Leucine dehydrogenase (LEUDH) Shows the same kinetic Wichmann et al. (1981)
and formate dehydrogenase (FDH) constants with native or
PEG-10000-NAD(H)
Glucose dehydrogenase (GlDH) Not active with PEG-NAD+ Kula and Kragle (2000)
Horse liver alcohol dehydrogenase Three to four times less active Vanhommerig et al. (1996)
(HLADH) with PEG-NAD+ compared to
native NAD+
Mandelic acid dehydrogenase (MADH) Active with PEG-NADH Vasič-Racki et al. (1989)
Alcohol dehydrogenase from Active with PEG-NAD(H) Röthig et al. (1990)
Thermoanaerobacter brokii (TBADH)
Membrane
Membrane
permeable to
permeable to
catabolites
nutrients
Fresh culture
medium with Exhaust culture
nutrients medium with
catabolites
Cell culture
medium
FIGURE 9.10 Cell culture assisted by two membranes functioning as nutrients supplier
(arteries) and catabolite removal (veins).
environment. This is the case, for example, of non-anchorage-dependent mamma-

lian cells growth assisted by an MBR. Here, cells are placed between two different
types of membranes (Figure 9.10).
One feeds nutrients while the other removes catabolites. This configuration can
keep physiological conditions for a long time, allowing cell growth and biotransfor-
mation functions for much longer time compared to batch systems.
Other examples of components supply through the membrane are constituted
by the need to avoid contact of waste streams with the biomass and/or the release
of biodegradation compounds into the purified stream. For example, micropol-
lutants contained in wastewater can be separated by a membrane, which supplies
them to a transformation tank where the biomass biodegrades them into non-
harmful components. This type of concept was used to transport organic micro-
pollutants through polymeric membranes (Livingston et al., 1998; Splendiani
et al., 2003) or ionic micropollutants through ion exchange membranes (Velizarov
et al., 2002).
9.2.2 Biocatalytic Membrane Reactors with Biocatalysts

Immobilized at the Membrane Level
The use of immobilized biocatalysts at the membrane level permits to greatly
intensify the production process as it can carry out the reagent supply, conversion,
and product separation in a single step by means of a high-throughput system. On
the other hand, this may also lead to a lower degree of freedom in running the
process. In the past years, the application of immobilized enzymes for production
and processing on a large scale accounted for few examples compared to what one
may have expected considering the numerous advantages the technology can offer.
Recently, the need for very precise processes to face sustainability through mass
intensive and low energy processes as well as waste prevention is promoting great
attention toward unparalleled selective properties of biocatalysts, such as enzymes.

It is nowadays well understood and clear that the major advantages of immobilized
enzymes include the increase of catalytic stability, their simple separation from
reaction components, and therefore their reuse. In addition to these advantages,
which are shared by enzymes immobilized on almost all kinds of support, enzyme
immobilization in membranes includes the mass transport control through the solid
support. In fact, fluid dynamics and hydrostatic conditions at the membrane inter-
face, the membrane matrix, morphology, and structure can greatly enhance the
mass transfer through the membrane by acting on the electrochemical potential
between the two faces of the membrane. Indeed, membranes can promote convec-
tive transport through its nanostructured matrix functionalized with enzyme, while
most of the other carrier supports work in diffusive conditions, which may limit
process efficiency.
One of the aspects to improve in developing BMRs is the development of specifi-
cally designed membranes, instead of using membranes currently available, which
have originally developed for other types of processes. Figure 9.11 illustrates some
of the membranes that have been used.
The most common BMRs with immobilized biocatalysts (mainly enzymes) as
well as the main methods for immobilization of enzymes on membranes will be
illustrated.
Polytetrafluoro Polypropylene membrane Polyvinylidenfluo

ethylene F F H CH3 ride membrane
F H
membrane C C C C C C
F F H H F H
Aliphatic polyamide membrane Polysulfone membrane Cellulose membrane

(nylon) CH3 H OH CH2OH
H O O C O SO2 OH H H H
H
O O
OH H H
HH O
N (CH2)5 C CH3 O
CH2OH H OH
FIGURE 9.11 Membranes commonly used in other applications and adapted in biocatalytic
membrane reactors.
9.2.2.1 Immobilization Techniques

9.2.2.1.1 Immobilization by Physical Methods (Entrapment/Gelification)
Biocatalysts can be entrapped within a membrane matrix during the membrane for-
mation process or after the membrane has been formed. In the first case, during the
preparation of the polymer solution, once the polymer is homogeneously solubilized
within the solvent, the biocatalyst is added, then the polymer + enzyme solution is
cast and the membrane formed according to various methods available (Strathmann
et al., 2011). The most common method used for biocatalyst entrapment during mem-
brane preparation is the phase inversion method. The major challenge of this method
is the biocatalyst stability to solvent used to dissolve the polymer and wash the pre-
pared membrane, as well as the leakage of enzyme during phase inversion when the
coagulation bath is constituted by water; in fact, given the fact that the enzyme is
soluble in water, it can be removed from the polymer matrix into the water during
the de-mixing phase.
The entrapment of biocatalyst within the already-formed membrane can be
obtained by simply filtering an enzyme solution through a porous membrane in condi-
tions favoring the irreversible fouling on/within the membrane caused by the protein
itself. In other words, the method takes advantage of the well-known fouling phe-
nomenon, the major drawback of membrane filtration operation. This method permits
to stably load enzymes to the membrane surface or within the membrane matrix,
depending on the relative enzyme and membrane pore size and physico-chemical
properties. When the enzyme is larger than the membrane pore size, it is accumulated
on the membrane surface forming a catalytically active protein cake layer. When
proteins reach a high concentration, they precipitate, forming a stable gel layer on the
membrane surface. The final result is then a composite catalytic biohybrid membrane.
In the case where the size of the enzyme is larger than the pore size on the mem-
brane surface in contact with the enzyme solution, but smaller than the pore size
on the other side of the membrane (i.e., an enzyme solution is pressed through an
asymmetric membrane from the side of the larger pore), the enzyme enters within
the polymer matrix and it remains entrapped within it. Depending on the physico-
chemical properties of the membrane, the method can also be influenced/enhanced
by physical adsorption (promoted by hydrophobic interactions such as van der Waals
interactions, London forces) and by ionic bond.
The entrapment in asymmetric membranes by cross-flow ultrafiltration is very
simple; it preserves the structural and functional integrity of the enzyme; it is a very
stable method, as enzyme leakage is not observed during operation; on the other hand,
it permits the removal of the enzyme from the membrane support when necessary
(e.g., when the enzyme has reduced its activity or the membrane needs to be cleaned
to remove fouling), by simply back flushing in conditions that can switch the chemi-
cal interactions between enzyme and polymer (temperature, pH, ionic strength, etc.).
Sometimes, cross-linking after entrapment is also carried out in order to make the
immobilization on the membrane surface more stable. In this case, the regeneration
of the support implies the loss of the biocatalyst. For example, the use of inorganic
membrane matrix allows the carbonization of the organic matter and the reuse of the
membrane.
9.2.2.1.2 Immobilization by Chemical Methods

9.2.2.1.2.1 Covalent Bond Enzymes can be immobilized by covalent bond
between the protein and the membrane or agents attached to the membrane. Only
the reactions promoting chemical bond in mild conditions, that is, those that do not
cause enzyme deactivation can be performed. A number of functional groups of pro-
teins that can be involved in covalent binding in conditions that do not damage the
catalytic properties of enzymes is listed in Table 9.4.
Most of reactions have been designed to couple with functional groups on the pro-
tein other than the amino and phenolic residues. A few reactions involved carboxylic
acid residues or thiol residues of a protein.
In some cases, it is possible to increase the number of reactive residues of an
enzyme in order to increase the yield of heterogenization and to provide alternative
reaction sites to those essential for enzymatic activity. The wide variety of bind-
ing reactions, and membrane supports with functional groups capable of covalent
coupling, or being activated to give such groups, makes this a generally applicable
method of immobilization, even if very little is known about the protein structure or
active site of the enzyme to be coupled. A common strategy to preserve the active
site during covalent binding is to carry out the reaction in the presence of a substrate
or inhibitor so that active site is combined with such molecules, preventing its func-
tional groups to be involved in the binding.
9.2.2.1.2.2 Ionic Bond and hydrophobic Interaction Membrane functional-

ization with biomolecules can also be carried out by ionic binding. This technique
consists of the interaction of a charged biomolecule with the support that has an
opposite charge. The stable attachment of the biocatalyst depends on the number of
interactions between the membrane and the biomolecule.
The simplest method to prepare a biohybrid membrane is to promote enzyme
attachment on membrane support by weak interactions, such as hydrophobic interac-
tions promoted mainly by van der Waals forces. By this method, the interaction bio-
catalyst/membrane occurs by nonspecific interaction between the biomolecule and
the surface of the membrane, as a consequence of surface energy. The main advan-
tage of this biomolecule immobilization technique is that no reagents are needed and
only a minimum of activation steps are required. As a consequence, the method is
less expensive and easy to carry out. In addition, the weak bonds involved mainly
obtained by van der Waals and hydrogen bond bear the greatest similarity to the in
vivo situation found in biological membrane; this is the reason why it is the most used
to understand the mechanisms of in vivo systems.
9.3 MEMBRANE BIOREACTORS APPLICATIONS IN FOOD

9.3.1 Membrane Bioreactors in Milk and Whey Processing
Whey is the by-product of cheese and casein manufacturing. It is composed of 50%–
65% of the initial milk solids, most of the initial lactose, 20% of the initial proteins,
and most of the initial vitamins and minerals. Proteins and lactose, if recovered, are
TABLE 9.4
List of Protein Functional Groups Involved in Covalent Bond with Support in
Mild Conditions
Protein Chemical Group Structure
Epsilon amino groups of lysine O
H2N OH
NH2
Epsilon amino groups of arginine NH O
H2N N OH
H
NH2
Beta and gamma carboxyl groups of aspartic and O
glutamic acids HO
OH
O NH2
Phenol ring of tyrosine O
OH
NH2
HO
Thiol group of cysteine

O OH O
HO OH OH
NH2 NH2
Hydroxyl groups of serine and threonine
O OH O
HO OH OH
NH2 NH2
Imidazole group of histidine O
H
N
OH
N NH2
Indole group of tryptophan O
OH
N NH2
H
components that can be used to produce functional foods and to avoid allergenic
reaction.
The hydrolysis of lactose present in milk or in cheese whey by MBRs systems is
a technique running on a large scale.
The need to hydrolyze the lactose and high-molecular-weight proteins present
in milk is due to the growing interest in the food field to intolerance and allergy,
and also to the possibility to use hydrolyzed compounds as nutraceuticals and food
ingredients. The other applications of MBRs include the hydrolysis of proteins into
peptides of low molecular mass to produce nutrients useful as baby food and the
hydrolysis of fat to obtain functional food with low calorie content.
9.3.1.1 Lactose Hydrolysis

Every year, 3.2 million tons of lactose, dissolved in whey, is accrued by cheese pro-
duction worldwide. Almost half of this amount is used for human and animal nutri-
tion. The rest is waste, which is difficult to dispose of, and add to environmental
pollution. Following the strategy of waste minimization and valorization, new efforts
have been made to develop further utilization possibilities of whey-derived lactose.
In addition, there is an increasing interest in the food industry toward lactose
hydrolysis due to the continuous demand of safe products such as nutraceuticals or
food with low allergenic compounds.
A lot of people suffer from intestinal dysfunction because they cannot digest lac-
tose due to the lack of β-galactosidase. Lactose is a compound that has high biochem-
ical oxygen demand (BOD), low sweetness, low solubility, and a strong tendency to
adsorb flavors and odors when compared with its hydrolysis products, glucose and
galactose. Another important process in which lactose hydrolysis is needed is in
the production of refrigerated dairy products, because some technological problems
occur due to the presence of lactose crystals. In addition, the hydrolysis products
of lactose, such as lactic acid, glucose, and galactose, can be used as natural food
ingredients (Ladero et al., 2000).
Several reactor configurations were used in which the biocatalyst extracted from
fungi or yeasts were analyzed. The main enzymes used for lactose hydrolysis were
extracted from Kluyveromyces yeast and Aspergillus fungi, which are considered
“generally recognized as safe” (GRAS).
One of the first cases of the application of BMR in food processes was the produc-
tion of milk with low lactose content by the entrapment of β-galactosidase on cellulose
acetate fibers (Pastore and Morisi, 1976). More recently, Grano et al. (2004) studied
nonisothermal lactose hydrolysis through immobilized β-galactosidase. In this noniso-
thermal BMR, the skim milk flows along both sides of the reactive membrane at dif-
ferent temperatures. This technology was proposed where an increase of the enzymatic
reaction rate was observed when the catalyst was immobilized on a hydrophobic porous
membrane separating two substrate solutions kept at different temperatures. The activ-
ity increase was attributed to the process of thermodialysis driven by the temperature
gradient that addresses the substrate toward the catalytic site and removes the reaction
products from it. These nonisothermal fluxes add to the diffusive ones, ever present.
An alternative hollow-fiber membrane diffusion reactor process was developed
by Neuhaus et al. (2006). In this system, skim milk is pumped through the hollow
fiber and molecules with a lower size than the membrane cutoff value such as small
proteins, salts, and lactose pass through into the shell side. There the lactose is enzy-
matically converted into glucose, galactose, and a small amount of oligosaccharides
by immobilized β-galactosidase. The product transfer back into the tube side is
also affected by concentration gradient-driven diffusion. The system showed that
the aimed productivity of 360 g/(L.h) was achievable at temperatures of 15(±2)°C
(240 U/mL of Maxilact), 23(±2)°C (120 U/mL of Maxilact), and 58(±2)°C (790 U/mL
of β-glycosidase).
The major problems associated with the use of an MBR for this application is
microbial contamination. The strategies used to control and limit this problem
are the periodic washing and pasteurization, the installation of a sterile filtration
module, and the application of UV irradiation. The problem of microbial contami-
nation can also be solved by exploiting the temperature property of the enzyme.
The isolation of pyschrophilic bacteria with cold active β-galactosidase has opened
up the possibility of processing of milk and whey even at low temperatures. On the
other side, thermostable enzymes have the unique ability to retain their activity at
higher temperatures for prolonged periods, and the process is less prone to microbial
contamination due to higher operating temperature.
9.3.1.2 Lactic Acid Production

Lactic acid (2-hydroxypropanoic acid, CH3CHOHCOOH) is a colorless liquid organic
acid. It has a variety of applications in food. The Food and Drug Administration
(FDA) approved lactic acid and its salts to be GRAS. The process of lactic acid
production includes two key stages: fermentation and product recovery. Lactic acid
fermentation is characterized by product inhibition, which affects cell growth and
metabolism and, thus, limits its production. Cell compartmentalization is one of the
most attractive methods for maintaining a high cell concentration.
Most publications on the use of MBRs for fermentation process concentrated
on various aspects, such as the effect of cell recycle along membrane modules on
productivity, cell bleeding, nitrogen concentration, microbial physiology, membrane
materials and fouling, by-product formation, and substrate limitation conditions.
Lactic acid represents an important field of application of MBRs (Table 9.5), due to
its potential use as monomer material for the preparation of environmental-friendly
packaging material together with its use as food ingredient.
In MBRs, the component that needs to be continuously separated from the fer-
mentation broth (which contains microbial cells, proteins, nutrients unconverted
carbon sources, water, and lactic acid) is lactic acid. The membrane that can play
an effective role in the separation of these components are micro/ultra/nano, reverse
osmosis, and electrodialysis membranes.
The main organisms used are Lactobacillus helveticus, Lactobacillus casei, and
Lactobacillus bulgaricus. Many studies regard Bifidobacterium longum. This is a
bacterium that can both convert lactose into lactic acid and produce an antibacterial
compound, which can boost the immune system in its host. Until the early 2000s,
there has been no report on the use of B. longum to produce lactic acid from cheese
whey. Studies carried out by Doleyres et al. (2002) and Song et al. (2003) relate to
increase in B. longum cell production by cell compartmentalization and to optimize
316
TABLE 9.5
Examples of Membrane Bioreactors for Lactic Acid, Prebiotic, and Oligosaccharide Production
Reactor
Biocatalyst Product Membrane Configuration References
Bacteria Lactobacillus rhamnosus Lactic acid Ceramic MBR Moueddeb et al. (1996)
Lactobacillus casei ssp. Mineral Olmos-Dichara et al. (1997)
rhamnosus
Lactobacillus bulgaricus Polysulfone, Giorno et al. (2002)
polyamide
Lactobacillus helveticus Polymeric Shahbazi et al. (2005)
Enzymes ß-Galactosidase from Galactose, glucose, and Polysulfone Neuhaus et al. (2006)
Kluyveromyces lactis oligosaccharides
ß-Galactosidase from Galacto-oligosaccharide Polyethersulfone Splechtna et al. (2007)
Lactobacillus reuteri (GOS) prebiotic
β-Glycosidase, recombinant Skim milk Eupergit C BMR Splechtna et al. (2002)
CelB from Pyrococcus furiosus
Note: MBR: membrane bioreactor; BMR: biocatalytic membrane reactor.

pH conditions. A particular kind of Bifidobacterium sp. produces a high yield of

l (+) lactic acid compared with d (−) lactic acid.
MBR is the most used reactor configuration type for lactic acid production.
Different studies were developed to solve problems related to concentration polar-
ization, fouling, and product inhibition. Xu et al. (1999) claimed to have controlled
the problem of concentration polarization and fouling effect by controlling tangential
flow in the Polyvinylidene fluoride (PVDF) microfiltration membrane (Millipore)
combined with a fermentor for downstream separation of cells of Lactobacillus
paracasei. A shear-enhanced cross-flow ultrafiltration was suggested by Toräng
et al. (1999).
To eliminate the product inhibition problem through direct removal of acid from
the fermentation broth, Giorno et al. (2002) integrated one cross-flow membrane
module fitted with microfiltration or ultrafiltration capillary membranes with a
2.5 L stirred fermentor. They studied the conversion of glucose to lactic acid by
Lactobacillus bulgaricus. Capillary polysulfone ultrafiltration membranes of
molecular weight cutoff (MWCO) of 100 kDa and polyamide Ultrafiltration (UF)
membrane of MWCO value 50 kDa were used. 0.1 μm pore size polyamide microfil-
tration membrane for separation and recycle of cells from the broth were also tested.
With an initial g lucose concentration of 17 g/L, the achieved lactic acid concentra-
tion was 10.8 g/L, the average yield being 62% and productivity 0.43 g/L. Polyamide
membranes showed lower flux reduction than polysulfone types but direct ultrafiltra-
tion of broth without prior microfiltration resulted in quick reversible fouling as the
system was operated at low cross-flow velocity to protect the microbes from shear.
In several membrane-based studies, successful separation of the components
of fermentation broth by integrated micro-, ultra-, nano-, and reverse osmosis and
electrodialysis (ED) membranes has been achieved. However, the combination of
single membrane unit with the fermentor did not permit to achieve all the goals
of process intensification in the manufacture of lactic acid. It appears that the
integration of a microfiltration membrane in the first stage followed by a nanofil-
tration membrane in the second can help reach the targets of commercial produc-
tion of monomer-grade lactic acid with high productivity and concentration in an
environmentally benign process.
9.3.1.3 Protein Hydrolysis

Dietary proteins are traditionally known to provide a source of energy and the amino
acids essential for growth and maintenance of various body functions. In addition,
they contribute to the physicochemical and sensory properties of protein-rich foods.
In recent years, food proteins have gained increasing value due to the rapidly expand-
ing knowledge about physiologically active peptides. Milk proteins provide a rich
source of peptides that are latent until released and activated, for example, during
gastrointestinal digestion or milk fermentation. Once activated, these peptides are
potential modulators of many regulatory processes in living systems. In particular,
they can affect cardiovascular, nervous, gastrointestinal, and immune system.
In addition, enzymatic hydrolysis of whey proteins is a well-known method to
modify their solubility, viscosity, and emulsifying and foaming properties and,
more importantly, to improve their nutritional properties for the production of active
peptides (Nielsen, 1997). Whey protein hydrolysates are considered to be ideal

ingredients in the formulation of human milk substitutes due to their high nutritional
value, low bitterness, and low antigenicity. Antigenic peptide structures may remain
intact even after an extensive hydrolysis. In this case, membrane processing can be
a solution as short peptides can be obtained in the permeate of an ultrafiltration unit
while long, antigenic sequences are retained. On the other hand, it has to be consid-
ered that an excessive hydrolysis should be avoided since it produces a high content
of free amino acids involving negative effects such as bad sensory properties and
high osmolality. Therefore, the hydrolytic reaction has to be strictly controlled.
The peptides can be produced in three ways: (a) through hydrolysis by diges-
tive enzymes, (b) through hydrolysis by proteolytic microorganisms, and (c) through
the action of proteolytic enzymes derived from microorganisms or plants. The pro-
duction of bioactive peptides from milk proteins has been limited by the lack of
suitable large-scale technologies. Until now, membrane separation techniques have
provided the best technology available for the enrichment of peptides (Korhonen
and Pihlanto, 2006) with a specific molecular weight range (Korhonen and Pihlanto,
2003). Ultrafiltration is routinely employed to enrich bioactive peptides from protein
hydrolysates. The use of enzymatic membrane reactors with immobilized enzyme
for continuous production of specific peptide sequences was introduced during the
late 1980s (Lasch et al., 1987). However, their use has not been widespread because
of high losses in activity (mainly due to diffusional restrictions) and expensive
immobilization procedures. So, the main configuration for peptide hydrolysis still
remains an MBR where hydrolysis occurs in bulk and separation is achieved with a
combined ultrafiltration unit.
In Table 9.6, the biocatalysts commonly used and specific application fields for
protein hydrolysis in MBR are reported.
A special kind of bioreactor was proposed by Righetti et al. (1997) using mul-
ticompartment enzyme reactor operating under an electric field for the continuous
hydrolysis of milk proteins (Figure 9.12).
The enzyme trypsin is trapped, with zwitterionic buffering ions and its substrate
α-casein, in solution between two isoelectric membranes having pI values encom-
passing the isoelectric point of the enzyme. Additionally, α-casein is blocked inside
the same reaction chamber with the aid of sieving membranes, since its pI is too
far away from the pI of trypsin. This setup permits the continuous operation at the
optimum activity pH. The peptides, arising from tryptic hydrolysis of α-casein, are
removed under the influence of the electric field and collected in different chambers
in which they are isoelectric and isoionic as well, with the aid of properly chosen
isoelectric membranes. This setup allows continuous harvesting of some biologically
active peptides in a pure form.
Other strategies are based on the simultaneous use of more biocatalysts in com-
bination with the membrane.
Nakamura et al. (1995) used two proteases to reduce the antigenicity of whey
proteins by 1000 times.
An important drawback when proteases are used is enzyme autolysis. Cabrera-
Padilla et al. (2009) proposed a novel configuration of membrane bioreactor to over-
come this problem. In this system, carboxypeptidase A (CPA) was immobilized in
TABLE 9.6
Biocatalysts and Substrates Used to Produce Peptides in Membrane Bioreactor
Biocatalyst Substrate Peptides Produced References
Enzymes Alcalase Casein Caseinopeptides Mannheim and Cheryan (1990)
Caseinomacropeptides Antithrombotic peptides Bouhallab and Touzé (1995)
Trypsin Casein Caseinomacropeptides Martin-Orue and Bouhallab (1999);
Prata-Vidal et al. (2001)
Soy protein Soy protein peptides Chiang et al. (1999)
Chymotrypsin, pancreatin, elastase, β-Lactoglobulin, (ACE) inhibitory peptides Philanto-Lappälä et al. (2000)
carboxypeptidase α-lactalbumin
Papain Goat whey protein Mixture peptides and Sannier et al. (2000)
concentration of
β- lactoglobulin
Food Applications of Membrane Bioreactors
Trypsin Casein (ACE) inhibitory calcium- FitzGerald et al. (2004); Gobbetti

binding phosphopeptides et al. (2004)
Pepsin (ACE) inhibitory peptides Korhonen and Pihlanto (2006)
Protease N Whey proteins Different peptides Cheison et al. (2006)
Terrylitin Casein and fibrinogen Casein and fibrinogen peptides Solov’ev et al. (2006)
Protease from Aspergillus niger Casein Casein hydrolysates Chiang et al. (1995)
Carboxypeptidase A Whey prehydrolyzed Different peptides Cabrera-Padilla et al. (2009)
Bacteria Lactococcus helveticus Casein, whey proteins ACE inhibitory peptides Nakamura et al. (1995)
Aspergillus oryzae Casein Different peptides Chiang et al. (1995)
Lactobacillus. delbruecki ssp. bulgaricus ACE inhibitory peptides Gobbetti et al. (2000)
Lactococcus lactis Casein, milk Korhonen and Pihlanto (2006)
Bacillus licheniformis Whey protein concentrate Protein hydrolysates Prieto et al. (2008)
319
Sieving
membrane
Peptide (114–169)
Peptide (33–48)
Peptide (49–97)
Peptides –
+
A = pI 3
Sodium hydroxide
Sodium hydroxide
B = pI 5
C = pI 6
pH 12
pH 2
D = pI 6.5
E = pI 7.5
A B C D E F G
F = pI 8.1 Isoelectric membranes
G = pI 9.5
Reaction
compartment
Power
supply
FIGURE 9.12 Scheme of the experimental setup of multicompartment enzyme reactor.
agarose gel particles, while the substrate used is whey previously hydrolyzed with
immobilized chymotrypsin. The research carried out in this field permitted to under-
stand the limits and potentialities of MBR in protein hydrolysis until the develop-
ment of some patents related to the production of bioactive peptides from casein
(Qi, 2004; Hua et al., 2011). One of these patents (Qi, 2004) relates to a process for
continuous production of casein bioactive peptides by enzymolysis and membrane
filtration. This was realized by the production of a multistage enzyme membrane
reactor, in which the enzyme was immobilized by entrapment.
9.3.1.4 Hydrolysis of Milk Fat

Lipases are extensively used in dairy industry for the hydrolysis of milk fat. Current
applications include flavor enhancement of cheeses, acceleration of cheese ripen-
ing, manufacturing of cheese-like products, and lipolysis of butterfat and cream. In
recent years, enhanced consumer interest in the relationship of diet to good health
has led to an increased demand for low-fat dairy products. Cheese ripening is com-
posed of a complex sequence of events and is the result of many transformation
processes such as proteolysis and lipolysis in milk by indigenous microflora. Cheese
texture is related to the fat content, and aroma is generated by fat degradation, lead-
ing to primary and secondary products. The right equilibrium between the specific
primary and secondary products is reached with the help of numerous enzymes. In
a regular cheesemaking process, milk fat is hydrolyzed during lipolysis to liberate
free fatty acids, which contribute directly to the aroma and also acts as precursors for
methyl ketones, secondary alcohols, and aliphatic and aromatic esters. The addition
of exogenous lipase accelerates the ripening process. The free fatty acids generated
by the action of lipases on milk fat endow many dairy products, particularly soft
cheeses, with their specific flavor characteristics. Lipases also play a crucial role in
the preparation of the so-called enzyme-modified cheeses (EMC). EMC is cheese
that is incubated in the presence of enzymes at elevated temperature in order to pro-
duce a concentrated flavor for use as an ingredient in other products (dips, sauces,
dressings, soups, snacks, etc.).
Immobilization of lipases is widely used in milk fat treatment for hydrolysis and
transesterification. Adsorption of lipases on food-grade microporous membranes
made of polypropylene enhances the productivity of lipases, improves their thermal
stability, permits regeneration of the support with fresh enzyme, eliminates the need
for addition of emulsifiers, and decreases the potential for the contamination of the
product by residual lipase, thus avoiding the need for downstream thermal treatment
(Malcata et al., 1991). Consequently, the use of an immobilized lipase should facil-
itate the development of continuous, large-scale commercial processes that could
compete successfully with batch-scale operations that employ soluble lipases. The
continuous process also provides opportunities for better control of both the process
and product quality.
Malcata and Hill (1995) have employed an immobilized lipase in the hydrolysis
of melted butterfat. A lipase from a strain of Aspergillus niger was immobilized by
adsorption on polypropylene hollow fibers. The work focused on a design methodol-
ogy for use of this technology on an industrial basis, and a preliminary assessment of
the economic viability of the said process. This process is advantageous from an eco-
nomic point of view compared to the traditional process (in terms of units of product
manufactured per unit of enzyme consumed) about two orders of magnitude greater
than that for the corresponding free enzyme process. Lipase from Candida rugosa
was also immobilized by adsorption on flat sheets made of microporous polypropyl-
ene membrane and placed into a reactor in a spiral wound (axial-annular flow) con-
figuration (Garcia et al., 1992). The operation of the reactor yielded relatively high
conversions at short space times, thus indicating that this type of reactor is an inter-
esting option for use on an industrial scale for the production of lipolyzed butter oil.
The organoleptic quality and nutritional value of goat cheese can be improved by
lipid milk fraction transesterification. Immobilized lipase from Mucor miehei was used
to decrease the amount of short- and medium-chain fatty acids (C4–C14) by enrichment
of the reaction mixture with long-chain (C18:1 and C18:2) fatty acids (Caponio et al.,
1998). This milk fat could be reincorporated into skimmed milk for cheese production.
9.3.2 Membrane Bioreactors in Fruit Juices Processing

Membrane operations in fruit processing have been applied for clarification (micro-
filtration and ultrafiltration), concentration (reverse osmosis), and deacidification
(ED). The use of other membrane process such as nanofiltration, osmotic distillation,
and pervaporation for the concentration and recovery of aroma compounds have also
been applied (Strathmann et al., 2011).
Usually, pectinases are used to improve membrane flux by reducing membrane

fouling during juice and pulp pretreatment. Generally, this process is carried out in
batch systems, before juice filtration, but the use of MBR also permits to overcome
product inhibition phenomena that occur in this process.
The enzymes responsible for pectin hydrolysis are pectinolytic, which can be
divided into three broader groups as follows:
1.
Protopectinases: Degrade the insoluble protopectin and give rise to highly
polymerized soluble pectin
2.
Esterases: Catalyze the de-esterification of pectin by the removal of
methoxy esters
Depolymerases: Catalyze the hydrolytic cleavage of the α-(1-4)-glycosidic
3.
bonds in the d-galacturonic acid moieties of the pectic substances
Commercial pectinolytic enzymes and their catalytic action are reported in

Table 9.7, while Table 9.8 indicates the source of the extraction of the more impor-
tant pectinases.
TABLE 9.7
Enzymes Present in Pectinolytic Preparation
Enzyme Type Enzymatic Action
Polygalacturonases (PGs, EC 3.2.1.15) Hydrolase Split the α-(1-4) linkage between two
galacturonic acids
Pectin methylesterases (PME, EC 3.1.1.11) Esterase Release the methyl groups
Arabinases (EC3.2.1.99), Galactanases Hydrolases Specific for α-(1-5) between Ara residues,
(EC 3.2.1.89) and β-(1-4) linkages between Gal residues
Rhamnogalacturonan Hydrolase Cleaved galactopyranosyluronic-
rhamnopyranosyl linkages.
TABLE 9.8
Pectinase and Its Derivation Strain
Pectinase Strain
Polygalacturonase Aspergillus niger
Rhizopus stolonifer
Saccharomyces pastorianus
Neurospora crassa
Pectin lyase Amycolata sp.
Bacillus macerans
Penicillium italicum
Bacillus sp. TS47
Pectin lyase/polygalacturonase Aureobasidium pullulans
Endo-polygalacturonase Saccharomyces cerevisiae
Cryptococcus albidus var. albidus
Many microorganisms can produce pectinases; numerous reports have appeared

on the optimization of fermentation and microbiological parameters and different
fermentation strategies for the production of pectinases. In order to use pectinases
as a suitable industrial biocatalyst and to apply these in various research fields, the
purification of enzymes is very important.
A. niger pectinases are most widely used in industries because this strain pos-
sesses GRAS status, so that metabolites produced by this strain can be used safely.
The pectinases produced from this strain are polymethylgalacturonase (PMG), poly-
galacturonase (PG), and pectinesterase (PE). However, particular pectinases are
used for specific purpose, for example, PG in baby food products.
For what concerns the substrate, the American Chemical Society classified pectic
substances into four main types as follows:
1.
Protopectin: The water-insoluble pectic substance present in intact tissue.
Protopectin on restricted hydrolysis yields pectin or pectic acids.
2.
Pectic acid: The soluble polymer of galacturonans that contains negligible
amount of methoxy groups. Normal or acid salts of pectic acid are called
pectates.
Pectinic acids: The polygalacturonan chain that contains >0 and <75%
3.
methylated galacturonate units. Normal or acid salts of pectinic acid are
referred to as pectinases.
4.
Pectin (polymethyl galacturonate): The polymeric material in which there
is at least 75% of the carboxyl groups.
The oligosaccharides derived from pectins have been shown to have application
as repressors of liver lipid accumulation in rats (Yamaguchi et al., 1994). Important
applications of pectic oligosaccharides are as antifungal phytoalexin elicitors in
plants (Bishop et al., 1984), inducers of flowering and antibacterial agents (Iwasaki
et al., 1998).
The main food processes in which pectic enzymes are involved are production of
nonalcoholic juice, wine, cider to increase juice yield, juice clarification, liquefaction
process, and tissue fruit maceration to produce nectar.
Juice production includes the following preparation steps (Figure 9.13): fruit
crushing, pressing, clarification, centrifugation or filtration, concentration, and
pasteurization.
During fruit crushing, the solubilization of pectins occurs. In the industrial fruit
juice production process, the addition of pectolytic enzymes is needed in the press-
ing and clarification steps. In the pressing step (Figure 9.14), pectolytic enzymes
degrade the cell wall of the pulp, increasing pigments and aroma recovery and also
process yield. In the clarification step, usually carried out by filtration, the use of
pectolytic enzymes eliminate cloud particles (pectins and proteins) that can cause
filter clog and fouling phenomena.
The aim of the maceration process is to produce a suspension of intact cells,
resulting in a pulpy product used for nectars, baby food, and ingredient for dairy
products. For this action, it is necessary affect the middle lamella pectins and should
therefore contain PG (Zetelaki-Horvath and Gatai, 1977) or pectin lyase (Ishii and
Crushing
Use of pectinases
Pressing
Clarification
Centrifugation or
filtration
Concentration
Pasteurization
FIGURE 9.13 Use of pectinases in fruit juice processing.
Yokotsuka, 1973). In the liquefaction process, a complete degradation of cell wall

is needed and the action of pectolytic enzymes is coupled with cellulose-degrading
enzymes. This technology is used intensely for apples and tropical fruits.
Different works were carried out about pectin hydrolysis with MBR (Table 9.9).
Alkorta et al. (1995) and Rodriguez-Nogales et al. (2008) studied the reduction in
the viscosity of pectin solutions catalyzed by pectin lyase from Penicillium italicum
in an MBR. This enzyme seems to be the only pectic enzyme capable of cleaving,
without the prior action of other enzymes, the α-1,4 glycosidic bond of highly esteri-
fied pectins, decreasing the viscosity and clarifying juices without damaging the
volatile compounds responsible for the specific aroma of various fruits.
Cell recycle
brane
UF mem
Fermentor
Permeate
Feed
Sodium
carbonate
FIGURE 9.14 Continuous membrane fermentor apparatus with ultrafiltration cell-recycle

system.
TABLE 9.9
Pectin Hydrolysis by Membrane Bioreactor Systems
Bioreactor
Configuration Biocatalyst Application References
Membrane bioreactor Pectin lyase Production of Alkorta et al. (1995)
oligosaccharides
Polygalacturonase Production of monomer Bélafi-Bako et al.
of pectin to be used as (2007)
nutraceutical
Polygalacturonase Wine clarification Rodriguez-Nogales
and pectin lyase et al. (2008)
Endo- Production of Olano-Martin et al.
polygalacturonase oligosaccharides (2001)
Endopectidase Apple pectin hydrolysis Rodriguez-Nogales
et al. (2008)
Biocatalytic membrane Rapidase liquid plus Juice clarification Giorno et al. (2002)
reactor Polygalacturonase Production of Szaniawski and
from Aspergillus oligosaccharides Spencer (1996)
niger
Pectin lyase decreased the viscosity of pectins in the membrane with more effi-
ciency (60% in 30 min) compared to the batch system (46% in 30 min).
In order to apply the system on an industrial scale, long-time operation is required.
Bélafi-Bako et al. (2007) studied the enzymatic hydrolysis of pectins using PG from
A. niger in a flat-sheet MBR. The system worked with excellent stability for more
than 50 h. A recent work (Rodriguez-Nogales et al., 2008) proposed a system for
the study of the enzymatic hydrolysis of pectins in an MBR for a long-term period
(15 days). Through the use of this system, a viscosity reduction of about 88% was
reached only after 15 min. The performance of MBRs toward the hydrolysis of pec-
tins was also tested, immobilizing directly the pectinase on the membrane (Alkorta
et al., 1995), using a BMR system. The use of pectinase immobilized on ultrafil-
tration membranes permits the hydrolysis of low-molecular-weight species (mainly
anhydrogalacturonic acid, AGA) at the membrane interface, resulting in an increase
of the permeate flux or at least an extension of the membrane operation without
cleaning (Carrin et al., 2000). Pectinase was immobilized on different supports and
using different immobilization procedures, such as physical immobilization on tita-
nia microfiltration membrane (Szaniawski and Spencer, 1996) and on polysulfone
hollow fiber (Carrin et al., 2000), or coimmobilized in combination with amylase,
by physical absorption on polysulfone hollow-fiber membrane for the simultaneous
hydrolysis of pectins and starch. The coimmobilization showed an improvement of
flux up to 35% as compared with the same process without enzymes. Endo-PG and
pectin lyase, among others, have been immobilized on different organic and inor-
ganic supports (Carrin et al., 2001).
9.3.3 Membrane Bioreactors Using Plant as Material

Source for Biotransformation
Plants are a very good source of a variety of chemicals and food additives, including
flavors, pigments, and agrochemicals. Some of the chemical reactions occurring in
plants are complex and difficult to reproduce by the synthetic route. The possibility
to conduct biotransformation using plant materials is of huge interest because they
have the great potential to generate novel products or to produce known products
more efficiently. Plant cell cultures exhibit a vast biochemical potential for the pro-
duction of specific secondary metabolites. The formation and accumulation of some
important secondary metabolites do not occur in plant cell cultures. However, such
cultures may retain an ability to transform exogenous substrates into products of
interest. The chemical compounds, which can undergo biotransformations mediated
by plant enzymes, are varied in nature. They include aromatic, steroid, alkaloid,
coumarin, terpenoid, lignan, and other molecular species. It is not necessary for the
compounds to be natural intermediates in plant metabolism. The substrates can also
be of synthetic origin. Plant cell cultures and enzymes have the potential to trans-
form cheap and plentiful substances, such as industrial by-products, into rare and
expensive products.
Plant systems, on the other hand, produce a more limited range of enzymes, and
undifferentiated plant cells have longer doubling times than microbial cells. In addi-
tion, the desired enzymes are often produced in minute quantities. Despite these
drawbacks, the plant kingdom contains some unique enzymes, which produce a
variety of chemicals. Chemical synthesis of some of these compounds is extremely
complicated and costly. Hence, biotransformations using plant cells and isolated
enzymes have immense potential for production of important compounds. Plant
enzyme biocatalysts may be applied to the production of totally new food molecules
and may also be used to modify existing molecules by improving their bioactivity
spectrum.
Some of the more important biotransformations with plant material types are
described in Table 9.10.
A large number of reports on enzymes isolated from plant cell cultures used in
bioconversion are reported in the literature.
Some examples of important reactions that involve food processes are described
in the following:
• Papain can hydrolyze peptide bonds, and in some cases can also cleave ester
linkages. High concentration of thiol-protease papain is found in the leaves
and in the fruit of Carica papaya (Azarkan et al., 1997). This enzyme is
very useful in biotechnology application and particularly in food, because
the easy manipulation of the reaction direction, by changing the water con-
tent and because of the high specificity of cleavages for peptides involving
Phe, Val, or Leu (Faber, 2000).
Some examples in the use of this enzyme in MBR technology are
reported in the literature (Bhardwaj et al., 1996; Sannier et al., 2000; Wang
et al., 2007).
TABLE 9.10
Biotransformation Using Plant Biocatalysts
Biocatalyst Biotransformation Status Substrate References
Cells from Nicotiana Glucosylation Free Phenols, butyric acid to produce Kamel et al. (1992)
plumbaginifolia inhibitor of tumor cell
Cells from Catharanthus roseus Hydroxylation of exogen From geraniol, nerol, (+) and (−) carvone Hamada et al. (1993)
substrate by introduction of to 5β-hydroxyneodihydroxycarveol
oxygenated functions
Cell extract or broth from Reduction of carbonyl groups Free Ketones and aldehydes Botta et al. (1996)
Nicotiana sylvestris or for alcohol production
Catharanthus roseus
β-Glucosidase from almond Hydrolysis Free Immobilized Oleuropein Capasso et al. (1997);
Mazzei et al. (2009)
Avena sativa peroxygenase Epoxidation, modification of Immobilized Fatty acids Piazza et al. (2000)
cytotoxic sesquiterpenes
327
• Hydroxynitrile lyases are stereoselective enzymes and produce only one

enantiomer; they operate in plants to produce antipathogenic compounds.
The natural substrates are (R)-amygdalin, (S)-durrin, limarin, prunasin,
etc. (R)-Hydroxynitrile lyases are mainly used for the synthesis of (R)-
mandelonitrile and its derivatives, which can subsequently be hydrolyzed
to their corresponding carboxylic acids. Examples of the application of this
enzyme on MBR are not yet present in the literature.
• The phenoloxidase responsible for the hydroxylation of monophenols to
catechols with regiospecificity has application in almost all food sectors;
in plants, it is particularly abundant in Mucuna pruriens. This enzyme
was used in about all fields of the food sector, because it is involved in the
phenol oxidation in different processes: wine stabilization, in fruit juice
processing, beer stabilization, treatment of drinking water, and also waste
material from food industries (such as olive mill wastewater [OMWW]).
• Lipoxygenase is a nonheme iron-containing enzyme that catalyzes the
incorporation of dioxygen into suitable unsaturated substrates. The natu-
ral substrate of the enzyme is linoleic acid, but it can accept a number of
substrates provided they contain a Z,Z-1,4-diene unit with a substituent (R)
of 3–10 carbons and a carboxylic acid group (Holland, 2000). A combina-
tion of lipoxygenase and hydroperoxide lyase (soy flour) has been used to
convert plant polyunsaturated fatty acids to a mixture of hexenal, hexan-
1-ol, E-2-hexenal, E-2-hexen-1-ol, and Z-3-hexen-1-ol, the so-called natu-
ral “green note” flavor components present in plants such as mint (Mentha
arvensis), which are in high demand by the food industry.
An interesting and innovative field of using plant materials in the food field,
as a source of biomass and biotransformation, is the use of algae. Owing to their
high content of proteins, vitamins, and other nutrient compounds, this class of veg-
etable materials is recognized as health food. They have been included as human
food from blue-green and green algae. Soda ash, iodine, and alginic acid have been
included from brown algae, and agar and carrageenans have been included from
red algae.
The cultivation of algae in wastewater offers the combined advantages of treat-
ing wastewaters and simultaneously producing algal biomass, which can be further
exploited for protein complements and food additives (for aquaculture, animal, and
human feed) (Mallick, 2002). Nowadays, they are becoming very attractive for
energy feedstock production.
One of the major and practical limitations in algal treatment systems is harvest-
ing or separation of algal biomass from the treated water discharge. An efficient
removal of algal biomass is essential for recycling the wastewater. Numerous efforts
have been devoted to develop a suitable technology for harvesting microalgae rang-
ing from simple sand filtration to energy-intensive centrifugation. In this context,
immobilization of algal cells for wastewater treatment has been proposed for cir-
cumventing the harvest problem as well as retaining the high-value algal biomass
for further processing. Application of immobilization technology to algal wastewa-
ter treatment provides more flexibility in the reactor design when compared with
conventional suspension systems (Mallick, 2002). Different kinds of bioreactor were

developed for algae cultivation: fluidized-bed bioreactors (FBR), packed-bed biore-
actors (PBR), parallel-plate bioreactors (PPR), air-lift bioreactors (ALR), and MBR
using hollow fiber.
Despite the interest in the field, so far, few examples of MBR development are
reported for algae cultivation.
Robinson (1998) developed an MBR using hollow fibers with 50 cylindrical tubes
of polysulfone bundled and sealed in a transparent cartridge of 20 cm in length.
Such a cartridge could be operated with algal cells contained within the lumen of
each fiber and the nutrients pumped in through the shell space or vice versa. In
this system, biomass settling is observed that determines the decline in phosphate
uptake rate. To overcome this problem, cells were suspended in a solution of 1%
Na-alginate. These reactors attained a steady-state removal rate quickly, which was
found to remain constant for several weeks. Such bioreactors are physically stable
and can be cleaned and restocked with new biomass when the removal rate falls
below an acceptable standard.
Kumar et al. (2010) also designed a hollow-fiber photobioreactor with polyvinyl
chloride (PVC) tubing on a laboratory scale with the thermophilic cyanobacterium
Phormidium laminosum. The photobioreactor comprises a transparent PVC tubing
containing cellulose hollow fibers, a peristaltic pump, a heater, and two cool white
fluorescent lamps. Cells were immobilized in hollow fibers and placed in the PVC
tubing. Immobilization was accomplished by the addition of cell culture to the reac-
tor using the peristaltic pump. Two days after cell inoculation, the secondarily treated
sewage was passed through the photobioreactor at 43°C at a flow rate of 50 mL/day
with continuous fluorescent light of 60 μM photon/s.min. The removal rates of N and
P ions by this hollow-fiber reactor were 3.36 mg/day.L and 3.30 mg/day.L, respec-
tively, as compared to 8.88 mg/day·L and 1.47 mg/day.L, respectively, in the case of
the chitosan-immobilized Phormidium. This hollow-fiber immobilization presents a
better system for P removal than the chitosan immobilization. On the other hand, N
was better removed with the immobilized chitosan.
9.3.4 Plant Raw Material Used as Source

Vegetable material can also be an extraordinary source of substrate to generate food
with high nutritional value, such as starch and food additives like oligosaccharides,
stabilizers, etc.
9.3.4.1 Starch Hydrolysis

Starch represents the major source of available carbohydrate in the human diet and
is the most abundant (22%–45%) carbohydrate in the legume seed. The enzymes
commonly involved in starch hydrolysis are amylase in starch liquefaction and sac-
charification, pullulanase in saccharification, and cyclodextrin-glycosyltransferase
in cyclodextrin production.
Traditionally, the enzymatic hydrolysis of starch is performed in large-volume
batch reactors using soluble enzymes; this step is followed by the procedure of liq-
uefaction and saccharification. In the first part of the process, the starch is dissolved
TABLE 9.11
Membrane Bioreactors in Starch Hydrolysis
Biocatalyst Substrate Membrane Application References
Aspergillus niger Cassava flour Polysulfone Glucose syrup Lopez–Ulibarri
glucoamylase starch from root hollow-fiber and Hall (1997)
ultrafiltration
Exo-α-amylase Cassava starch Carbosep M4 Sugar syrups Paolucci-Jeanjen
Termamyl 120 l from obtained from membranes et al. (2000)
Bacillus licheniformis Manihot (50 kDa)
ultissima Pohl
Cyclodextrin Soluble potato Cellulose acetate Cyclodextrins Słomińska et al.
glucosyltransferase starch membrane (2002)
from (3 kDa, 10 kDa)
Thermoanerobacter
α-Amylase from Maltodextrin Tubular ceramic, Maltose syrup Grzeoekowiak-
Aspergillus oryzae with 7–9 DE hollow-fiber Przywecka and
obtained from polysulfone Słomińska
potato starch (2005)
α-Amylase from Oxidized starch Tubular ceramic Carbohydrate Kędziora et al.
Bacillus potato production (2006)
amyloliquefaciens
in water and hydrolyzed partially by α-amylase, giving maltodextrin. In the second

step, saccharification enzymes transform liquefied starch into low-molecular-weight
oligosaccharides, in particular glucose or maltose. The introduction of membrane
reactors brings the possibility of a continuous operation in lower-volume reactors in
shorter reaction time (Paolucci-Jeanjen et al., 2000). In particular, the MBR has been
applied to produce glucose, maltose, maltose syrup, maltotetraose, cyclodextrins,
and octenylsuccinate from octenylsuccinate starch derivatives to replace gum arabic
in flavor emulsions and as a stabilizer for other food.
Different sources and MBRs were used. Table 9.11 shows some examples of the
membrane used, product, and enzyme membrane reactor type.
Cassava root (Manihot esculenta) is an alternative source for starch that can
reduce the production cost of glucose syrup. The starch content in cassava (85%–
90%, dry matter) is higher compared to maize or potato; in addition, cassava is one
of the 10 most important crops (Lopez-Ulibarri and Hall, 1997). Typically, con-
tinuous saccharification of cassava flour starch in the hollow-fiber MBRs produces
99.6% of glucose with a starch conversion of 97.3%. The use of cassava flour for the
production of glucose syrup in a continuous stirred-tank membrane reactor resulted
in a better general performance compared with the system where the substrate is
obtained from cassava starch. A pilot plant for the hydrolysis of cassava starch
obtained from Manihot ultissima Pohl using exo-α-amylase Termamyl 120 l from
Bacillus licheniformis was carried out in continuous MBRs. Results showed that
an increase in enzyme concentration induces a better conversion, while at the same
time, reactor capacity and productivity are reduced (Paolucci-Jeanjean et al., 2000).
Another important product derived from starch hydrolysis is cyclodextrin.

Cyclodextrins are cyclic maltooligosaccharides formed by glucopyranose units
linked by α-1,4 bonds. These molecules have two portions, one external hydro-
philic and one hydrophobic cavity. This conformation makes these compounds
particularly suitable to form an inclusion complex with a variety of applications
in food. Their production from starch is obtained thanks to the enzymatic action
of cyclodextrin glucosyltransferase. Usually the use of glucosyltransferase for the
production of cyclodextrins needs a starch pretreatment with amylase. Studies on
simultaneous hydrolysis of cyclodextrins starting from starch were carried out in
continuous cell-recycle MBRs, using cellulose acetate ultrafiltration membranes
(Słomińska et al., 2002).
The most used configuration for starch processing are the MBRs with continuous
biocatalyst recirculation. The main problems of starch hydrolysis carried out in an
MBR system are enzyme inactivation, highly viscous solute produced by rapid gela-
tinization, and accumulation of higher oligosaccharide polymerization. Recently,
research efforts have been focusing on the development of an MBR system that
works at low temperature, with an additional settling tank, and further advances are
expected by the immobilization and/or fluidization operations.
9.3.4.2 Oil Processing

Fats and oils are produced worldwide at a level of approximately 60 million tons per
year, and a substantial part of this (more than 2 million tons per year) is utilized in
high-energy-consuming processes such as hydrolysis, glycerolysis, and alcoholysis.
Many different components from the processing of agricultural oils and fats can be
commercially utilized. The triglyceride fraction is used primarily as edible oil while
monoglycerides and fatty acids can be used as flavors and emulsifying agents, and
lecithin is widely used as a food ingredient, especially as an emulsifier in marga-
rines. Oilseeds that have been crushed and had the oil extracted have traditionally
been used as fertilizers or added to fermentation media (especially soy sauce) in
China and Japan, or used as animal feed in the rest of the world.
A broad range of enzymes can be used for the conversion of fats and oils.
Table 9.12 provides a list of enzymes used for lipid modification in the food field.
The versatile microbial lipases have an important role in the biocatalysis of lipids.
Lipases have a potential use in the industrial process as biocatalysts for different
reasons. They act under mild conditions and are highly stable in organic solvents.
Lipases show broad substrate specificity, and usually high regio- and/or stereoselec-
tivity in catalysis. Membrane technology is gradually gaining many potential appli-
cations in the oil processing industry. There are several BMRs with immobilized
lipases described in the literature that have been studied for the hydrolysis of ester
(including transesterification) in the fat and oleochemical fields.
The main application includes the production of high-added-value lipid com-
pounds, structured lipid with desirable spread properties, and food products with
low-calorie, cheaper cocoa butter substitutes.
In Table 9.13, some examples of BMRs employing lipases are described. Important
characteristics such as microorganism source, reaction type, method of immobiliza-
tion, support material, and reactor configuration are illustrated.
TABLE 9.12
Enzyme Used for Lipid Modification in the Food Field
Enzyme Applications Specific Application
Lipase Transesterification in organic solvents Cocoa butter equivalent
Human milk fat substitute
“Betapol”
Enrichment or incorporation of specific Polyunsaturated fatty acids from
fatty acids fish oil
Polyunsaturated fatty acids from
plant oil
Phospholipase Removal of phospholipids in vegetable Lysophospholipids from
oils (“degumming”) vegetable oils (rape seed,
soybean, sunflower seed)
Monooxygenase Hydroxylation of fatty acids Precursor for polyesters/lactones
Epoxidase Epoxidation of double bonds –
Lipoxygenase Synthesis of fatty acid hydroperoxide –
The lipase is frequently used in biphasic organic/aqueous membrane reactor.

Giorno et al. (1997) compared the efficiency of lipase to hydrolyze vegetable oil
triglycerides into fatty acids and glycerol using different reactor configurations: (1)
a traditional emulsion STR; (2) an emulsified organic–aqueous enzyme membrane
reactor (E-EMR; where the reaction occurred in emulsion and the aqueous phase
was ultrafiltered through a membrane, thus separating the product); and (3) a bipha-
sic organic–aqueous enzyme membrane reactor (B-EMR) (where the two phases
were separated by the membrane that also contained the immobilized enzyme). Free
enzyme showed a higher reaction rate but the catalytic activity of the immobilized
enzyme was considerably more stable.
Another oil processing application in which immobilized lipase is used is the
production of lipids with higher-added-value attributes (omega-3 polyunsaturated
fatty acid). Immobilized M. miehei lipase in organic solvent catalyzed the reactions
of enzymatic interesterfication for the production of vegetable oils such as corn oil,
sunflower oil, peanut oil, olive oil, and soybean oil containing fatty acids.
Enzymatic interesterification is now commonly used commercially to produce
high-value products, such as structured triglycerides (TAGs) for confectionery.
One example is the lipase-catalyzed production of cocoa butter used in the manu-
facture of chocolate from low-value oils. Another example is the modification of
palm olein by using immobilized lipase to produce fat of desirable melting point
characteristics.
As structured lipids, plastic fats intended for food applications, such as the pro-
duction of margarine, shortening, and modified butter, are solid in appearance and
possess low resistance to small stresses, thereby making them easy to spread and
rapidly melt in the mouth. The proportion of solid to liquid crystals is the key factor
that determines the hardness of the mixture. A solid fat content between 15% and
35% characterizes plastic fats that can be produced enzymatically or chemically.
TABLE 9.13
Examples of Membrane Bioreactors Employing Immobilized Lipase
Method of Support
Reaction Type Microorganism Source Substrate Immobilization Material References
Hydrolysis Candida cylindracea Olive oil Entrapment Polyamide Giorno et al. (1995)
Candida rugosa Sunflower oil Adsorption Cellulose Pronk et al. (1988)
Rhizopus sp. Sunflower oil Cross-linking PTFE Rucka et al. (1989)
Porcine pancreas Olive oil Covalent binding Cellulose beads Kéry et al. (1990)
Rhizopus sp. Sunflower oil Entrapment PVC Rucka and Turkiewicz
(1990)
Rhizopus sp. Sunflower oil Adsorption PVC Rucka and Turkiewicz

(1990)
Aspergillus niger Butterfat Adsorption Polypropylene Malcata et al. (1991)
Ester synthesis Candida rugosa Decanoic acid and glycerol Adsorption Cellulose Van der Padt et al. (1990)
Mucor miehei Propionic, butyric, hexanoic Covalent binding Nylon Manjón et al. (1991)
acids, ethyl, hexyl alcohols
Rhizopus miehei, Rhizopus niveus, Dodecanol and decanoic acid Adsorption Polypropylene Valivety et al. (1992)
Humicola sp., Candida rugosa particles
Transesterification Pseudomonas cepacea 5,7-Diacetoxyflavone and butanol Entrapping Zirconia Giorno et al. (1997)
Rhizopus oryzae (S)-Glycidol and n-butyrate Entrapping PVA Shinji Sakai et al. (2008)
333
Enzymatic approaches present several advantages: (1) no modification of the chemi-

cal properties of the original fat by interesterification, (2) constant fatty acid unsat-
uration levels, and (3) no cis–trans isomerization. Some interesting examples of
immobilized lipases for industrial applications will be illustrated in the following.
Econa® oil or diacylglycerol (DAG) oil was produced enzymatically from natu-
ral oil and contains 80% or more DAG. DAG oil was introduced to the market by
Novozymes and Kao and possesses virtually the same energy value as triacylglyc-
erol oil but is not transformed into body neutral fat. This oil represents the first
industrial application to obtain a food product using an immobilized lipase on anion
exchange resin (Houde et al., 2004).
The increased interest in the production of reduced calorie and substituted fats
has led to the production of low-calorie structured lipids with specific fatty acids at
the sn-1,3 positions by interesterifying tristearin (C18:0) with tricaprin (C10:0) or
tricaprylin (C8:0) with sn-1,3-specific immobilized lipase IM 60 from Rhizomucor
miehei on anionic exchange resin.
Cocoa butter (a mixture of oil and fat composed of triglycerides possessing pal-
mitic acid, stearic acid, and oleic acid as the major components) is a fat with a high
commercial value for the confectionery industry, in particular, chocolate, owing to
its useful properties such as gloss, snap, melting temperature, and bloom resistance.
The high price of cocoa butter is the result of its low availability. Consequently,
interesterification of abundant and less expensive fats, including illipe fat, shea
butter, sal fat, and kokum butter, offers a good alternative for the production of
cheaper cocoa butter substitutes. The introduction of palmitic or stearic acids at
the sn-1 and sn-3 positions by a selective lipase produces cocoa butter substitutes
with a cooling, melting sensation characteristic of chocolate and similar physical
properties at a lower cost. Unilever filed a patent describing a mixed hydrolysis and
synthesis reaction to produce a cocoa butter substitute using lipase immobilized
on the diatomaceous earth by adsorption, in the early 1980s (Coleman and Macrae
1980). A lipase from Rhizopus immobilized on anion exchange resin, specifically
incorporates stearic acid at the sn-1 and sn-3 positions of triglycerides in sun-
flower oil. Fuji Oil has exploited this process since 1993 to produce a cocoa butter
substitute.
Recent examples for successfully industrialized processes include lipase-cata-
lyzed production of zero-trans margarines (ADM and Novozymes) and diglyceride-
based cooking and frying oils (Kao Corp. and ADM). The zero-trans and reduced
trans oils and fats are produced on an industrial scale by transesterification using
lipase from Thermomyces lanuginosa (TL IM) in combination with a cost-effective
immobilization technology.
Some processes have been developed to produce aroma compounds in biore-
actors using lipase as the catalyst. The preparative synthesis of 35 short-chain
flavor esters by lipases from M. miehei, Aspergillus sp., C. rugosa, and Rhizopus
arrhizus was investigated in organic media. Acetic, propionic, butyric, valeric,
and caproic acids, as well as methanol, ethanol, butanol, i-pentanol, hexanol, cit-
ronellol, and geraniol were used as substrates. Most of the esters were synthesized
in good yield by at least one of the lipase preparations tested (Langrand et al.,
1990). M. miehei lipase has been adsorbed on Celite and covalently bound to nylon
to synthesize several flavoring esters in biphasic aqueous/organic media (Manjón

et al., 1991).
Several patents, summarized in Table 9.14, have been developed to produce fatty
acids by enzymatic hydrolysis of vegetable or animal oils or fats in an MBR.
9.3.5 Membrane Bioreactors in Alcoholic Beverages Processing

Alcoholic beverage production includes wine, beer, and liquor production. The
annual global production of wine is about 28,000 metric tonnes according to the sta-
tistical survey conducted by the United Nations Food and Agriculture Organization
(FAO). European countries (mainly Italy, France, and Spain) lead the ranking,
together producing about 20,000 tonnes. The United States is the other large-scale
wine producer (2500 tonnes); however, there are a large number of other countries
reporting wine production, including Chile and Australia.
The majority of efforts and applications in industrial or semi-industrial scale con-
cern beer.
The references for scaling-up efforts for winemaking are limited, probably due
to the strongly traditional character of the product. In traditional winemaking, must
fermentation takes place naturally and spontaneously through the action of yeasts
present in the raw material, which convert glucose to ethanol, CO2, and other metab-
olites. Both Saccharomyces and non-Saccharomyces yeasts are utilized for this
purpose. All yeasts are important in the winemaking process because during devel-
opment, they synthesize enzymes that directly influence the fermentation medium;
their effect may be harmful or beneficial, depending on the nature of the enzyme
and the environmental conditions. The major enzyme groups in winemaking are
oxidoreductase, pectinase, protease, and glucosidase (Table 9.15).
MBRs equipped with ultrafiltration membranes are powerful tools for studying
the stability of the β-glucosidase activity in bioconversions for winemaking. The
operational stability of biocatalyst in laboratory-scale continuous reactors was stud-
ied using β-glucosidase immobilized on chitosan pellets. Enzyme stability was not
dependent on substrate concentration and was considered satisfactory for an indus-
trial process (half-life of 1.2 years) (Gallifuoco et al., 1999).
α-l-Rhamnopyranosidase was immobilized using chitin, chitosan, and deriva-
tized chitosan, diethylaminoethyl chitosan (DE-chitosan), by cross-linking. This
biocatalyst allowed an increase in the aroma in a model wine solution containing
glycosidic precursors with a marked reduction in specificity toward tertiary mono-
terpenols as compared to the free enzyme (Spagna et al., 2001).
Cell immobilization for winemaking is a rapidly expanding research area,
although applications of this technology at the industrial scale are limited. The pur-
pose of using such techniques is to improve alcohol productivity and overall product
aroma, taste, and quality. Many materials for yeast immobilization in winemaking
have been proposed. These supports are mostly natural organic polysaccharides or
inorganic material abundant in nature. They may be used without much modification
or after minor treatment to alter their properties (porosity, surface charges, etc.); oth-
ers can be commercially synthesized. Examples of supports proposed in winemak-
ing with their advantages and disadvantages are shown in Table 9.16.
TABLE 9.14
Patents in Biocatalytic Membrane Reactors
Publication Publication
Title Inventor Applicant Number Data
Method of Sakata Masauri, Kao Corp. JP61173790 1986-08-05
hydrolyzing fat and Tanigaki
oil with lipase Masanobu,
Hashiba Ikizou,
Wada Hidetoshi
Hydrolysis of oil Tanigaki Kao Corp. JP61100196 (A) 1986-05-19
and fat with lipase Masanobu,
Hashiba Ikizou,
Wada Hidetoshi,
Sakata Masaru
Modification of oil Abe Shigemitsu, Ajinomoto KK JP63279794 (A) 1988-11-16
and fat Kawakita
Tetsuya, Tbe
Takahashi
Hironori,
Kurashige
Atsushi
Method for Nauth Kaiser R, Gen Foods Inc. CA2087243 (A1) 1993-07-28
manufacture of Kostak Barbara (US); Kraft
pre-cheese and Foods Inc. (US)
natural cheese
Production of fatty – Kao Corp. JP6038778 (A) 1994-02-15
acid
Method for catalytic Tan Tianwei, Liu Univ Beijing CN1621528 (A) 2005-06-01
synthesis of Tao, Yin Chemical
vitamin A fatty Chunhua
acid ester using
immobilized lipase
Method for Belafine Bako Pannon Egyetem HU0401348(A2) 2006-07-28
enzymatic Katalin, Nagy
hydrolysis of fats/ Endre
oils and for
complex separating
of products
Grease catalysis Xiaojun Huang, Univ Zhejiang CN101265448(A) 2008-09-17
separation biphasic Zhikang Xu,
enzyme-film Lingshu Wan, Fu
bioreactor and its Huang, Anguo Yu
preparation and
application
TABLE 9.15
Enzymes Used in Alcoholic Beverage
Enzymes Application Activity
β-Glucosidase Aroma enhancement in Hydrolyze the monoterpene
α-l-Rhamnopyranosidase winemaking glycosides
Glucose oxidase Low-alcohol, “reduced-alcohol,” Glucose oxidase consumes some
and dealcoholized wines of the glucose present, making
them unavailable for alcohol
fermentation, thereby resulting
in wine with reduced alcohol
Assess the antimicrobial activity Hydrogen peroxide generated
against acetic acid bacteria and may reduce the activity or
lactic acid bacteria growth of the S. cerevisiae used
for alcohol fermentation
Pectinase Wine clarification Degradation of pectin
Protease Wine clarification Protein hydrolysis
Few examples of industrial-level winemaking are reported. Takaya et al. (2002)

studied the efficiency of two MBR systems for continuous dry winemaking. Their
first system was a single-vessel bioreactor in which cells were entrapped by a cross-
flow-type microfilter and the second configuration included two vessels: one oper-
ated as a continuous stirred-tank reactor and the other an MBR. The single-vessel
system was found unsuitable for dry winemaking due to high residual sugar con-
centrations, while the double-vessel system was suitable and had 28 times higher
productivity than a batch system.
Malolactic fermentation (MLF) is an important secondary reaction in wine-
making and generally occurs just after alcoholic fermentation has been completed.
Although MLF is generally done for dry red wines, it can also be carried out for
some dry white wines such as Chardonnay, Sauvignon Blanc, and Pinot Gris, but
it is not recommended for sweeter wines such as Riesling, Gew-ürztraminer, and
Muscat. During MLF, l-malic acid is converted to l-lactic acid and carbon dioxide
by lactic acid bacteria, predominately of the genera Oenococcus, Lactobacillus,
and Pediococcus. Lactic acid as a monoacid is “less acidic” than malic acid and
as a consequence of this reaction, the total acidity of wine decreases (deacidifica-
tion or demalication), leading to improvement in the organoleptic properties and
biologic stability of the wines. In addition, from several other components of wine,
the production of by-products, mainly acetaldehyde, acetic acid, ethyl acetate,
diacetyl, and higher alcohols, is considered to affect wine flavor positively. After
MLF, the wine flavor profile is characterized as being more smooth, round, and
complex. The improved stability of the product after MLF is due to the reduced
possibility of microbial spoilage, by inhibition of microbial growth due to the for-
mation of lactic acid and the consumption of reducing residual sugars. Without
controlled MLF, wine not adequately preserved with SO2 might go through the
process in the bottle by the wild bacterial microflora, which would transform resid-
ual sugars into lactic acid, acetic acid, and other by-products, causing undesirable
338
TABLE 9.16
Supports Materials Used in Winemaking
Support Material Microorganism Disadvantages Advantages References
Inorganic Mineral kissiris S. cerevisiae High Usually abundant and cheap, improved fermentation Bakoyianis et al.
supports concentrations productivity and wine aroma (1992, 1993);
of mineral Argiriou et al.
residues found (1996)
Porous in the product Loukatos et al.
α-alumina (2000)
Glass pellets S. cerevisiae and Ogbonna et al.
covered with a Schizosaccharomyces (1989)
membrane of pombe
alginates
Organic supports Calcium alginate S. cerevisiae High cost and Improve sparkling wine technology Colagrande et al.
low chemical (1994); Suzzi
and mechanical et al. (1996)
Candida stellata and stability that Ciani and Ferraro
S. cerevisiae leads to cell and (1996)
residues release
in the wine
Natural supports Delignified Saccharomyces Low chemical A significant increase in fermentation rates. Less Bardi and
cellulose cerevisiae and mechanical higher-alcohol contents and increased ethyl acetate Koutinas (1994)
Gluten pellet Saccharomyces stability concentrations on total volatiles in produced wines Bardi et al.
cerevisiae improved organoleptic quality and a distinct fruity (1996a,b, 1997)
aroma. Food-grade purity, very cheap, abundant,
and easy to prepare industrially
wine turbidity and development of off-flavors. There are generally three methods
employed to produce MLF during the maturation process: (1) spontaneous MLF
using indigenous bacteria, (2) starter cultures of MLF, and (3) high cell concentra-
tion of MLF bacteria. In the third method, the MLF is carried out directly at a high
concentration of cells without the necessity of cell growth, using (a) free cells, (b)
immobilized cells, or (c) an MBR. In Table 9.17, examples of bioreactors used in
winemaking are reported.
There are only few reports on MBR systems in the wine-making process. A sim-
ple 300 cm3 cell-recycle MBR system was applied for conducting continuous MLF
of red wine (Gao and Fleet, 1995). A membrane module of 240 cm2 surface area and
0.45 μm pore size acted as the filtration unit. After several batch cultures had been
transferred to a vessel in the MBR system, the system was used continuously for 8 h
during the day, after which it was stored overnight at 4°C and used again the next
day. The reactor, with a charge of 1010 cfu/cm3 Oenococcus oeni and operating at a
flow rate of 0.36 dm3/h, was run for 56 h, giving >95% degradation of l-malic acid
in a range of red and white wines. The stability of malic acid-degrading activity and
long-term performance of the reactor varied with O. oeni strain, wine, and tempera-
ture. An MBR with a 35-L working volume was made up in a vessel coupled to a
1-m2 0.2 μm ceramic membrane module using two pumps, one to give high cross-
flow velocity (1 m/s) and the other to pressurize the system (up to 1 bar) and recycle
flow back to the reactor vessel. Using O. oeni and Lactobacillus brevis cultured in
the MBR, it has been possible to run the MLF with over 50% malate removal for over
40 days at residence times between 3 and 12 h. The system was robust and showed
little loss of performance over this period (Lovitt et al., 2006). The use of immobi-
lized Lactobacillus bulgaricus cells in the vegetative stage on polymeric membranes
made of polysulfone (100 kDa cutoff) was investigated by Giorno et al. (2002). The
BMR was tested with white wine. It was demonstrated that the system was able to
simultaneously adjust the pH and sterilize the wine during its passage through the
cell-loaded microfiltration membrane (Figure 9.14).
Considering the general advantages that MBR technology offers, including the
reduction of the risk of undesirable flavor formation, for example, acetic acid or
diacetyl, it is particularly suitable for winemaking application. In fact, MBRs may
offer practical advantages in the deacidification of wines and ciders. The ultimate
acceptance of the technology will depend on its impact on the sensory quality of the
final product.
In beer, cider, potable alcohol, and distillates, the use of MBR technology is lim-
ited, but the potentiality of the technology could be particularly suitable to solve
some problems related to the development on an industrial scale. For example, the
application of MBR technology in beer fermentation can solve some practical prob-
lems related to contamination risk and variation in beer flavors. In traditional cider
production by natural fermentation, the main drawback is the production of an unsta-
ble product of variable quality. The introduction of MBR in cider MLF is expected to
improve cider quality and stability, increasing productivity and accelerating matura-
tion. Some preliminary works are present in the literature (Jung and Lovitt, 2010). In
Table 9.18, some useful information is reported about the material and the microor-
ganisms used in beer, cider, and potable alcohol production.
340
TABLE 9.17
Bioreactors Used in Winemaking
Microorganism Support Material Reactor References
Free cell at high Membrane Oenococcus oeni – MBR Gao and Fleet (1995)
concentration bioreactor Oenococcus oeni and Ceramic membrane Lovitt et al. (2006)
Lactobacillus brevis
Batch system Oenococcus oeni – Screw tubes Gao and Fleet (1994); Lafon-lafourcade
(1970); Maicas et al. (2000)
– Shake flask Maicas et al. (2000)
Continuous system Lactobacillus sp. – CSTR Caillet and Vayssier (1984)
Oenococcus oeni – Maicas et al. (1999)
Immobilized cells Batch system Oenococcus oeni k-Carrageenan Shake flask McCord and Ryu (1985)
Polyacrylamide Rossi and Clementi (1984)
Cellulose sponge Maicas et al. (2001)
Continuous system Oenococcus oeni k-Carrageenan CSTR Spettoli et al. (1987)
Lactobacillus sp. Crapisi et al. (1987)
Oenococcus oeni Crapisi et al. (1987)
Calcium alginate Cuenat and Villetaz (1984)
Shieh and Tsay (1990)
Spettoli et al. (1987)
Spettoli et al. (1982)
Fluidized system Lactobacillus sp. FBR Naouri et al. (1991)
Note: MBR: membrane bioreactor; CSTR: continuous stirred-tank reactor; FBR: fluidized-bed reactor.
TABLE 9.18
Support Materials, Microorganisms, Bioreactor Type in Beer and Cider Making, and Potable Alcohol Production
Support Material Microorganism Bioreactor Type Application Reaction Type References
Inorganic Porous, spherical glass beads S. cerevisiae Tubular packed-bed reactor Beer making AF Yamauchi et al. (1995a,b)
supports S. cerevisiae (S. uvarum) Fluidized-bed reactor Tata et al. (1999)
Cylindrical porous silicon S. cerevisiae (S. uvarum) Cartridge reactors Tata et al. (1999)
Mineral kissiris S. cerevisiae Batch-stationary Potable Kana et al. (1989b)
Multistage fixed-bed tower alcohol Bakoyianis and Koutinas
reactor (1996); Koutinas et al. (1997)
γ-Alumina pellets Batch-stationary Kana et al. (1989a)
Stainless-steel wire spheres Bekers et al. (1999)
Stainless-steel wire spheres; Zymomonas mobilis Bekers et al. (2001)
Al2O3 granules
Ceramic membrane L. brevis and O. oeni Membrane bioreactor Cider making MLF Jung and Lovitt (2010)
Organic Calcium pectate, k-alginate; S. cerevisiae Gas-lift reactor Beer making AF Smogrovicová and Dömény
supports DEAE-cellulose (1998)
Calcium alginate S. cerevisiae – Pátková et al. (2000)
O. oeni Sleeved reactor Cider making MLF Cabranes et al. (1998)
Erlenmeyer flask Herrero et al. (2001)
S. cerevisiae + O. oeni Herrero et al. (1999)
Fluidized-bed reactor Nedovic et al. (2000)
Calcium pectate S. uvarum Gas-lift reactor Smogrovicova et al. (1998)
(Continued)
341
342
TABLE 9.18 (Continued)

Support Materials, Microorganisms, Bioreactor Type in Beer and Cider Making, and Potable Alcohol Production
Support Material Microorganism Bioreactor Type Application Reaction Type References
Natural Delignified cellulose S. cerevisiae Batch-stationary Beer making AF Bardi et al. (1996a)
supports Packed-bed reactor Bekatorou et al. (2001b)
Gluten pellet Fluidized-bed reactor Bardi et al. (1997)
Porous cellulose carriers S. pastorianus Batch-shaken flasks Potable Sakurai et al. (2000)
alcohol
Neutral cross-linked S. cerevisiae and Packed-bed reactor Cider making AF MLF Scott and O’Reilly (1996)
cellulose L. plantarum
Luffa cylindrica sponge S. cerevisiae + Candida Potable AF Ogbonna et al. (1997)
chitosan brassicae alcohol
Agar layer; microporous S. cerevisiae + Candida Two-chambered reactor; Lebeau et al. (1997)
membrane filters brassicae batch
Wood blocks S. cerevisiae Packed-bed reactor Guenette and Duvnjak (1996)
Dried figs S. cerevisiae Bekatorou et al. (2001a)
Note: AF: alcoholic fermentation; MLF: malolactic fermentation.

9.3.6 Membrane Bioreactors for Wastes Coming

from Food Processing Industry
Biological treatment technologies have been utilized in wastewater remediation for

over a century. With the emergence of less expensive and more effective membrane
modules and the implementation of ever-tightening water discharge standards, mem-
brane systems regained interest. There are several advantages associated with the
MBR, which make it a valuable alternative over other treatment techniques. First
of all, the retention of all suspended matter and most soluble compounds within the
bioreactor leads to excellent effluent quality capable of meeting stringent discharge
requirements and opening the door to direct water reuse. The possibility of retaining
all bacteria and viruses results in a sterile effluent, eliminating extensive disinfection
and the corresponding hazards related to disinfection by-products. The membrane
not only retains all biomass but also prevents the escape of exocellular enzymes and
soluble oxidants, creating a more active biological mixture capable of degrading a
wider range of carbon sources. MBRs eliminate process difficulties and problems
associated with settling, which is usually the most troublesome part of wastewater
treatment.
The potential for operating the MBR at very high solid retention times without
having the obstacle of settling allows high biomass concentrations in the bioreactor.
Consequently, higher-strength wastewater can be treated and lower biomass yields
are realized. This also results in more compact systems than conventional processes,
significantly reducing plant footprint and making it desirable for water recycling
applications. High-molecular-weight soluble compounds, which are not readily bio-
degradable in conventional systems, are retained in the MBR. Thus, their residence
time is prolonged and the possibility of oxidation is improved.
Concentration polarization and other membrane fouling problems can lead to
frequent cleaning of the membranes, which stop the operation and require clean
water and chemicals. Another drawback can be problematic waste activated sludge
disposal. Since the MBR retains all suspended solids and most soluble organic mat-
ter, waste activated sludge may exhibit poor filterability and settleability proper-
ties. Additionally, when operated at high solid retention times, inorganic compounds
accumulating in the bioreactor can reach concentration levels that can be harmful to
the microbial population or membrane structure.
From an environmental perspective, the majority of food-processing facili-
ties are characterized by very high water consumption and high-organic-strength
wastewater generation. Major waterborne pollutant loadings are biological/chemical
oxygen demand, total suspended solids, fats–oils–greases, and nutrients. Most facili-
ties employ on-site primary treatment prior to sending their wastewater to munici-
pal wastewater treatment plants. Large volumes of high-strength wastewater both
increase the cost of disposal for food-processing facilities and present difficult chal-
lenges for the municipal wastewater treatment plant operators.
Since MBRs are capable of treating high-strength wastewater, attempts were
made to evaluate their effectiveness with food-processing effluents. Table 9.19 sum-
marizes some applications of MBRs in the treatment of food industry wastewater.
TABLE 9.19
Membrane Bioreactors Used in Food Industry Wastewater Treatment
Membrane
Operation
Source Module Membrane Size of Country of
Wastewater Configuration Configuration Operation Application References
Pomegranate Submerged Hollow fiber Lab-scale China Rongqing et al.
juice pilot (2010)
Olive mill Microfiltration/ Monochannel Tunisia and Dhaouadia and
external France Marrot (2008)
Seafood Microfiltration/ Flat sheet Thailand Sridang et al.
processing submerged (2006)
Food Hollow fiber China Wang et al.
processing (2005)
factory
Dairy Batch scale South Korea Bae et al. (2003)
industry
Fermentation Ultrafiltration/ Rotary disk Japan Lu et al. (2000)
external
Food Microfiltration/ – Full scale USA Cantor et al.
ingredients submerged (1999)
Maize/egg Ultrafiltration/ South Africa Ross et al. (1992)
processing external
Liquor Pilot scale Japan Nagano et al.
production (1992)
In the early years, external or side-stream membrane unit was the most used
plant configuration. At the time of these applications, external membranes were
thought to be more suitable for high temperature, high organic strength, and dif-
ficult-to-filter waste streams. High-pressure requirements and capital investment
costs resulted in the lack of large-scale implementation of many such systems. The
emergence of submerged MBRs that utilize fairly economical polymer-based mem-
branes and require less energy than external MBRs have revolutionized municipal
wastewater treatment and has tremendous potential in larger-scale, high-volume-
throughput facilities across the globe. There is still a large use of both side-stream
and submerged membrane modules. The potential of reusing the MBR product
water on-site for washing or transport purposes offers many cost benefits such as
reduced freshwater requirements, lower sewer costs, and possibility for direct dis-
charge to surface waters.
9.3.6.1 Valorization of Waste by Membrane Bioreactor

Waste and by-products contain a huge amount of high-added-value bioactive com-
ponents as valorizable substances from which novel products with key nutritional,
therapeutic, and defense properties can be obtained. MBR technology offers new
solutions not only in waste treatment, but also in the production and/or recovery of
TABLE 9.20
Olive Oil Production Methods
Three-Phase Decanter Two-Phase Decanter
Process Process
Oil extraction capacity (%) 85 86
Vegetable water (L/100 kg of olives) 97.2 8.3
Pomace (kg/100 kg of olives) 50.7 72.5
functional biomolecules that can be used in food, pharmaceutical, and biotechnology

industries.
An important source of valuable compounds can be recovered during olive oil
production. In this process, a considerable amount of water is employed during the
continuous washing of the olive paste with warm water prior to the process of sepa-
ration of the oil from the paste (malaxation process). The water content depends on
the olive oil production methods used, as described in Table 9.20.
Up to now, a large variety of methods have been suggested for the treatment
of waste coming from plant material processing, including composting, anaerobic
digestion, aerobic treatment, mixing with municipal wastewater, direct land applica-
tion, chemical oxidation in combination with biological treatment, adsorption, and
even the utilization of fungi species, etc. However, the treatment of olive oil mill
waste (OMW) is extremely difficult due to its large volume and increased concentra-
tion of organic matter (BOD ranging between 15,000 and 50,000 mg/L and chemical
oxygen demand (COD) ranging in values as high as about 220 g/L). The major factor
of the environmental problem is the high concentration of polyphenols. These com-
pounds present phytotoxicity, toxicity against aquatic organism, or suppression of
soil microorganisms, and are difficult to decompose. Although polyphenols can be
considered an environmental problem, they are, on the other hand, a very important
category of antioxidant phytochemicals.
After olive oil production, the phenolic compounds present in the fruit are distrib-
uted between the olive oil (2%) and waste material (98%), which is further divided
into solid waste (45%) and wastewater (53%). In particular, the average composition
of OMWW is reported in Table 9.21 (Visioli et al., 1998, 1999). The composition of
the OMWW phenols compared to the phenols contained in the olives and in the olive
oil is different, and it is determined largely by their partition coefficient.
TABLE 9.21
Average Composition of Olive Mill Wastewater
Water (%) 83
Minerals (carbonates, phosphates, potassium and sodium salts, etc.) (%) ∼2
Organic compounds (%) ∼15
• Sugars ∼2–8
• Proteins, pectins, macromolecules, etc. ∼1.2–5
• Polyphenols ∼0.5–1.8
TABLE 9.22
Major Biophenols in OMW
Biophenol Bioactivity
Hydroxytyrosol Antioxidant, cardioprotective, and antiatherogenic
Chemopreventive, antimicrobial, anti-inflammatory
Skin bleaching
Oleuropein Antioxidant, antiatherogenic, and cardioprotective
Hypoglycemic, antihypertensive, antimicrobial, and antiviral
Anti-inflammatory, cytostatic, endocrinal activity, enzyme modulation
Tyrosol Antioxidant, anti-inflammatory, antiatherogenic, cardioactive
Caffeic acid Antioxidant, chemoprotective, antiatherogenic, antimicrobial,
anti-inflammatory
Antidepressive-like activity
Vanillic acid Antioxidant, antimicrobial
Verbascoside Antioxidant, chemoprevention, cardioactive, antihypertensive,
anti-inflammatory
Antiatherogenic, sedative
Elenolic acid Antimicrobial, antiviral
p-Coumaric acid Antioxidant, antimicrobial, chemoprevention
Catechol Phytotoxic, antimicrobial, carcinogenic activity, antioxidant, and anticancer
Rutin Antioxidant, antiatherogenic, anti-inflammatory, chemopreventive
More than 30 biophenols and related compounds have been identified in OMW in
Table 9.22. The major biophenols in OMW are reported with their active properties.
The biophenol hydroxytyrosol is the most active component of OMW extracts,
which is amphiphilic and thus acts at the oil–water interface and in systems where
both oil and water are present like emulsions (Auroma, 1997). Hydroxytyrosol has
also been referred to as a potent chemopreventive agent (Manna et al., 2000), and is
considered to be the component present in olive oil residues with higher antioxidant
potency. Manna et al. (2000) proved that this compound is able to protect several
cellular human systems from the toxicity induced by reactive oxygen species. The
ability of hydroxytyrosol to induce DNA modifications has also been investigated
(Deiana et al., 1999). Visioli et al. (2000) have also shown that, depending on the
dosage, this biophenolic compound is well absorbed by humans, being excreted in
urine as glucuronate conjugates.
Oleuropein, the ester 2′-(3′,4′-dihydroxypheny-1)ethanol (hydroxytyrosol), is
present in the olive tree (Olea europaea) and in particular in the leaves in high
amounts (60–90 mg/g dry weight) although it has also been found in peel, pulp,
and seed (Soler-Rivas et al., 2000) and largely in the OMW. This compound con-
fers resistance to pathogen attack and has been individuated as the bitter principle
that must be eliminated from olives before they can be made palatable. Oleuropein
is hydrolyzed by the action of β-glucosidase; its hydrolysis products (elenoic acid
and aglycone) inhibit the activity not only of Lactobacillus plantarum strains but
also of other bacteria such as L. brevis, Leuconostoc mesenteroides, Geotrichum
candidum, Rhizopus sp., Rhizoctonia solani, and Pediococcus cerevisiae involved

in the lactic fermentation of green olives. The dyaldeidic form of elenoic acid linked
to hydroxytyrosol, an isomer of oleuropein aglycon and hydroxytyrosol, has been
identified, and quantitatively they represent the most important secoiridoids pres-
ent in the oil. The former group of compounds was mainly held responsible for the
antioxidant capacity of the olive oil (Soler-Rivas et al., 2000). The antimicrobial
activity of oleuropein and its hydrolysis products has been demonstrated toward the
inhibition of the production of enterotoxin B by Staphylococcus aureus, the growth
of Salmonella enteriditis, and the germination and outgrowth of Bacillus cereus
T spores. The bactericidal effect was observed against a broad spectrum of other
Gram-positive and Gram-negative bacteria. The possibility to reprocess the oleu-
ropein present in OMW during olive oil production is of great interest, because it
permits the recovery of a substance discharged and to produce high-added-value
compounds.
Other studies demonstrated that the hydrolysis products of oleuropein have a
much more marked inhibitory effect than oleuropein. In particular, the aglycon, pro-
duced by oleuropein hydrolysis, is well known as a pharmacologically active mol-
ecule. In fact, it is described for its potential application as an antimicrobial agent in
some fairly common diseases of olive trees and also for its strong active antioxidant
property (Visioli et al., 1995; Gordon et al., 2001; Rodis et al., 2002; Paiva-Martins
et al., 2003; Vissers et al., 2004).
β-Glucosidases, the enzyme responsible for oleuropein hydrolysis, for the produc-
tion of the above-mentioned active compounds, belongs to the large family of hydro-
lases. The broad optimum pH and temperature range make this enzyme particularly
useful for application in biotechnology processes and in particular for use in BMRs
(Table 9.23).
This enzyme can also hydrolyze the monoterpene glycosides that naturally occur
in wines and determine aroma enhancement, and in addition is an important enzyme
involved in the degradation of cellulose to produce ethanol.
β-Glucosidase from different sources has been studied in various systems, includ-
ing MBR, free or attached to different supports (Yeoh, 1991; Montero and Romeu,
1993; Nagamoto et al., 2005). The immobilization of β-glucosidase from almond in
nylon tubing for the hydrolysis of cellulose was carried out in a membrane reactor
using nylon tubing and measuring the glucose production during the time (Hsuanyu
and Laidler, 1986). β-Glucosidase from almond was also immobilized on polysul-
fone hollow-fiber membranes (Mazzei et al., 2009, 2010, 2012) for the development
of a BMR; the kinetic performance of the immobilized system was compared with
a stirred-tank reactor. The results obtained demonstrated that the heterogenized
enzyme has the same kinetic parameters of a batch system, maintaining the same
activity for about 30 h of continuous operation. A qualitative analysis was also evalu-
ated on an immobilized enzyme by measuring the activity in situ and by monitoring
the spatial distribution of the enzyme on the membrane. This was possible by inte-
grating molecular biology and membrane techniques (Mazzuca et al., 2006).
The biocatalytic membrane system, previously described, was implemented to
produce phenolic compounds, responsible for olive oil antioxidant properties, such
as the isomer oleuropein aglycon. The difficulty related with the production of this
TABLE 9.23
Use of β-Glucosidase in Bioreactor Technology
Biocatalyst System Support Application References
Cassava β-glucosidase STR Hydrophilic Antioxidant Yeoh (1991)
photo-cross- compounds
linkable resins
β-Glycosidase from Chitosan Briante et al.
Sulfolobus (2000)
solfataricus
Candida molischaina Duolite A-568 Aromatic potential Gueguen et al.
35M5N β-glucosidase resin of fruit juice and (1996)
wines
β-Glucosidase Polymer Wine aroma Gallifuoco
enhancement et al. (1998)
MBR Chitosan pellets Gallifuoco
Cellulose acetate et al. (1999)
membrane
β-Glucosidase from MBR Nylon tubing Aroma production Hsuanyu and
almond Laidler (1986)
STR Concanavalin A Kinetic study Montero and
sepharose Romeu (1993)
BMR Polysulfone Fitoterapic Mazzei et al.
membrane (2009, 2010)
Note: MBR: membrane bioreactor; BMR: biocatalytic membrane reactor; STR: stirred-tank reactor.
phytotherapic by β-glucosidase hydrolysis is connected with its low solubility in

water. A new configuration of biocatalytic membrane system was created, integrat-
ing BMR with ME concepts. This system was the first example in the literature for
the production of low-water-soluble compounds by hydrolysis and its simultaneous
isolation from the reaction mixture by creating a simulated in vivo multiphasic sys-
tem (Mazzei et al., 2010, 2012). A schematic representation of the innovative system
is reported in Figure 9.15. The results obtained demonstrated that the isomer of oleu-
ropein aglycon was produced and extracted into the organic phase of water-in-oil
emulsions also processing OMWW containing oleuropein (Conidi et al., 2014).
9.3.7 Membrane Bioreactors in Integrated Membrane Operations

Integrated membrane processes are generally used to treat a heterogeneous fluid
system, which required a sequential separation process in order to decrease the solu-
tion complexity.
In addition to classical pressure-driven membrane operations such as microfil-
tration (MF)/UF/nanofiltration (NF), forward osmosis (FO), membrane or osmotic
distillation (MD/OD), ME, BMR, and ED have emerged as new technologies with
great potential of integration.
Dispersed phase
Oleuropein
Enzyme loaded membrane
Unreacted Products
substrate
Continuous phase
II unit:
Membrane
Longitudinal section of emulsificator
biocatalytic membrane
Integrated membrane system

I unit:
Biocatalytic Aqueous phase (oleuropein)
membrane
reactor IN
Enzyme loaded membrane

Isomer of Unreacted
oleuropein oleuropein
aglycon
Aglycon Glucose
in water
Out
Organic phase
FIGURE 9.15 Cross- and longitudinal section of innovative biocatalytic membrane that is the integration of a biocatalytic membrane with a membrane
emulsificator. (After Mazzei, R., Drioli, E., Giorno, L. 2010. J. Membr. Sci., 352, 166–172.)
349
This can enhance the recovery, concentration, and formulation of high-added-

value coproducts with reclamation of good-quality water.
An example of an integrated membrane process has been proposed for the sepa-
ration and purification of organic acid from a biomass fermentation process, which
includes three steps: (1) clarification of fermentation broth, (2) organic acid separation
(NF and RO), and (3) dewatering (FO) that can be applied to achieve energy-efficient
and environmental-friendly organic acid removal and recovery (Cho et al., 2012).
A commercially unavailable antioxidant compound was also produced by an inte-
grated membrane process consisting of MF/UF/BMR (Conidi et al., 2014), starting
from OMWW. In particular, the biocatalytic system is an example of process inten-
sification, in which the catalysis of oleuropein, thanks to the biocatalytic membrane,
was coupled to an ME process with the aim to produce and simultaneously extract
the poor-water-soluble compound of interest. By this integrated process, it was pos-
sible to recover water-insoluble oleuropein aglycon into the organic phase.
Other innovative integrated membrane processes, such as MD and MBR
(Phattaranawik et al., 2008), OD and MBR (Holloway et al., 2015), and ED and
MBR (Wisniewski et al., 2002), are at the moment used in wastewater treatment and
water reuse. However, these systems represent advanced strategies with potential
future application in the food field, since they fully respond to the development of
sustainable systems, are able to intensify processes with lower productive costs, and
are able to obtain high-quality products.
9.4 CONCLUSIONS
Despite the great advantages that MBR technology offers compared to the traditional
systems, few examples are reported of the development at the food industrial scale,
such as lactose and pectin hydrolysis in milk and juice production and wastewater
treatment. Other sectors whose technology robustness has been proved by patent
development include the production of fatty acids and active peptides from casein.
MBR, where the membrane acts as separation unit, is the main configuration
used for food application, while wastewater treatment is the main research field of
application.
This trend is guided from the high need of potable water and from a restrictive
legislation in the development of sustainable processes, with low economic and envi-
ronmental impact.
A further future development of MBR technology will be pushed by a multidisci-
plinary approach between membrane biotechnology, process design, and modeling.
REFERENCES
Alkorta, I., Garbisu, C., Llama, M.J., Serra, J.L. 1995. Betatranselimination of citrus pectin
catalyzed by Penicillium italicum pectin lyase in a membrane reactor. Appl. Biochem.
Biotechnol., 55, 249–259.
Argiriou, T., Kanellaki, M., Voliotis, S., Koutinas, A.A. 1996. Kissiris-supported yeast cells:
High biocatalytic stability and productivity improvement by successive preservations
at 0°C. J. Agric. Food Chem., 44, 4028–4031.
Auroma, O.I. 1997. Extracts as antioxidant prophylactic agents. Int. News Fats Oils Relat.
Mater., 8, 1236–1242.
Azarkan, M., Amrani, A., Nijs, M., Vanderneers, A., Zerhouni, S., Smolders, N., Looze, Y.
1997. Carica papaya latex is a rich source of a class II chitinase. Phytochemistry, 46,
1319–1325.
Bae, T., Han, S.-S., Tak, T.-M. 2003. Membrane sequencing batch reactor system for the treat-
ment of dairy industry wastewater. Process Biochem., 39, 221–231.
Bakoyianis, V., Kana, K., Kalliafas, A., Koutinas, A.A. 1993. Low temperature continuous
wine-making by kissiris-supported biocatalyst: Volatile by-products. J. Agric. Food
Chem., 41, 465–468.
Bakoyianis, V., Kanellaki, M., Kalliafas, A., Koutinas, A.A. 1992. Low temperature wine-
making by immobilized cells on mineral kissiris. J. Agric. Food Chem., 40, 1293–1296.
Bakoyianis, V., Koutinas, A.A. 1996. A catalytic multistage fixed-bed tower bioreactor in an
industrial-scale pilot plant for alcohol production. Biotechnol. Bioeng., 49, 197–203.
Bardi, E., Koutinas, A.A. 1994. Immobilization of yeast on delignified cellulosic material for
room temperature and low-temperature wine making. J. Agric. Food Chem., 42, 221–226.
Bardi, E., Koutinas, A.A., Kanellaki, M. 1997. Room and low temperature brewing with yeast
immobilized on gluten pellets. Process Biochem., 32, 691–696.
Bardi, E., Koutinas, A.A., Soupioni, M., Kanellaki, M. 1996a. Immobilization of yeast on
delignified cellulosic material for low temperature brewing. J. Agric. Food Chem., 44,
463–467.
Bardi, E.P., Bakoyianis, V., Koutinas, A.A., Kanellaki, M. 1996b. Room temperature and
low temperature wine making using yeast immobilized on gluten pellets. Process
Biochem., 31, 425–430.
Bekatorou, A., Koutinas, A.A., Kaliafas, A., Kanellaki, M. 2001a. Freeze-dried
Saccharomyces cerevisiae cells immobilized on gluten pellets for glucose fermenta-
tion. Process Biochem., 36, 549–557.
Bekatorou, A., Koutinas, A.A., Psarianos, K., Kanellaki, M. 2001b. Low-temperature brewing
by freeze-dried immobilized cells on gluten pellets. J. Agric. Food Chem., 49, 373–377.
Bekers, M., Laukevics, J., Karsakevich, A., Ventina, E., Kaminska, E., Upite, D., Vina, I.,
Linde, R., Scherbaka, R. 2001. Levan-ethanol biosynthesis using Zymomonas mobilis
cells immobilized by attachment and entrapment. Process Biochem., 36, 979–986.
Bekers, M., Ventina, E., Karsakevich, A., Vina, I., Rapoport, A., Upite, D., Kaminska, E.,
Linde, R. 1999. Attachment of yeast to modified stainless steel wire spheres, growth of
cells and ethanol production. Process Biochem., 35, 523–530.
Bélafi-Bako, K., Eszterle, M., Kiss, K., Nemestóthy, N., Gubicza, L. 2007. Hydrolysis of pec-
tin by Aspergillus niger polygalacturonase in a membrane bioreactor. J. Food Eng., 78,
438–442.
Bhardwaj, A., Lee, J., Glauner, K., Ganapathi, S., Bhattacharyya, D., Allan Butterfield, D.
1996. Biofunctional membranes: An EPR study of active site structure and stability
of papain non-covalently immobilized on the surface of modified poly(ether) sulfone
membranes through the avidin-biotin linkage. J. Membr. Sci., 119, 241–252.
Bishop, P.D., Pearce, G., Bryant, J.E., Ryan, C.A. 1984. Isolation and characterization of the
proteinase inhibitor-inducing factor from tomato leaves. Identity and activity of poly-
and oligogalacturonide fragments. J. Biol. Chem., 259(21), 13172–13177.
Botta, B., Monache, G.D., Riccardi, P., Vitali, A., Vinciguerra, V., Misiti, D., Kutney, J.P.,
Stoynov, N. 1996. Studies with plant cell cultures of Cassia didymobotrya: VII.
Enzyme-catalyzed biotransformation of dibenzylbutanolides to podophyllotoxin ana-
logues and related compounds. Heterocycles, 2443–2456.
Bouhallab, S., Touzé, C. 1995. Continuous hydrolysis of caseinomacropeptide in a membrane
reactor: Kinetic study and gram-scale production of antithrombotic peptides. Lait, 75,
251–258.
Briante, R., La Cara, F., Febbraio, F., Baroni, R., Piccialli, G., Carolla, R., Mainolfi, P. et al.
2000. Hydrolysis of oleuropein by recombinant β-Glycosidase from hyperthermophilic
archaeon Sulfolobus solfataricus immobilized on chitosan matrix. J. Biotechnol., 77,
275–286.
Cabranes, C., Moreno, J., Mangas, J.J. 1998. Cider production with immobilized Leuconostoc
oenos. J. Inst. Brew., 104, 127–130.
Cabrera-Padilla, R.Y., Pinto, G.A., Giordano, R.L.C., Giordano, R.C. 2009. A new concep-
tion of enzymatic membrane reactor for the production of whey hydrolysates with low
contents of phenylalanine. Process Biochem., 44, 269–276.
Caillet, M.M., Vayssier, Y. 1984. Utilisation des biomasses de bactéries lactiques pour le
déclenchement de la fermentation malo-lactique. Rev. Fr. Oenol. 24, 65–69.
Cantor, J., Sutton, P.M., Steinheber, R., Myronyk, M. 1999. Membrane filtration: An inter-
nal membrane bioreactor helps solve treatment plant’s operational problems. Ind.
Wastewater, 7(2), 18–22.
Capasso, R., Evidente, A., Visca, C., Gianfreda, L., Maremoti, M., Greco, G. 1997. Production
of glucose and bioactive aglycone by chemical and enzymatic hydrolysis of purified
oleuropein from Olea europaea. Appl. Biochem. Biotechnol., 61, 365–377.
Caponio, F., Alloggio, V., Pallavicini, C. 1998. Modification of goat milk fat triglycerides by
immobilized lipase. Fett/Lipid, 100(3), 74–78.
Carrin, M.E., Ceci, L.N., Lozano, J.E. 2000. Effects of pectinase immobilization during hol-
low fiber ultrafiltration of apple juice. J. Food Process Eng., 23, 281–298.
Carrin, M.E., Ceci, L.N., Lozano, J.E. 2001. Ultrafiltration fibers like bioreactors. Latin Am.
Appl. Res., 31, 241–245.
Cheison, S.C., Wang, Z., Xu, S. 2006. Hydrolysis of whey protein isolate in a tangential flow
filter membrane reactor: II. Characterisation for the fate of the enzyme by multivariate
data analysis. J. Membr. Sci., 286, 322–332.
Chiang, W.D., Cordle, C.T., Thomas, R.L. 1995. Casein hydrolysate produced using a formed-
in-place membrane reactor. J. Food Sci., 60, 1349–1352.
Chiang, W.D., Shih, C.J., Chu, Y.H. 1999. Functional properties of soy protein hydrolysate
produced from a continuous membrane reactor system. Food Chem., 65, 189–194.
Cho, Y.H., Lee, H.D., Park, H.B. 2012. Integrated membrane processes for separation and
purification of organic acid from a biomass fermentation process. Ind. Eng. Chem. Res.,
51(30), 10207–10219.
Ciani, M., Ferraro, L. 1996. Enhanced glycerol content in wines made with immobilized
Candida stellata cells. Appl. Environ. Microbiol., 62, 128–132.
Colagrande, O., Silva, A., Fumi, M.D. 1994. Recent applications of biotechnology in wine
production. Rev. Biotechnol. Progr., 10, 2–18.
Coleman, M.H.m., Macrae, A.R. 1980. UK Patent No 1577933.
Conidi, C., Mazzei, R., Cassano, A., Giorno, L. 2014. Integrated membrane system for the
production of phytotherapics from olive mill wastewaters. J. Membr. Sci., 454, 322–329.
Crapisi, A., Spettoli, P., Nuti, M.P., Zamorani, A. 1987. Comparative traits of Lactobacillus
brevis, Lactobacillus fructivorans and Leuconostoc oenos immobilized cells for the
control of malolactic fermentation in wine. J. Appl. Bacteriol., 63, 513–521.
Cuenat, P., Villetaz, J.C. 1984. Essais de fermentation malolactique des vins par bactéries
lactiques immobilisées du genre Leuconostoc. Rev Suisse Vitic Arboric Hortic 16,
145–151.
Deiana, M., Aruoma, O.I., Bianchi, M.P., Spencer, J.P.E., Kaur, H., Halliwell, B., Aeschbach,
R., Banni, S., Dessì, M.A., Corongiu, F.P. 1999. Inhibition of peroxynitrite dependent
DNA base modification and tyrosine nitration by the extra virgin olive oil-derived anti-
oxidant hydroxytyrosol. Free Rad. Biol. Med., 26, 762–769.
Dhaouadia, H., Marrot, B. 2008. Olive mill wastewater treatment in a membrane bioreactor:
Process feasibility and performances. Chem. Eng. J., 145, 225–231.
Doleyres, Y., Paquin, C., LeRoy, M., Lacroix, C. 2002. Quantitative determination of the
spatial distribution of pure and mixed strain immobilized cells in gel beads by immu-
nofluorescence. Appl. Microbiol. Biotechnol., 60, 168–173.
Drioli, E., Giorno, L. 1999. Biocatalytic Membrane Reactors: Application in Biotechnology
and the Pharmaceutical Industry, Taylor & Francis Publisher, London, UK.
Faber, K. 2000. Biotransformations in Organic Synthesis, 4th ed. Berlin: Springer, 374.
FitzGerald, R.J., Murray, B.A., Walsh, D.J. 2004. Hypotensive peptides from milk proteins.
J. Nutr., 134, 980S–988S.
Gallifuoco, A., Alfani, F., Cantarella, M., Spagna, G., Pifferi, P.G. 1999. Immobilized
β-glucosidase for the winemaking industry: Study of biocatalyst operational stability
in laboratory-scale continuous reactors. Process Biochem., 35, 179–185.
Gallifuoco, A., D’Ercole, L., Alfani, F., Cantarella, M., Spagna, G., Pifferi, P.G. 1998. On
the use of chitosan-immobilized b-glucosidase in wine-making: Kinetics and enzyme
inhibition. Process Biochem., 33, 163–168.
Gao, C., Fleet, G.H. 1994. The degradation of malic acid by high density cell suspensions of
Leuconostoc oenos. J. Appl. Bacteriol., 76, 632–637.
Gao, C., Fleet, G.H. 1995. Cell-recycle membrane bioreactor for conducting continuous malo-
lactic fermentation. Aust. J. Grape Wine Res., 1, 32–38.
Garcia, H.S., Xavier Malcata, F., Hill, C.G., Jr., Amundson, C.H. 1992. Use of Candida
rugosa lipase immobilized in a spiral wound membrane reactor for the hydrolysis of
milkfat. Enzyme Microb. Technol., 14(7), 535–545.
Giorno, L., Chojnacka, K., Donato, L., Drioli, E. 2002. Study of a cell-recycle membrane fer-
mentor for the production of lactic acid by Lactobacillus bulgaricus. Ind. Eng. Chem.
Res., 41, 433–440.
Giorno, L., Molinari, R., Drioli, E., Bianchi, D., Cestic, P. 1995. Performance of a bipha-
sic organic/aqueous hollow fibre reactor using immobilized lipase. J. Chem. Technol.
Biotechnol., 64, 345–352.
Giorno, L., Molinari, R., Natoli, M., Drioli, E. 1997. Hydrolysis and regioselective trans-
esterification catalyzed immobilized lipases in membrane bioreactors. J. Membr. Sci.,
125, 177–187.
Gobbetti, M., Ferranti, P., Smacchi, E., Goffredi, F., Addeo, F. 2000. Production of angiotensin
I-converting-enzyme-inhibitory peptides in fermented milks started by Lactobacillus
delbrueckii subsp. bulgaricus SS1 and Lactococcus lactis subsp. cremoris FT4. Appl.
Environ. Microbiol., 66, 3898–3904.
Gobbetti, M., Minervini, F., Rizzello, C.G. 2004. Angiotensin I-converting-enzyme-
inhibitory and antimicrobial bioactive peptides. Int. J. Diary Technol., 57, 172–188.
Gordon, M.H., Paiva-Martins, F., Almeida, F. 2001. Antioxidant activity of hydroxytyrosol acetate
compared with that of other olive oil polyphenols. J. Agric. Food Chem., 49, 2480–2485.
Grano, V., Diano, N., Rossi, S., Portaccio, M., Attanasio, A., Cermola, M., Spiezie, R., Citton,
C., Mita, D.G. 2004. Production of low-lactose milk by means of nonisothermal biore-
actors. Biotechnol. Progr., 20, 1393–1401.
Grzeoekowiak-Przywecka, A., Słomińska L. 2005. Continuous potato starch hydrolysis pro-
cess in a membrane reactor with tubular and hollow-fiber membranes. Desalination,
184(1–3), 105–112.
Gueguen, Y., Chemardin, P., Janbon, G., Arnaud, A., Galzy, P. 1996. A very efficient
β-glucosidase catalyst for the hydrolysis of flavor precursors of wines and fruit juices.
J. Agric. Food Chem., 44(8), 2336–2340.
Guenette, M., Duvnjak, Z. 1996. Wood blocks as a carrier for Saccharomyces cerevisiae used
in the production of ethanol and fructose. Biochem. Eng. J., 61, 233–240.
Hamada, H., Fuchikami, Y., Jansing, R.L., Kaminsky, L.S. 1993. Regioselective hydroxyl-
ation of warfarin by cell suspension cultures of Catharanthus roseus. Phytochemistry,
33, 599–600.
Herrero, M., de la Roza, C., Garcia, L.A., Diaz, M. 1999. Simultaneous and sequential fermen-
tation with yeast and lactic acid bacteria in apple juice. J. Ind. Microbiol. Biotechnol.,
22, 48–51.
Herrero, M., Laca, A., Garcia Luis, A., Diaz, M. 2001. Controlled malolactic fermentation in
cider using Oenococcus oeni immobilized in alginate beads and comparison with free
cell fermentation. Enzyme Microb. Technol., 28, 35–41.
Holland, H.L. 2000. Stereoselective hydroxylation reaction. In: Patel, R.N., ed. Stereoselective
Biocatalysis. Marcel Dekker, New York, 131–152.
Holloway, R.W., Achilli, A., Cath, T.Y. 2015. The osmotic membrane bioreactor: A critical
review. Environ. Sci. Water Res. Technol., 1, 581–605.
Houde, A., Kademi, A., Leblanc, D. 2004. Lipases and their industrial applications. Appl.
Biochem. Biotechnol., 118, 155–170.
Hsuanyu, Y., Laidler, K.J. 1986. Flow kinetics of immobilized β-glucosidase. Biochem. Cell
Biol., 64, 139–145.
Hua, Y., Kong, X., Huang, W., Dong, D., Zhang, C. 2011. Method for preparing immuno-
competent soybean peptide by enzymolysis and membrane separation, CN 101974589.
Ishii, S., Yokotsuka, T. 1973. Susceptibility of fruit juice to enzymatic clarification by pectin
lyase and its relation to pectin in fruit juice. J. Agric. Food Chem., 21, 269–272.
Iwasaki, K., Inoue, M., Matsubara, Y. 1998. Continuous production of pectic oligosaccha-
rides in an enzyme membrane reactor. Biosci. Biotech. Biochem., 62, 262–272.
Jung, I.S., Lovitt, R.W. 2010. A comparative study of an intensive malolactic transformation
of cider using Lactobacillus brevis and Oenococcus oeni in a membrane bioreactor.
J. Ind. Microbiol. Biotechnol., 37, 727–740.
Kamel, S., Brazier, M., Desmet, G., Fliniaux, M., Jacquin-Dubreuil, A. 1992. Glucosylation of
butyric acid by cell suspension culture of Nicotiana plumbaginifolia. Phytochemistry,
31, 1581–1583.
Kana, K., Kanellaki, M., Papadimitriou, A., Psarianos, C., Koutinas, A.A. 1989a.
Immobilization of Saccharomyces cerevisiae on g-alumina pellets and its ethanol pro-
duction in glucose and raisin extract fermentation. J. Ferment. Bioeng., 68, 213–215.
Kana, K., Kanellaki, M., Psarianos, C., Koutinas, A.A. 1989b. Ethanol production by
Saccharomyces cerevisiae immobilized on mineral kissiris. J. Ferment. Bioeng., 68,
144–147.
Kędziora, P., Le Thanh, J., Lewandowicz, G., Prochaska, K. 2006. An attempt to application
of continuous recycle membrane reactor for hydrolysis of oxidised derivatives of potato
starch. J. Membr. Sci., 282, 14–20.
Kéry, V., Haplovà, J., Tihlárik, K., Schmidt, S.J. 1990. Factors influencing the activity and
thermostability of immobilized porcine pancreatic lipase. Chem. Tech. Biotechnol., 48,
201–207.
Korhonen, H., Pihlanto, A. 2003. Bioactive peptides: Novel application for milk proteins.
Appl. Biotechnol. Food Sci. Policy, 1, 133–144.
Korhonen, H., Pihlanto, A. 2006. Bioactive peptides: Production and functionality. Int. Diary
J., 16, 945–960.
Koutinas, A.A., Bakoyianis, V., Argiriou, T., Kanellaki, M., Voliotis, S.A. 1997. Qualitative
outline to industrialize alcohol production by catalytic multistage fixed bed tower
(MFBT) bioreactor. Appl. Biochem. Biotechnol., 66, 121–131.
Kula, M-R, Kragle, U. 2000. Dehydrogenases in the synthesis of chiral compounds. In: Patel,
R.N., ed. Stereoselective Biocatalysis. Marcel Dekker, New York.
Kumar, A., Yuan, X., Sahu, A.K., Dewulf, J., Ergasa, S.J., Van Langenhove, H. 2010. A hol-
low fiber membrane photo-bioreactor for CO2 sequestration from combustion gas cou-
pled with wastewater treatment: A process engineering approach. J. Chem. Technol.
Biotechnol., 85, 387–394. DOI 10.1002/jctb.2332
Ladero, M., Santos, A., Garcia-Ochoa, F. 2000. Kinetic modeling of lactose hydrolysis with
an immobilized beta-galactosidase from Kluyveromyces fragilis. Enzyme Microb.
Technol., 27, 583–592.
Lafon-Lafourcade, S. 1970. Study of the degradation of L-malic acid by resting cells of lactic
acid bacteria isolated from wines. Ann. Technol. Agric., 19, 141–154.
Langrand, G., Rondot, N., Triantaphylides, C., Baratti, J. 1990. Short chain flavour esters
synthesis by microbial lipases. Biotechnol. Lett., 12(8), 581–586.
Lasch, J., Koelsch, R., Kretschmer, K. 1987. Continuous production of protein hydrolysates in
immobilized enzyme reactors. Acta Biotechnol., 7, 227–235.
Lebeau, T., Jouenne, T., Junter, G.A. 1997. Simultaneous fermentation of glucose and
xylose by pure and mixed cultures of Saccharomyces cerevisiae and Candida she-
hatae immobilized in a two-chambered bioreactor. Enzyme Microb. Technol., 21,
265–272.
Livingston, A.G., Arcangeli, J.-P., Boam, A.T., Zhang, S., Maragon, M., Freita dos Santos,
L.M. 1998. Extractive membrane bioreactors for detoxification of chemical industry
wastes: Process development. J. Membr. Sci., 151, 29–44.
Lopez-Ulibarri, R., Hall, G.M. 1997. Saccharification of cassava flour starch in a hollow-fiber
membrane reactor. Enzyme Microb. Technol., 21(6), 398–404.
Loukatos, P., Kiaris, M., Ligas, I., Bourgos, G., Kanellaki, M., Komaitis, M., Koutinas, A.A.
2000. Continuous wine-making by g-alumina-supported biocatalyst. Quality of the
wine and distillates. Appl. Biochem. Biotechnol., 89, 1–13.
Lovitt, R., Jung, I., Jones, M. 2006. The performance of a membrane bioreactor for the malo-
lactic fermentation of media containing ethanol. Desalination, 199, 435–437.
Lu, S.G., Imai, T., Ukita, M., Sekine, M., Fukagawa, M., Nakanishi, H. 2000. The per-
formance of fermentation wastewater treatment in ultrafiltration membrane bioreac-
tor by continuous and intermittent aeration processes. Water Sci. Technol., 42(3–4),
323–329.
Maicas, S., Natividad, A., Ferrer, S., Pardo, I. 2000. Malolactic fermentation in wine with
high densities of non-proliferating Oenococcus oeni. World J. Microb. Biotechnol., 16,
805–810.
Maicas, S., Pardo, I., Ferrer, S. 1999. Continuous malolactic fermentation in red wine using
free Oenococcus oeni. World J. Microb. Biotechnol., 15, 737–739.
Maicas, S., Pardo, I., Ferrer, S. 2001. The potential of positively charged cellulose sponge for
malolactic fermentation of wine using Oenococcus oeni. Enzyme Microb. Technol., 28,
415–419.
Malcata, F.X., Hill, C.G., Jr. 1995. Industrial utilization of a hollow-fiber membrane reactor
for the controlled lipolysis of butterfat. Ann. N. Y. Acad. Sci., 750(1), 401–407.
Malcata, F.X., Hill, C.G., Amundson, C.H. 1991. Use of a lipase immobilized in a membrane
reactor to hydrolyze the glycerides of butter oil. Biotechnol. Bioeng., 38, 853–868.
Mallick, N. 2002. Biotechnological potential of immobilized algae for wastewater N, P and
metal removal. A review. Bio Metals, 15, 377–390.
Manjón, A., Iborra, J.L., Arocas, A. 1991. Short-chain flavour ester synthesis by immobilized
lipase in organic media. Biotechnol. Lett., 13, 339–344.
Manna, C., Galletti, P., Maisto, G., Cucciolla, V., D’Angelo, S., Zappia, V. 2000. Transport
mechanism and metabolism of olive oil hydroxytyrosol in Caco-2 cells. FEBS Lett.,
470, 341–344.
Mannheim, A., Cheryan, M. 1990. Continuous hydrolysis of milk protein in a membrane
bioreactor. J. Food Sci., 55, 381–385.
Martin-Orue, H., Bouhallab, S. 1999. Tryptic hydrolysis of k-caseinomacropeptides: Control
of the enzymatic reaction in a continuous membrane reactor. Enzyme Microb. Technol.,
24, 173–180.
Mazzei, R., Drioli, E., Giorno, L. 2010. Biocatalytic membrane reactor and membrane emul-
sification concepts combined in a single unit to assist production and separation of
water unstable reaction. J. Membr. Sci., 352, 166–172.
Mazzei, R., Drioli, E., Giorno, L. 2012. Enzyme membrane reactor with heterogenized
β-glucosidase to obtain phytotherapic compound: Optimization study. J. Membr. Sci.,
390–391, 121–129.
Mazzei, R., Giorno, L., Piacentini, E., Mazzuca, S., Drioli, E. 2009. Kinetic study of a bio-
catalytic membrane reactor containing immobilized glucosidase for the hydrolysis of
oleuropein. J. Membr. Sci., 339, 215–223.
Mazzuca, S., Giorno, L., Spadafora, A., Mazzei, R., Drioli, E. 2006. Immunolocalization of
β-glucosidase immobilized within polysulphone capillary membrane and evaluation of
its activity in situ. J. Membr. Sci., 285, 152–158.
McCord, J.D., Ryu, D.D.Y. 1985. Development of malolactic fermentation process using
immobilised whole cells and enzyme. Am. J. Enol. Vitic., 36, 214–218.
Montero, M.A., Romeu, A. 1993. Properties of almond β-glucosidase immobilized on con-
canavalin A-sepharose. Biochem. Mol. Biol. Int., 30, 685–689.
Moueddeb, H., Sanchez, J., Bardot, C., Fick, M. 1996. Membrane bioreactor for lactic acid
production. J. Membr. Sci., 114, 59–71.
Nagamoto, H., Matsushita, Y., Sugamoto, K., Matsui, T. 2005. Preparation and properties of
gelatin-immobilized β-glucosidase from Pirococcus furious. Biosci. Biotechnol., 69,
128–136.
Nagano, A., Arikawa, E., Kobayashi, H. 1992. The treatment of liquor wastewater containing
high-strength suspended solids by membrane bioreactor system. Water Sci. Technol.,
26(3–4), 887–895.
Nakamura, Y., Yamamoto, N., Sakai, K., Okubo A., Yamamzaki, S., Takano, T. 1995.
Purification and characterization of angiotensin I-converting enzyme inhibitors from
sour milk. J. Dairy Sci., 78, 777–783.
Naouri, P., Bernet, N., Chagnaud, P., Arnaud, A., Galzy, P. 1991. Bioconversion of L-malic
acid into l-lactic acid using a high compacting multiphase reactor (HCMR). J. Chem.
Technol. Biotechnol., 51, 81–95.
Nedovic, V.A., Durieux, A., Van Nedervelde, L., Rosseels, P., Vandegans, J., Plaisant, A.M.,
Simon, J.P. 2000. Continuous cider fermentation with co-immobilized yeast and
Leuconostoc oenos cells. Enzyme Microb. Technol., 26, 834–839.
Neuhaus, W., Novalin, S., Klimacek, M., Splechtna, B., Petzelbauer, I., Szivak, A., Kulbe,
K.D. 2006. Optimization of an innovative hollow-fiber process to produce lactose-
reduced skim milk. Appl. Biochem. Biotechnol., 134, 1–14.
Nielsen, P.M. 1997. Functionality of proteins hydrolysates. In Damodaran, S., Paraf, A., eds.
Food Proteins and Their Applications. Marcel Dekker, New York, 443–472.
Ogbonna, J.C., Amano, Y., Nakamura, K., Yokotsuka, K., Shimazu, Y., Watanabe, M., Hara,
S.A. 1989. Multistage bioreactor with replaceable bioplates for continuous wine fer-
mentation. Am. J. Enol. Vitic., 40, 292–297.
Ogbonna, J.C., Tomiyama, S., Liu, Y.C., Tanaka, H. 1997. Efficient production of ethanol
by cells immobilized in Loofa (Luffa cylindrica) sponge. J. Ferment. Bioeng., 84,
271–274.
Olano-Martin, E., Mountzouris, K.C., Gibson, G.R., Rastall, R.A. 2001. Continuous pro-
duction of pectic oligosaccharides in an enzyme membrane reactor. J. Food Sci., 66,
966–971.
Olmos-Dichara, A., Ampe, F., Ulibearrea, J.-L., Parelleiux, A. 1997. Growth and lactic acid
production by Lactobacillus casei ssp. rhamnosus in batch and membrane bioreactor:
Influence of yeast extract and tryptone enrichment. Biotechnol. Lett., 19, 709–714.
Paiva-Martins, F., Gordon, M.H., Gameiro, P. 2003. Activity and location of olive oil pheno-
lic antioxidants in liposomes. Chem. Phys. Lipids, 124, 23–36.
Paolucci-Jeanjen, D., Belleville, M.P., Rios, G.M., Zakhia, N. 2000. The effect of enzyme
concentration and space time on the performance of a continuous recycle membrane
reactor for one-step starch hydrolysis. Biochem. Eng. J., 5, 17–22.
Pastore, M., Morisi, F. 1976. Lactose reduction of milk by fiber-entrapped β-galactosidase.
Methods Enzymol., 44, 822–830.
Pátková, J., Šmogrovičová, D., Dömény, Z., Bafrncová, P. 2000. Very high gravity wort fer-
mentation by immobilised yeast. Biotechnol. Lett., 22, 1173–1177.
Phattaranawik, J., Fane, A.G., Pasquier, A.C.S., Bing, W. 2008. A novel membrane bioreactor
based on membrane distillation. Desalination, 223(1–3), 386–395.
Philanto-Lappälä, A., Koskinen, P., Piilola, K., Tupasela, T., Korhonene, H. 2000. Angiotensin
I-converting inhibitory properties of whey protein digests: Concentration and charac-
terization of active peptides. J. Diary Res., 67, 53–64.
Piazza, G.J., Foglia, T.A., Nunez, A. 2000. Epoxidation of fatty acids with membrane-sup-
ported peroxygenase. Biotechnol. Lett., 217–221.
Prata-Vidal, M., Bouhallab, S., Henry, G., Aimar, P. 2001. An experimental study of caseino-
macropeptide hydrolysis by trypsin in a continuous membrane reactor. Biochem. Eng.
J., 195–202.
Prieto, C.A., Guadix, E.M., Guadix, A. 2008. Influence of temperature on protein hydrolysis
in a cyclic batch enzyme membrane reactor. Biochem. Eng. J., 42, 217–223.
Pronk, W., Kerkhof, P.J.A.M., Van Helden, C., Riet, K.v. 1988. The hydrolysis of triglycerides
by immobilized lipase in a hydrophilic membrane reactor. Biotechnol. Bioeng., 32,
512–518.
Qi, H.Z. 2004. Patent No. CN1546682.
Righetti, P.G., Nembri, F., Bossi, A., Mortarino, M. 1997. Continuous enzymatic hydrolysis
of β-casein and isoelectric collection of some of the biologically active peptides in an
electric field. Biotechnol. Progr., 13, 258–264.
Robinson, P.K. 1998. Immobilized algal technology for wastewater treatment purposes. In:
Wong, Y.-S., Tam, N.F.Y., eds. Wastewater Treatment with Algae. Springer-Verlag &
Landes Bioscience, Berlin, 1–16.
Rodis, P.S., Karathanos, V.T., Mantzavinou, A. 2002. Partitioning of olive oil antioxidants
between oil and water phases. J. Agric. Food Chem., 50, 596–601.
Rodriguez-Nogales, J.M., Ortega, N., Perez-Mateos, M., Busto, M. 2008. Pectin hydrolysis
in a free enzyme membrane reactor: An approach to the wine and juice clarification.
Food Chem., 107, 112–119.
Rongqing, Z., Yuxiang, J., Wenhao, T. 2010. Applied research on the treatment of wastewater
from the concentrated pomegranate juice production by MBR process. Chin. Agric.
Sci. Bull., 10, 072.
Ross, W.R., Barnard, J.P., Strohwald, N.K.H., Grobler, C.J., Sanetra, J. 1992. Practical appli-
cation of the ADUF process to the full-scale treatment of maize-processing effluent.
Water Sci. Technol., 25(10), 27–39.
Rossi, J., Clementi, F. 1984. L-Malic acid catabolism by polyacrylamide gel entrapped
Leuconostoc oenos. Am. J. Enol. Vitic., 36, 100–102.
Röthig, T.R., Kulbe, K.D., Bückmann, F. et al. 1990. Continuous coenzyme dependent ste-
reoselective synthesis of sulcatol by alcohol dehydrogenase. Biotechnol. Lett., 12,
353–356.
Rucka, M., Turkiewicz, B. 1990. Ultrafiltration membranes as carriers for lipase immobiliza-
tion. Enzyme Microb. Technol., 12(1), 52–55.
Rucka, M., Turkiewicz, B., Tomaszewska, M., Chlubek, N. 1989. Hydrolysis of sunflower oil by
means of hydrophobic membrane with lipolytic activity. Boitechnol. Lett., 11(3), 167–172.
Sakai, S., Antoku, K., Yamaguchi, T., Kawakami, K. 2008. Transesterification by lipase
entrapped in electrospun poly (vinyl alcohol) fibers and its application to a flow-through
reactor. Journal of bioscience and bioengineering 105(6), 687–689.
Sakurai, A., Nishida, Y., Saito, H., Sakakibara, M. 2000. Ethanol production by repeated
batch culture using yeast cells immobilized within porous cellulose carriers. J. Biosci.
Bioeng., 90, 526–529.
Sannier, F., Bordenave, S., Piot, J.M. 2000. Purification of goat β-lactoglobulin from whey by
an ultrafiltration membrane enzymic reactor. J. Dairy Res., 67, 43–51.
Scott, J.A., O’Reilly, A.M. 1996. Co-immobilization of selected yeast and bacteria for controlled
flavour development in an alcoholic cider beverage. Process Biochem., 31(2), 111–117.
Shahbazi, A., Mims, M.R., Li, Y., Shirley, V., Ibrahim, S.A., Morris, A. 2005. Lactic acid
production from cheese whey by immobilized bacteria. Appl. Biochem. Biotechnol.,
121–124, 529–540.
Shieh, Y.M., Tsay, S.S. 1990. Malolactic fermentation by immobilized Leuconostoc sp. M-I.
J. Chin. Agric. Chem. Soc., 28, 246–257.
Słomińska, L., Szostek, A., Grześkowiak, A. 2002. Studies on enzymatic continuous produc-
tion of cyclodextrins in an ultrafiltration membrane bioreactor. Carbohydr. Polym., 50,
423–428.
Smogrovicová, D., Dömény, Z. 1998. Beer volatile by-product formation at different fermen-
tation temperature using immobilised yeasts. Process Biochem., 34, 785–794.
Smogrovicova, D., Domeny, Z., Svitel, J. 1998. Effect of immobilized cell concentration on
beer quality in continuous fermentation. Food Biotechnol., 12, 123–137.
Soler-Rivas, C., Espin, J.C., Wichers, H.J. 2000. Oleuropein and related compounds. J. Sci.
Food Agric., 80, 1013–1023.
Solov’ev, A.Y., Shiryaev, A.P., Basin, B.Y., Shataeva, L.K. 2006. A membrane bioreactor with
immobilized proteinase. Russian J. Appl. Chem., 79, 1333–1337.
Song, S.H., Kim, T.B., Oh, H.I., Oh, D.K. 2003. Optimization of Bifidobacterium longum
growth by use of calcium carbonate-alginate beads. World J. Microbiol. Biotechnol.
19, 727–731.
Spagna, G., Barbagallo, R.N., Casarini, D., Pifferic, P.G. 2001. A novel chitosan derivative to
immobilize α-L-rhamnopyranosidase from Aspergillus niger for application in bever-
age technologies. Enzyme Microb. Technol., 28(4–5), 8 March 2001, 427–438.
Spettoli, P., Bottacin, A., Nuti, M.P., Zamorani, A. 1982. Immobilization of Leuconostoc
oenos ML 34 in calcium alginate gels and its application to wine technology. Am. J.
Enol. Vitic., 33, 1–5.
Spettoli, P., Nuti, M.P., Crapisi, A., Zamorani, A. 1987. Technological improvement of malo-
lactic fermentation in wine by immobilized microbial cells in a continuous flow reactor.
Ann. N.Y. Acad. Sci., 501, 386–389.
Splechtna, B., Nguyen, T., Haltrich, D. 2007. Comparison between discontinuous and con-
tinuous lactose conversion processes for the production of prebiotic galacto-oligosac-
charides using beta-galactosidase from Lactobacillus reuteri. J. Agric. Food Chem.,
55(16), 6772–6777.
Splechtna, B., Petzelbauer, I., Kuhn, B., Kulbe, K.D., Nidetzky, B. 2002. Hydrolysis of lactose
by β-glycosidase CelB from hyperthermophilic archaeon Pyrococcus furiosus. Appl.
Biochem. Biotechnol., 98–100, 473–488.
Splendiani, A., Nicolella, C., Livingston, A.G. 2003. Control of membrane-attached biofilms
using surfactants. Biotechnol. Bioeng., 83(1), 8–19.
Sridang, P.C., Kaiman, J., Pottier, A., Wisniewski, C. 2006. Benefits of MBR in seafood
wastewater treatment and water reuse: Study case in Southern part of Thailand.
Desalination, 200(1–3), 712–714.
Strathmann, H., Giorno, L., Drioli, E. 2011. Introduction to Membrane Science and
Technology (Vol. 544). Weinheim: Wiley-VCH.
Suzzi, G., Romano, P., Vannini, L., Turbanti, L., Domizio, P. 1996. Cell-recycle batch fermen-
tation using immobilized cells of flocculent Saccharomyces cerevisiae wine strains.
World J. Microbiol. Biotechnol., 12, 25–27.
Szaniawski, A.R., Spencer, H.G. 1996. Effects of pectin concentration and crossflow veloc-
ity on permeability in the microfiltration of dilute pectin solutions by macropo-
rous titania membranes containing immobilized pectinase. Biotechnol. Progr., 12,
403–405.
Takaya, M., Matsumoto, N., Yanase, H. 2002. Characterization of membrane bioreactor for
dry wine production. J. Biosci. Bioeng., 93, 240–244.
Tata, M., Bower, P., Bromberg, S., Duncombe, D., Fehring, J., Lau, V., Ryder, D., Stassi, P. 1999.
Immobilized yeast bioreactor systems for continuous beer fermentation. Biotechnol.
Progr., 15, 105–113.
Toräng, A., Jönsson, A.S., Zacchi, G. 1999. Appl. Biochem. Biotechnol., 76, 143. doi:10.1385/
ABAB:76:2:143.
Valivety, R.H., Halling, P.J., Peilow, A.D., Macrae, A.R. 1992. Lipases from different sources
vary widely in dependence of catalytic activity on water activity. Biochim. Biophys.
Acta, 1122, 143–146.
van der Padt, A., Edema, M.J., Sewalt, J.J.W. 1990. Enzymatic acylglycerol synthesis in a
membrane bioreactor. J. Am. Oil Chem. Soc., 67, 347–352.
Vanhommerig, S.A.M., Sluyterman, L.A.Æ., Meijer, E.M. 1996. Kinetic and modelling stud-
ies of NAD+ and poly( ethylene glycol)-bound NAD+ in horse liver alcohol dehydroge-
nase. Biochimica et Biophysica Acta 1295, 125–138.
Vasič-Racki, D., Jonas, M., Wandrey, C. et al. 1989. Continuous (R)-mandelic acid production
in an enzyme membrane reactor, Appl. Microbiol. Biotechnol., 31, 215–222.
Velizarov, S., Crespo, J.G., Reis, M.A. 2002. Ion exchange membrane bioreactor for selective
removal of nitrate from drinking water: Control of ion fluxes and process performance.
Biotechnol. Progr., 18, 296–302.
Visioli, F., Bellomo, G., Galli, C. 1998. Free radical-scavenging of olive oil phenols. Biochem.
Biophys. Res. Commun., 247, 60–64.
Visioli, F., Bellomo, G., Montedoro, G., Galli, C. 1995. Antioxidant and other biological
activities of olive mill waste waters. Atherosclerosis, 117, 25–32.
Visioli, F., Caruso, D., Galli, C., Viappiani, S., Galli, G., Sala, A. 2000. Olive Oil rich in natu-
ral cathecolic phenols decrease isoprostane excretion in humans. Biochem. Biophys.
Res. Commun., 278, 797–799.
Visioli, F., Romani, A., Mulinacci, N., Zarini, S., Conte, D., Vincieri, F.F., Galli, C. 1999.
Antioxidant and other biological activities of olive mill waste waters. J. Agric. Food
Chem., 47, 3397–3401.
Vissers, M.N., Zock, P.L., Katan, M.B. 2004. Bioavailability and antioxidant effects of olive
oil phenols in humans: A review. Eur. J. Clin. Nutr., 58, 955–965.
Wang, J., Zhao, M., Zhao, Q., Jiang, Y. 2007. Antioxidant properties of papain hydrolysates of
wheat gluten in different oxidation systems. Food Chem., 101, 1658–1663.
Wang, Y., Huanga, X., Yuan, Q. 2005. Nitrogen and carbon removals from food process-
ing wastewater by an anoxic/aerobic membrane bioreactor. Process Biochem., 40,
1733–1739.
Wichmann, R., Wandrey, C., Bückmann, A.F., Kula, M.R. 1981. Continuous enzymatic trans-
formation in an enzyme membrane reactor with simultaneous NAD (H) regeneration.
Biotechnol. Bioeng., 23(12), 2789–2802.
Wisniewski, C., Persinb, F., Cherif, T., Sandeauxb, R., Grasmick, A., Gavachb, C., Lutin, F.
2002. Use of a membrane bioreactor for denitrification of brine from an electrodialysis
process. Desalination, 149, 331–336.
Xu, G., Chu, J., Wang, Y., Zhuang, Y., Zhang, S., Peng, H. 1999. Development of a continuous
cell-recycle fermentation system for production of lactic acid by Lactobacillus paraca-
sei. Process Biochem., 41, 2458–2463.
Yamaguchi, F., Shimizu, N., Hatanaka, C. 1994. Preparation and physiological effect of low-
molecular-weight pectin. Biosci. Biotechnol. Biochem., 58, 679–682.
Yamauchi, Y., Okamoto, T., Murayama, H., Kajino, K., Amikura, T., Hiratsu, H., Nagara,
A., Kamiya, T., Inoue, T. 1995a. Rapid maturation of beer using an immobilized yeast
bioreactor. 1. Heat conversion of alpha-acetolactate. J. Biotechnol., 38, 101–108.
Yamauchi, Y., Okamoto, T., Murayama, H., Kajino, K., Nagara, A., Noguchi, K. 1995b. Rapid
maturation of beer using an immobilized yeast bioreactor. 2. Balance of total diacetyl
reduction and regeneration. J. Biotechnol., 38, 106–116.
Yeoh, H. 1991. Kinetic properties of cassava β-glucosidase immobilized in photo-
crosslinkable resins. Biotechnol. Lett., 13, 697–700.
Zetelaki-Horvath, K. Gatai, K. 1977. Disintegration of vegetable tissues byendo-
polygalacturonase, Acta Aliment. 6, 227–240.
Index
A α-Lactalbumin, 118–119
α-Terpineol, 170
Acerola, 221 ALR, see Air-lift bioreactors
Acetic acid, 163 Amelioration, 59
“Acid” whey, 97 hydraulic cleaning methods, 61–62
Actinidia plant fruit, 231 indirect methods, 60–61
Activity-driven membrane processes mass transfer coefficient, 59–60
activity and activity coefficients, 69–70 membrane cleaning, 62–63
classification of membrane processes, 68 subscripts, 64
dialysis, 68–69 symbols, 63–64
GS and PV, 73–76 American Society for Testing and Materials
heat transport process, 80–82 (ASTM), 279
MD, 82–83 Amicon® stirred cell, 10
OD, 84–85 (R)-Amygdalin, 328
polymers for GS and PV, 70–73 Anhydrogalacturonic acid (AGA), 325
pore wetting, 78–79 Animal products industry; see also Dairy
solution-diffusion theory and link to activity, industry; Egg-processing industry;
76–78 Seafood processing industry
TPC, 79 blood, 136–140
Activity-driven nonwetted membrane gelatin, 140–142
processes, 19 Animal products processing, 94
Adsorption, 42, 72, 166 Anionic exchange membranes, 14
Aerobic bioreactors, 189 Anoxic pretreatment, 156
AGA, see Anhydrogalacturonic acid Anoxic treatment, 157
AGMD, see Air gap membrane distillation Anthocyanins, 154, 155, 182
Agrifood industry in Greece, 189 Antioxidants, 152
Air filtration, 15 activity, 153, 158
Air gap membrane distillation (AGMD), 82, 83 Apple juice aroma, 225, 228
Air-lift bioreactors (ALR), 329 Aqueous phase, 71, 97
Air pressure, 79 Aroma, 179, 221, 223–224
Albumen, 125–126 components, 169
Albumin, 171–172 compounds, 175, 180
Alcohol, 179, 180 Aroma recovery, 223–224
alcohol-free wines, 169 apple juice aroma, 225, 228
alcohol-rich permeate, 180 bilberries, 227
concentration, 171, 181 concentrated apple juice production, 225
content, 162, 163, 169, 174, 181, 187 EPDM, 226–227
industry, 181 natural aromas, 224
removal, 181 natural aromas, 224–225
Alcoholic beverage processing, MBRs in, 335 nature-identical aromas, 224
bioreactors in winemaking, 340 PDMS membrane, 225, 227, 229
enzymes used in alcoholic beverage, 337 permeability coefficient, 225
global production of wine, 335 pervaporation for, 180
materials, microorganisms, bioreactor type in plate-and-frame modules, 228
beer and cider making, 341–342 pomegranate, 227
MBR systems in wine-making process, 339 POMS membranes, 225, 227
patents in biocatalytic membrane reactors, 336 PV, 225, 227–230
supports materials in winemaking, 338 recovery of strawberry aroma compounds by
Alfa Laval/Raisio process, 256 PV, 226
α-Casein, 318 Aronia solutions, 217
α-l-Rhamnopyranosidase, 335 Arrhenius-type equation, 78
361
362 Index
Artificial aromas, 224 Bifidobacterium longum (B. longum), 315

Ascorbic acid, 209, 223 Bilberries (Vaccinium myrtillus L.), 227
Aspergillus fungi, 314 Bioactive peptides, 119
Aspergillus niger (A. niger), 321 Biocatalysts, 300, 301, 303, 311
pectinases, 323 biocatalytic membrane reactors, 309
Astaxanthin, 288 immobilization techniques, 311–312
ASTM, see American Society for Testing and MBRs with biocatalyst compartmentalized
Materials upstream or downstream membrane,
Astringency, 188 305–309
Asymmetric membranes, 12, 28 membranes commonly in other
Asymmetric organic membranes, 95 applications, 310
Australian Wine Research Institute, 180 Biocatalytic membrane reactors (BMRs),
Azeotropic distillation, 74 302, 303
with biocatalysts immobilized at membrane
B level, 309
in food processes, 314
“Back-shock” method, 62 immobilization techniques, 311–312
Backwash efficiency, 53–54 with immobilized biocatalysts, 310
Bacteria removal, 98 membranes commonly in other
commercial MF system for removal of applications, 310
bacteria from milk, 100 Biocatalytic membrane system, 347–348
depiction of membranes, 102 Biochemical membrane reactors, 301–302
homogeneous transmembrane pressure, 101 Bio-derived feedstock, 300
microfiltered–pasteurized milk, 103 Biodiesel production, 276–281
PDO, 104 Biofuels industry development, 269–270
principle of UTP system, 100 Biological demand in oxygen at 5 days
process for MF of whole milk, 99 (BDO5), 130
Bactofugation, 99 Biological membranes, 300–301
BAT, see Best available technology Biological oxygen demand (BOD), 117, 140, 189,
Batch system, 35 252, 262, 314, 345; see also Chemical
Batter process, 256 oxygen demand (COD)
BCJC production, see Black currant juice Biomass fermentation process, 350
concentrate production Biomembrane systems, 300, 301
BDO5, see Biological demand in oxygen at 5 days Bio-mimicking membrane reactors, 300
Beet sugar production, 247; see also Cane sugar Bio-mimicking reaction systems, 300
production Biophenols
applications, 252 hydroxytyrosol, 346
concentration of clarified thin juice, 251 in OMW, 346
demineralization of beet sugar juice, 250–251 Bioreactors in winemaking, 340
evaporator condensate polishing, 252 Biotransformation, 326–329
purification of raw beet juice, 249–250 Biphasic organic–aqueous enzyme membrane
recycling of ion exchange resin regeneration reactor (B-EMR), 332
waste, 252 Bipolar membranes (BM), 230
recycling of sugar beet press water and isolation Bitterness, 188
of pectin from beet pulp, 248–249 Black currant juice concentrate production
sweet water concentration, 252 (BCJC production), 222
B-EMR, see Biphasic organic–aqueous enzyme Blocked membrane, 76
membrane reactor Blood, 136
Benzyl alcohol, 170 anaerobic treatment and aerobic
Bergamot, 232 polishing, 140
Berries, 195 composition, 137
Berry-type fruits, 198 membrane processes, 139
Berry fruit black currant (Ribes nigrum), 203, 217 orange juice, 208
Best available technology (BAT), 242 plasma fraction, 137
β-Galactosidase, 314 processing, 138
β-Glucosidases, 347, 348 BM, see Bipolar membranes
β-Lactoglobulin (β-LG), 110 BMRs, see Biocatalytic membrane reactors
Index 363
BOD, see Biological oxygen demand manufacture of Quarg or cream cheese on

Botrytis cinerea (B. cinerea), 186 UF-based process, 109
Botrytized wines, 155–156 MMV process, 108
Bovine gelatins, 140 representations of traditional ways of making
Bovine serum albumin (BSA), 97 cheese, 107
“Brandy”, 181 Cheese milks, 103
“Breaker plants”, 124 Chemical cleaning of membranes, 169
Brine clarification, 121–122 Chemical method immobilization, 312
Brix, 246 covalent bond, 312
Brownian diffusion, 46 ionic bond and hydrophobic interaction, 312
BSA, see Bovine serum albumin Chemical oxygen demand (COD), 140, 189, 251,
252, 262, 345; see also Biological
C oxygen demand (BOD)
Chemical potential, 76–77
CA, see Cellulose acetate Chemotherapeutic agents, 159
Calcium chloride, 85 Cherry wines, 165
Camu-camu juice (Myrciaria dubia), 209 Chinese wines, 154
Candida rugosa (C. rugosa), 321 Chitosan addition, 201
Cane sugar production, 243 Cholupa, 223
applications, 252 CIP procedures, see Cleaning-in-place
concentration of clarified cane juice, 246 procedures
decolorization of remelted raw sugar, Cis-resveratrol, 152–153, 156–157, 182
246–247 Clarified cane juice concentration, 246
evaporator condensate polishing, 252 Classical thermal concentration techniques,
molasses treatment, 246 219–220
purification of raw sugar cane juice, 244–246 Cleaning-in-place procedures (CIP procedures),
recycling of ion exchange resin regeneration 32, 122–123
waste, 252 Cleaning method, 59
sweet water concentration, 252 hydraulic cleaning methods, 61–62
Capex, 53–54 indirect methods, 60–61
Capillary modules, 30 mass transfer coefficient, 59–60
Carbohydrates, category of, 242 membrane cleaning, 62–63
Carbon membranes, 24 subscripts, 64
Carboxypeptidase A (CPA), 318, 320 symbols, 63–64
Carman–Kozeny equation, 49 Cleaning solution recycling, 122–123
Casein Clostridium botulinum (C. botulinum), 103
fractionation, 113–114 Cocoa butter, 334
micelles, 97, 108 COD, see Chemical oxygen demand
Cassava root (Manihot esculenta), 330 “Cold energy”, 201–202
Cassette modules, 31 Colloidal calcium phosphate, 97
Catechin, 154 Colloids, 198
Cationic exchange membranes, 14 Color density, 155
Cell(s), 329 Color intensity, 179
compartmentalization, 315 Compartmentalization, 303
culture, 309 Concentration
factory in living organisms, 300 of clarified thin juice, 251
immobilization for winemaking, 335 concentrated apple juice production, 225
Cellulose acetate (CA), 5, 24 concentrated grape juice, 218
Centrifugation, 99, 198–199 concentrated must, 218
Ceramic membranes, 24, 101 macromolecules, 42–43
Ceramic membrane separator, 278 polarization, 41, 43
CFV, see Cross-flow velocity of protein hydrolysates, 135–136
CH3CHOHCOOH, see Lactic acid of serum proteins, 117–118
Champagne, 187 whey, 114–115
Cheese-making processes, 106 Constant liquid recycle, 174
Cheese manufacture, protein concentration Continuous distillation, 188
in, 106 Copolymers, 25
364 Index
Corn starch processing, 253 by pervaporation, 174–176

gluten concentration, 255 by RO and NF, 171–174
starch washing, 255 Decolorization of remelted raw sugar,
steeping water handling, 254 246–247
Corn wet milling process, 253 De Danske Sukkerfabrikker (DDS), 243
Covalent bond, 312 Degumming process, 271
Cow’s milk, 96 Delphinidin-3-glucoside, 155
CP, see Critical pressure Demineralization
CPA, see Carboxypeptidase A of beet sugar juice, 250–251
Cranberry juice (Vaccinium macrocarpon whey, 115–117
Ait.), 223 Dense membranes, 76
Critical flux, 51–53, 54 Deoxygenation, 260
Critical pressure (CP), 286 Depectinized bergamot juice, 222–223
Cross-flow filtration, 57 Depolymerases, 322
mode, 168 Deposition, 42
Cross-flow membrane emulsification, 284–285 Der Danske Sukkerfabrikker laboratory (DDS
process parameter sizing, 286–288 laboratory), 209
Cross-flow MF, 164 Destemming, 159–160
Cross-flow mode, 15 Dextrose equivalent (DE), 259
Cross-flow velocity (CFV), 200 DF, see Driving force
Crude red wine, 165 DG, see Diradylglycerolipids
Crude soybean, 275 Diacylglycerol oil (DAG oil), 334
Crushed grape, 159–160 Diafiltration, 13, 34
Crystallization, 305 mode, 173
Cyclodextrins, 331 Dialysis, 19, 68–69
Diatomaceous earth, 165
D Dietary proteins, 317
Diethylaminoethyl chitosan (DE-chitosan), 335
DAG oil, see Diacylglycerol oil Diffusion (D), 71
Dairy industry, 94; see also Animal products juice extraction method, 198
industry; Egg-processing industry; 2′-(3′,4′-Dihydroxypheny-1)ethanol
Seafood processing industry (hydroxytyrosol), 346
approximate particle sizes of milk Diradylglycerolipids (DG), 279–280
constituents for separation, 95 Direct-flow mode, 15
characteristics of milk and wheys, 96–98 Direct-flow modules, 31–33
membrane-separation technologies, 123 Direct contact membrane distillation (DCMD),
membrane separations applied to milk, 82, 83
98–114 Direct flow membrane emulsification,
membrane separations applied to whey and 284–285
derivates, 114–120 Direct osmosis concentration (DOC), 212–213,
protein and peptides fractions, 124 215, 233
treatment of effluents and technical fluids, Dispersed phase flux, 286
120–123 Dissolved solids (DS), 232
Darcy’s law, 47, 286 Distillation, 72, 170, 188
DCMD, see Direct contact membrane distillation DOC, see Direct osmosis concentration
DDS, see De Danske Sukkerfabrikker “Dough ball” process, see Martin process
DDS laboratory, see Der Danske Sukkerfabrikker dp, see Pore diameter
laboratory Dried grape, wine from, 186–187
DE-chitosan, see Diethylaminoethyl chitosan Driving force (DF), 286
DE, see Dextrose equivalent Dry degumming by membrane filtration, 274
Deacidification, 230 design of dry membrane degumming, 276
Dead-end mode, 15 disadvantage of, 275
Dealcoholization of wine, 170, 188 Dry membrane degumming, 272
by combined method, 180 Dry wine, 187
dealcoholized permeate, 180 DS, see Dissolved solids
by liquid emulsion membrane, 179 (S)-Durrin, 328
OD, 176–179 DVLO theory, 52
Index 365
E Ethanol, 71
content, 168, 169, 174, 175, 179, 181
Econa oil, 334
®
removal, 177, 179
Economic analysis, 176 solution, 177
ED, see Electrodialysis Ethanol reduction
E-EMR, see Emulsified organic–aqueous membrane methods for ethanol reduction in
enzyme membrane reactor wines, 170–171
Egg-processing industry, 94, 124; see also of wines, 170
Animal products industry; Dairy Ethyl butyrate (ETB), 226
industry; Seafood processing industry European Norms (EN), 279
characteristics of hen egg, 125–126 European Union regulation, 169
concentration and stabilization of egg white Evaporation method, 201
and whole egg, 126–129 Evaporative process, 84–85
extraction of egg-white proteins, 129 Evaporator condensate polishing, 252
membrane filtration, 130 Extended shelf life (ESF), 102
Eggshell membrane, see Albumen
Egg white and whole egg
concentration and stabilization of, 126 F
concentration before spray drying or storage FAME, see Fatty acid methyl esters
in liquid form, 126–128 FAO, see Food and Agriculture Organization
stabilization, 128 Fat globules, fractionation of, 104–105
types of filtration systems, 128–129 Fatty acid methyl esters (FAME), 277
Egg-white protein extraction, 129 FBR, see Fluidized-bed bioreactors
Egg yolk, see Albumen FDA, see Food and Drug Administration
(E)-2-hexen-1-ol, 228 Feed velocity, 177
Elastomers, see Rubbery polymers Fermentation, 160–161, 187
Electrodialysis (ED), 5, 14, 94, 115, 116, 169, Fermenter, 160
230, 321 Fick’s law of diffusion, 19
membranes, 27, 317 Filtration
performances, 230 process, 199
“Electronic nose”, 71 system types, 128–129
Electrostatic interactions, 18–19 Fish protein hydrolysates (FPH), 135
EMBR, see Enzymatic membrane bioreactor Flat-sheet
EMC, see Enzyme-modified cheeses membranes, 217
Emulsified organic–aqueous enzyme membrane systems, 31
reactor (E-EMR), 332 Flavan-3-ols, 158
Emulsions, 281 Flavonoids, 152, 158, 223
EN, see European Norms Flavonols, 158
End-of-pipe wastewaters treatment, 123 Flavonones, 199
Energy costs of premixed emulsification, 285 Fluidized-bed bioreactors (FBR), 329
Enology, 164 Fluids
Entrapment, 311 clarification of brine, 121–122
Enzymatic/enzymes, 300, 312 management, 31
activity with derivatized cofactor, 308 recovery of process waters, 121
cleaning, 63 recycling of cleaning solutions, 122–123
hydrolysis of whey proteins, 317–318 treatment of effluents, 120–123
membrane reactor, 303 treatment of end-of-pipe wastewaters, 123
Enzymatic membrane bioreactor (EMBR), 280 Flux, 10, 13–14, 76, 118
Enzyme-modified cheeses (EMC), 321 of component, 68
EPDM, 226–227 decay, 82
Epicatechin, 154 molar, 73
Epistemological approach, 8 net, 53
Escherichia coli (E. coli), 120 solvent, 172
ESF, see Extended shelf life FO, see Forward osmosis
Esterases, 322 Fomes fomentarius laccase, 200
Esters, 225 Food and Agriculture Organization (FAO), 335
ETB, see Ethyl butyrate Food and Drug Administration (FDA), 315
366 Index
Foodborne norovirus, 158 FPH, see Fish protein hydrolysates

Food emulsions, 282 Fractionation
Food industry, 4, 188 of casein micelles from serum proteins, 110
direct or cross-flow membrane emulsification, of caseins, 113–114
284–285 of fat globules, 104–105
emulsification techniques, 283 ideal whey, 111
encapsulation in, 281 MF plant for fractionation of milk
materials of emulsification membranes, protein, 112
285–286 of milk proteins, 109
membrane emulsification, 281 of peptides, 119–120
microencapsulation, 292–294 of protein hydrolysates, 135–136
O/W and W/O emulsion production, 288–289 of serum proteins, 118–119
possibilities in food nanotechnology, 290–292 UTP system, 113
premix membrane emulsification, 285 Frame modules, 31
sizing of cross-flow membrane emulsification Free radical-induced oxidative stress, 152
process parameters, 286–288 Freezing method, 201–202
specifications of membrane emulsification “French paradox”, 157, 159
operation, 283 Fruit juice, 195
structure of fine homogeneous O/W emulsion processing, MBRs in, 321–325
by ME, 282 Fruit juice processing applications; see also Fruit
Food nanotechnology juice production technology
nanostructured multilayer emulsions, Fruit juice production technology, 196
291–292 for fruit juice concentrate production,
nanostructured multiple emulsions, 291 201–202
possibilities in, 290 fruit juice concentration by membrane
simple nanoemulsions, 291 separation processes, 202–223
Food processing industry, MBRs for wastes for fruit juice production, 196
coming from, 343 juice clarification, 198–201
in food industry wastewater treatment, 344 juice extraction, 197–198
valorization of waste by membrane membrane separation process applications,
bioreactor, 344–348 223–232
Food sector, 270 Fruit nectars, 196
Forward osmosis (FO), 214, 348; see also Reverse FTIR spectroscopy, see Fourier transform
osmosis (RO) infrared spectroscopy
membrane process, 231–232
Foulants, 56–57 G
Fouled membranes, 165
Fouling, 41, 42, 54, 164 Gallic acid equivalent (GAE), 152, 153
amelioration and cleaning, 59–64 Gas-diffusion process, 23
characterization, 59 Gaseous pair, 71
combined MF + NF system, 168 Gas permeation, 14, 71
components of crude and centrifuged Gas separation (GS), 4, 68, 73
wines, 165 azeotropic distillation, 74
effect of concentration polarization, 50 comparison between pervaporation and
critical flux, 51–53 vapor/gas separation, 75
degrees of polymer penetration, 55 fouling mechanisms of dense membranes, 76
foulants, 56–57 polymers for, 70–73
macromolecules, 42–43 Gas sparging method, 200
MF, 164, 166, 167 Gelatin, animal products industry, 140–142
modeling UF in absence of, 47–50 Gelification, 311
modeling UF in presence of, 50–54 Generally recognized as safe (GRAS), 314
pores, 54–56 Geothermal energy, 82
robustness of UF membranes, 60 Glass membranes, 24
sustainable flux, 53–54 Glassy polymers, 26
TMP for dead-end and cross-flow, 58 Glucose, 127
Fourier transform infrared spectroscopy (FTIR Glucosides, 157
spectroscopy), 229 Gluten concentration, 255
Index 367
Glycerol, 171–172 Hydrolysis of milk fat, 320–321

Glycomacropeptide, 110, 120 Hydrophilic domains, 113
Grapes, 150, 154, 156, 189 Hydrophilic membranes, 61
cultivation, 150 Hydrophilic PV, 71
fermentation, 188 Hydrophobic domains, 113
must, 214 Hydrophobic membrane, 67, 83
skins, 161 contactor, 176
Grape wine lees (GWL), 188–189 Hydrophobic microporous membranes, 78
GRAS, see Generally recognized as safe module, 84
Graver Technologies, 24 Hydrophobic polymers, 78
“Green” methods, 270 5-Hydroxymethylfurfural (HMF), 221
GS, see Gas separation Hydroxynitrile lyases, 328
GWL, see Grape wine lees (R)-Hydroxynitrile lyases, 328
2-Hydroxypropanoic acid, see Lactic acid
H Hydroxytyrosol, 346
Hyperfiltration, 18
Hagen–Poiseuille equation, 49, 286
HD process, see High-pressure disintegration I
process
Heat transfer, 80–82 Ice wine, 186
coefficient, 80, 81 Igs, see Immunoglobulins
equations, 79 Immobilization, 303, 311, 329
Heat-treatment processes, 180 by chemical methods, 312
Hemodialysis, 9 of lipases, 321
Hemoglobin, 138 by physical methods, 311
Hen egg characteristics, 125–126 Immobilized lipase, 332
Heptane, 179 Immobilized M. miehei lipase, 332
Herbs, 219 Immunoglobulins (Igs), 119
Hesperidin, 199 Indirect methods, 60–61
Hexane, 179 Industrial-size membrane contactor, 179
Hexane–oil mixture, 272 Industrial RO, 173
HFCS, see High-fructose corn syrup Inertial lift mechanism, 46
HFSs, see High-fructose syrups Infrasonic pulsing, 167
High-fructose corn syrup (HFCS), 259 Inorganic membranes, 23–24
42-HFCS, 260 Inorganic precipitates, 56
55-HFCS, 259 Integrated membrane
90-HFCS, 259 MBRs in integrated membrane operations,
High-fructose syrups (HFSs), 258–259 348–350
High heat short time (HTST), 103 process, 211–212
High-pressure disintegration process (HD Interfacial polymerization, 27
process), 256 Ion exchange, 115, 116
Hippophae rhamnoides L., see Sea buckthorn mechanism, 13–15
HMF, see 5-Hydroxymethylfurfural resin regeneration waste recycling, 252
Hollow fiber resins, 5
hydrophobe PP membrane, 179 Ionic bond and hydrophobic interaction, 312
membrane diffusion reactor process, Isomerization process, 260
314–315 Isothermal membrane distillation, see Osmotic
modules, 30 distillation (OD)
systems, 6 Italian wines, 154
Homogeneous transmembrane pressure, 101
Homogenization systems, 283–284 J
Homogenous polymer, 25
HTST, see High heat short time Jatropha oil, 275–276
Hybrid processes, 69, 168 Juices, 195–196; see also Fruit juice production
Hydraulic cleaning methods, 61–62 technology
Hydraulic diameter, 46 clarification, 198–201
Hydrocyclone process, 256 extraction, 195–198
368 Index
K Magnesium addition, 260

Maize starch processing, 253
κ-Casein, 110 gluten concentration, 255
Kluyveromyces yeast, 314 starch washing, 255
Knudsen diffusion, 80 steeping water handling, 254
Malaga wine, 187
L Maldivin-3-glucoside, 155
Malic acid, 163
l-ascorbic acid, 200 Malolactic fermentation (MLF), 337, 339
Lactic acid, 254, 337 (R)-Mandelonitrile, 328
membrane bioreactors for, 316 Manihot esculenta, see Cassava root
production, 315–317 Manual harvesting, 159
Lactose hydrolysis, 314–315 Marc, 198, 203
Laplace equation, 78 Marsala wine, 187
Layer-by-layer (LbL), 292 Martin process, 255
Le Chatelier’s principle, 302–303 Mass transfer
LEP, see Liquid entry pressure equations, 79
Light processes, 80
middlings, 255 Maubois, Mocquot, Vassal process (MMV
scattering, 167 process), 95, 106, 108
wine, 161 MBRs, see Membrane bioreactors
Limarin, 328 MD, see Membrane distillation
Linalool, 170 MD020CP2N®, 223
Linear hydraulic resistance, 100, 101 ME, see Membrane emulsification
Lipases, 289, 320, 331 Mechanical clarification, 198–199
Liposomes, 293–294 Mechanical cleaning, 62
Lipoxygenase, 328 Medical effects of wine, 157–159
Liqui-Cel systems, 31 Membrane, 9
Liquid-phase activity coefficients, 75 classification, 16–19, 23
Liquid emulsion membrane, 171 combined MF + NF system, 168
wine dealcoholization by, 179 components of crude and centrifuged
Liquid entry pressure (LEP), 78, 84 wines, 165
Liquid–liquid extraction, 72 contactor technique, 170–171
Liquid pressure, 79 costs, 7–8
Listeria monocytogenes (L. monocytogenes), 129 degumming, 272
Low-alcohol wine production, 169 ED, 27, 169
combined method, dealcoholization by, 180 evaporation, see Osmotic distillation (OD)
liquid emulsion membrane, dealcoholization fouling, 8, 54, 200
by, 179 functionalization, 312
membrane methods for ethanol reduction in in food industry, 242
wines, 170–171 inorganic membranes, 23–24
OD, dealcoholization by, 176–179 materials, type, and structures, 22–28
pervaporation, dealcoholization by, 174–176 membrane-based separation, 126
pervaporation for aroma recovery, 180 methods for ethanol reduction in wines,
RO and NF, dealcoholization by, 171–174 170–171
traditional methods and modern method for MF, 164, 166, 167
ethanol reduction of wines, 170 modules, 28–33
Low-temperature distillation, 170 morphology, 27–28
“Lutfish” production, 134 polymer, 25–26
Lysozyme, 129 polymeric membranes, 24–27
processes, 212–213
M proposed membrane processes, 163
systems, 33–39
Maceration process, 323–324 technologies, 22–23, 213–214
Macromolecules, 42–43, 63 technology market, 189
Macropores, 16 wine clarification, sterilization, and
Madeira wine, 187 stabilization, 164
Index 369
in wine making, 162 module type and membrane processes, 30

Membrane bioreactors (MBRs), 123, 280, 299, 301 tubular modules, 28
in alcoholic beverages processing, 335–342 Membrane processes, 4, 8, 243
applications in food, 312 activity-driven nonwetted membrane
with biocatalyst compartmentalized upstream processes, 19
or downstream membrane, 305–309 beet sugar production, 247–251, 252
biocatalysts, 301, 304 cane sugar production, 243–247, 252
biocatalytic membrane reactors with chemical engineering, 8–9
biocatalysts immobilized, 309–312 classification, 10
biomembrane systems, 301 conventional separation processes, 9–10
in fruit juices processing, 321–325 dialysis, 19
in integrated membrane operations, 348–350 ion-exchange mechanism, 14–15
and membrane supplies reagents to membrane and conventional processes, 11
biocatalyst, 303 membrane classification, 16
in milk and whey processing, 312–321 membrane process, 13
using plant as material source for MF, 17
biotransformation, 326–329 modes of operation, 15
plant raw material used as source, 329–335 nanofiltration, 18–19
for wastes coming from food processing nonporous membrane processes, 19
industry, 343–348 observed rejection coefficient, 10
Membrane distillation (MD), 7, 67, 78, 82–83, pressure-driven membrane processes, 15–16
202, 348 RO, 18
Membrane emulsification (ME), 282, 303 separation mechanism, 13–14
direct or cross-flow membrane emulsification, stirred cell membrane system, 12
284–285 UF, 17–18
and encapsulation in food industry, 281 Membrane-related aspects of physical
materials of emulsification membranes, chemistry, 19
285–286 osmotic pressure, 19–22
microencapsulation, 292–294 vapor pressure, 22
O/W and W/O emulsion production, 288–289 Membrane separation processes, 4, 6–7, 130–131,
possibilities in food nanotechnology, 270, 305
290–292 Acerola, 221
premix membrane emulsification, 285 alcohol content, 217–218
sizing of cross-flow ME process parameters, applied to milk, 98–114
286–288 applied to whey and derivates, 114–120
specifications, 283 aroma recovery, 223–230
structure of fine homogeneous O/W BCJC production, 222
emulsion, 282 berry juice black currant, 206–207
techniques, 283 CA, 5–6
Membrane filtration, 9, 130, 161, 170, 219 Camu-camu, 209–210
biodiesel production using ultrafiltration Cholupa, 223
membrane separation technology, clarified fruit juice, 203–204
276–281 classical thermal concentration techniques,
conventional water and membrane 219–220
degumming, 271 concentrated pomegranate juice production,
dry degumming by membrane filtration, 222
274–276 concentration, 4–5
miscella membrane degumming, 272–274 cost of transportation, 204–205
in vegetable oil purification, 270 deacidification, 230
Membrane level, biocatalysts immobilized at depectinized bergamot juice, 222–223
biocatalytic membrane reactors, 309 food safety, 202–203
immobilization techniques, 311–312 fruit juice aroma components, 210
membranes commonly in other fruit juice concentration by, 202
applications, 310 HMF, 221
Membrane modules, 28 integrated membrane process, 211–212,
design, 29 222–223
direct-flow modules, 31–33 kiwifruit juice concentration, 208–209
370 Index
Membrane separation processes (Continued) lactose hydrolysis, 314–315

MD, 205–206 protein functional groups, 313
membrane-related aspects of physical protein hydrolysis, 317
chemistry, 19–22 Milk proteins
MF, 214–215 concentration of proteins in cheese
natural products, 220–221 manufacture, 106–109
novel products, 231–232 fractionation of milk proteins, 109–113
OD, 207–208, 223 standardization and concentration of, 105
OMD, 216 standardization of proteins, 106
PP hollow fiber modules, 218–219 Miscella membrane degumming, 272–274
sensory analysis, 215–216 MLF, see Malolactic fermentation
vegetable juice processing and concentration MMV process, see Maubois, Mocquot, Vassal
by, 232–234 process
watermelon, 221 Modern wines, 169
Membrane systems, 33 Molar flux, 73
basic, 33–34 Molasses treatment, 246
layout, 35–37 Molecular transport, 80
prediction of required membrane area, 38–39 Molecular weight cut-off membranes (MWCO
process design, 37–38 membranes), 17, 127, 221, 272, 317
UF diafiltration, 34–35 Monoradylglycerolipids (MG), 279–280
Mesopores, 16 MTB, see Methyl butyrate
Metal membranes, 24 Mucor miehei (M. miehei), 321
Methanol (MeOH), 279 Multilayer coextrusion process, 71
Methyl butyrate (MTB), 226 MWCO membranes, see Molecular weight
MEUF, see Micelle-enhanced ultrafiltration cut-off membranes
MF, see Microfiltration Myofibrillar proteins, 131
MFGM, see Milk fat globule membrane Myrciaria dubia, see Camu-camu juice
MG, see Monoradylglycerolipids
Micelle-enhanced ultrafiltration (MEUF), 272 N
Microencapsulation, 292–294
Microfiltered–pasteurized milk, 103 NaCl retention, 171–172
Microfiltration (MF), 4, 17, 43, 47, 56, 94, 162, NADH, 307
164–165, 199, 255, 348; see also NAD(P)H dependent enzymes, reactions of
Nanofiltration (NF); Pervaporation interest catalyzed by, 307
(PV); Ultrafiltration (UF) Nanoemulsions, 291
asymmetric membranes, 62 Nanofiltration (NF), 16, 18–19, 94, 115, 162–163,
membranes, 16 167–168, 180, 202, 246, 348; see also
unit, 305 Microfiltration (MF); Pervaporation
Micropollutants, 309 (PV); Ultrafiltration (UF)
Micropores, 16 anthocyanin concentration, 183
microporous inorganic membrane, 279–280 concentrations of original red wine, 182
microporous membranes, 5, 80 ethanol reduction, 184
Milk initial red wine, 182
characteristics of, 96–98 membranes, 71
cow’s milk, 96 resveratrol concentration, 183
fractionation of caseins, 113–114 wine concentration with, 181
fractionation of fat globules, 104–105 wine dealcoholization by, 171–174
fractionation of milk proteins, 109–113 Nanostructured multilayer emulsions, 291–292
membrane separations applied to, 98 Nanostructured multiple emulsions, 291
products, 94 Nanotechnology, 290
removal of bacteria and spores, 98–104 NAP, see New Applexion Process
standardization and concentration of milk Narirutin, 199
proteins, 105–109 National Nanotechnology Initiative, 290
Milk fat globule membrane (MFGM), 96 Natural aromas, 224
Milk processing, MBRs in, 312 Nature-identical aromas, 224
hydrolysis of milk fat, 320–321 NDS, see Nondissolved solid
lactic acid production, 315–317 Nernst–Plank equation, 19
Index 371
Net flux, 53 Osmotic evaporation (OE), see Osmotic

New Applexion Process (NAP), 245 distillation (OD)
NF, see Nanofiltration Osmotic membrane distillation, 216
Nitrocellulose membranes, 5 Osmotic pressure, 19–22, 41–42
NMWCO, see Nominal molecular weight cut-off O/W emulsion, see Oil-in-water
“Noble rot”, 186 O/W/O emulsions, see Oil-in-water-in-oil
Nominal molecular weight cut-off (NMWCO), 199 emulsions
Non-Saccharomyces yeasts, 335
Nondissolved solid (NDS), 275 P
Nonflavonoids, 152, 158
Nonisothermal membrane separation PA, see Polyamide
processes, 82 Packed-bed bioreactors (PBR), 329
Nonporous membrane processes, 19 PAN, see Polyacrylnitrile
Nonporous pervaporation membrane, 176 Parallel-plate bioreactors (PPR), 329
Nonporous processes, 9, 14, 16, 67 Particle blocking, 76
Nonthermal concentration methods, 196 Pasteurization, 98–99
Novel products, 231–232 PBR, see Packed-bed bioreactors
NRTL model, 188 PDMS membrane, see Polydimethylsiloxane
Nusselt number (Nu), 82 membrane
PDO, see Protected designation of origin
O PE, see Pectinesterase
Peclet number, 45
Observed rejection coefficient, 10–11 Pectic acid, 323
OD, see Osmotic distillation Pectin, 171–172, 323
Oenococcus oeni (O. oeni), 339 Pectinases, 322, 323, 325
Oil-in-water-in-oil emulsions (O/W/O emulsions), Pectinesterase (PE), 323
291 Pectinic acids, 323
Oil-in-water (O/W emulsion), 281–282, 284, Pectinolytic enzymes, 322
288–289 PEF treatment, see Pulsed electric field treatment
Oil processing, 331–335 PEG, see Polyethylene glycol
Olea europaea, see Olive tree Peonidin-3-glucoside, 155
Oleuropein, 346 Peptides, 136, 318
Oligosaccharides, 323 fractionation, 119–120
Olive mill wastewater (OMWW), 328, 345 Permeability, 172
Olive oil mill waste (OMW), 345 “Permeance”, 78
biophenols in, 346 Permeate, 10, 13, 162, 163
Olive oil production methods, 345 fluxes, 174–175, 181
Olive tree (Olea europaea), 346 Permeation, 171
OMD, 216, 222, 231 PERVAP 1070 (Hydrophobic membrane), 226
membrane process, 231–232 Pervaporation (PV), 6, 68, 73, 170, 211–212,
OMW, see Olive oil mill waste 229–230; see also Microfiltration
OMWW, see Olive mill wastewater (MF); Nanofiltration (NF);
Opex, 53–54 Ultrafiltration (UF)
Optimal transmembrane pressure, 164 applicability of, 228
Organic compounds, 180 for aroma recovery, 180, 225
Organic membrane, 162 azeotropic distillation, 74
Organic molecules, 14 comparison between pervaporation and
Organic precipitates, 56 vapor/gas separation, 75
Organoleptic properties, 180 fouling mechanisms of dense membranes, 76
Organoleptic quality, 165 hollow fiber module, 227–228
Osmosis, 5 hydrophobic, 228–229
Osmotic agent, 171 membranes, 173–174
Osmotic distillation (OD), 68, 78, 84–85, polymers for, 70–73
170–171, 176–179, 202, 207, 348 wine dealcoholization by, 174–176
applications, 79 PES, see Polyethersulfone
Cranberry juice, 223 Petunidin-3-glucoside, 155
wine dealcoholization by, 176–179 PG, see Polygalacturonase
372 Index
pH, 259–260 hollow fiber modules, 218–219

differential method, 157 hollow fiber ultrafiltration membrane, 276
Pharmaceutical industry, 140 Polysaccharides, 166
Phase inversion method, 311 Polysulfone (PS), 6, 134
PHBV, see Poly(3-hydroxybutyrate-co-3- hollow fiber membranes, 222
hydroxyvalerate) Polytetrafluoroethylene (PTFE), 78, 85, 209, 210
Phenol, 157 membranes, 6, 275, 286
Phenolic compounds, 152, 185 Polyvalent anions, 116
Phenolics, 154 Polyvinyl chloride (PVC), 329
Phenoloxidase, 328 Polyvinylidene-difluorite, see Polyvinylidene
Phormidium laminosum (P. laminosum), 329 fluoride (PVDF)
Phospholipid removal, 274 Polyvinylidene fluoride (PVDF), 6, 78, 199,
Physical methods, immobilization by, 311 272, 317
Pigmented polymers, 155 membranes, 24–25
Pilot-size membrane contactor, 179 Pomegranate (Punica granatum L.), 227
PLA, see Poly(lactic acid) POMS membranes, see Polyoctylmethyl siloxane
Plant raw material as source, 329 membranes
oil processing, 331–335 POMS/PEI, see Polyoctylmethylsiloxane
starch hydrolysis, 329–331 supported by polyetherimide
Plate-and-frame modules, 228 Porcine gelatins, 140
Plate modules, 31 Pore
PMG, see Polymethylgalacturonase blockage, 42
Polarization, 343 sizes, 16
Polishing, 262 wetting, 78–79
aerobic, 140 Pore diameter (dp), 287
evaporator condensate, 252 Porous membranes, 9, 14
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Porous processes, 67
(PHBV), 71 Porto wine, 187
Poly(lactic acid) (PLA), 71 Portuguese wine, 152
Poly(vinylalcohol) (PVA), 71 Potassium bitartrate, 167–168
Poly(vinylidene fluoride) (PVDF), 176 Potato starch processing, 257–258
Polyacrylnitrile (PAN), 6, 71 concentration of proteins from potato fruit
Polyamide (PA), 24 water, 258
Polycarbonate, 6 Potent chemopreventive agent, 346
Polydimethylsiloxane membrane (PDMS PP, see Polypropylene
membrane), 71, 225 PPR, see Parallel-plate bioreactors
Polyethersulfone (PES), 6, 166 Prandtl number (Pr), 82
membranes, 25, 118–119 Premix membrane emulsification, 285
Polyethylene glycol (PEG), 307 Pressing method, juice extraction by, 197–198
Polygalacturonase (PG), 323 Pressure-driven membrane processes, 15–16, 94
Polymeric membranes, 24 Pretreatment agents, 168
chemical structure of polymers, 25–27 Pretreatment methods, 60–61
PVDF membranes, 24–25 Proanthocyanidins, 155, 188
Polymers Process engineering, 8
chemical structure, 25–27 Product demineralization, 262
for GS and PV, 70–73 Protected designation of origin (PDO), 104
Polymethylgalacturonase (PMG), 323 Proteins, 96, 116
Polymethyl galacturonate, see Pectin concentration in cheese manufacture, 106–106
Polyoctylmethyl siloxane membranes (POMS functional groups, 313
membranes), 225 hydrolysate fractionation and concentration,
Polyoctylmethylsiloxane supported by 135–136
polyetherimide (POMS/PEI), 71 hydrolysis, 317–320
Polypeptides, 140 from potato fruit water concentration, 258
Polyphenols, 155, 166 standardization, 106
compounds, 153 from Surimi production, 131–134
content, 168 Proteolysis, 320
Polypropylene (PP), 6, 78, 166 Protopectin, 323
Index 373
Protopectinases, 322 Rubbery polymers, 26, 71

Prunasin, 328 “Rudolf Diesel”, 276–277
PS, see Polysulfone RVF, see Reduction volume factor
PTFE, see Polytetrafluoroethylene RVFs, see Rotary vacuum filter
Pulsed electric field treatment (PEF treatment), 185
Punica granatum L., see Pomegranate S
Purification
of raw beet juice, 249–250 Saccharification step, 259–260
of raw sugar cane juice, 244–246 Saccharomyces cerevisiae (S. cerevisiae),
PV, see Pervaporation 166–167
PVA, see Poly(vinylalcohol) SAT process, 245
PVC, see Polyvinyl chloride Saturation vapor pressure, 22
PVDF, see Poly(vinylidene fluoride), Scanning electron microscopy (SEM),
Polyvinylidene fluoride 166–167, 217
Schmidt number (Sc), 45
Q Sea buckthorn (Hippophae rhamnoides L.), 219
Seafood processing industry, 130; see also
Quality wine, 163 Animal products industry; Dairy
Quasi-chemical theories, 70 industry; Egg-processing industry
Quercetin, 154 fractionation and concentration of protein
hydrolysates, 135–136
R recovery of proteins from Surimi production,
131–134
Raoult’s law, 69 treatment of effluents, 134–135
Rapeseed oils, 275 Selectivity, 10
Raw beet juice purification, 249–250 SEM, see Scanning electron microscopy
Raw sugar cane juice purification, 244–246 Sensory analysis, 184, 185, 215–216
Red blood cells fraction (RBC fraction), 137 Sensory attributes, 198
Reduction volume factor (RVF), 218 Separation mechanism, 13–14, 198–199
Red wines, 158, 160–161, 179, 185 “Serocolostrum”, 119
Response surface methodology (RSM), 281 Serum proteins, 97, 104
Resveratrol, 155–157, 159 concentration of, 117–118
concentration in original red wine, 183 fractionation of, 118–119
content, 153 SGMD, see Sweeping gas membrane
in dried roots, 158 distillation
enhanced wine, 187 Shell dissociation, 292
extraction, 187 Shell porosity modulation, 292
Retentate, 10, 13, 181, 184 Sherry wines, 187
concentrations, 172 Sherwood number (Sh), 45
Reverse osmosis (RO), 4, 6, 18, 43, 71, 76, 84, 94, Shirasu porous glass (SPG), 282
162–163, 216, 246, 252, 262; see also Sicilian red wines, 154
Forward osmosis (FO) Sieving mechanism, 13–14
with cellulose acetate membranes, 251 SMBR, see Submerged membrane bioreactor
concentration, 173 Sodium chloride, 85
membrane, 184 Sodium metabisulfite, 171–172
membranes, 216 Sodium sulfate (Na2SO4), 217
RO + OD, 180 Sodium sulfite (Na2SO3), 217
wine dealcoholization by, 171–174 Solar energy, 82
wine ingredients content by, 184–186 Soluble proteins, see Serum proteins
Reynolds numbers (Re), 31, 45, 82, 177 Solution-diffusion mechanism, 13–14
Ribes nigrum, see Berry fruit black currant Solution-diffusion theory, 73–76
Ripe grape, 162 and link to activity, 76–78
RO, see Reverse osmosis Solvent-resistant nanofiltration (SRNF), 278–279
Rosé wines, 153, 160, 170 Solvent flux, 172
Rotary vacuum filter (RVFs), 260 Sparkling wine, 187–188
Rotor-stator systems, 283–284 SPG, see Shirasu porous glass
RSM, see Response surface methodology Spiral-wound modules, 31
374 Index
Spirit “Sweet” whey, 97

production, 188 Sweetener demudding, 261–262
from wine, 188 Sweet water concentration, 252, 262, 263
Spore removal, 98–104 Symmetric membranes, 28
commercial MF system for removal of Synthetic wine, 179
bacteria from milk, 100 Syrup/raw syrup, 244
depiction of membranes, 102 Systematic back pulse, 166–167
homogeneous transmembrane pressure, 101 Systematic membrane cleaning, 166
microfiltered–pasteurized milk, 103
PDO, 104 T
principle of UTP system, 100
process for MF of whole milk, 99 TAA, see Total antioxidant activity
SRNF, see Solvent-resistant nanofiltration TAC, see Total antioxidant capacity
Stabilization, 129, 164 TAGs, see Triglycerides
combined MF + NF system, 168 Tannic acid, 171–172
components of crude and centrifuged Tannin, 157
wines, 165 Tartaric acid, 163, 171–172, 188
ED, 169 Tartaric stabilization, 169
MF, 164, 166, 167 Tartrate crystals, 167–168
Starch and starch-based sweetener industry, 252 Temperature polarization (TPC), 79
corn/maize starch processing, 253–255 TG, see Triradylglycerolipids
potato starch processing, 257–258 Thermodynamic equilibrium, 69
starch-based sweetener, 258–262 Thermomyces lanuginosa (TL IM), 334
wheat starch processing, 255–257 Thermostable enzymes, 315
Starch-based sweetener, 258 Thin liquid film, 171
evaporator condensate polishing, 262 Threshold flux, 53
product demineralization and polishing, 262 TMP, see Transmembrane pressure
production, 260 TOC, see Total organic carbon
sweetener demudding, 261–262 Tokaji Aszu Wine, see Tokay Wine
sweet water concentration, 262, 263 Tokay Wine, 186
Starch(es), 242 Tomato juice clarification, 233, 234
hydrolysis, 329–331 Tonality of wine, 179
slurry, 259 Total anthocyanin content, 185
washing, 255 Total antioxidant activity (TAA), 199
Steeped corn, 253 Total antioxidant capacity (TAC), 152
Steeping water handling, 254 Total antioxidant potential, 153
Stereoisomerism, 26 Total heat flux, 81
Sterilization, 4–5, 161, 164, 202 Total monomer anthocyanin, 157
combined MF + NF system, 168 Total monomeric anthocyanin content, 182
components of crude and centrifuged Total organic carbon (TOC), 189
wines, 165 Total phenolic content (TPC), 152
MF, 164, 166, 167 Total solid (TS), 257
Stilbenes, 158 Total soluble solid (TSS), 199
concentration, 152 TPC, see Temperature polarization; Total
Stirred-tank reactor (STR), 307 phenolic content
STR, see Stirred-tank reactor Traditional fining process, 164
Stripping solutions, 176, 177, 179 Traditional methods for ethanol reduction of
Strong acids, 63 wines, 170
Submerged membrane bioreactor (SMBR), 280 Trans-resveratrol, 152–158, 182–183
Sugar cane production, see Cane sugar production Transmembrane pressure (TMP), 16, 41, 47, 181,
Sugars, 184, 187–188, 242 199, 273, 286
Supercritical fluid extraction, 170 Transverse flow modules, 31
Surface blocking, 76 Triglycerides (TAGs), 332
Surimi production, proteins from, 131–134 Triradylglycerolipids (TG), 279–280
Sustainable flux, 53–54 Trypsin, 318
Sweeping gas membrane distillation (SGMD), TS, see Total solid
82, 83 TSS, see Total soluble solid
Index 375
Tubular membranes, 217 Volume reduction ratio (VRR), 99, 107, 108
Turkish wines, 154 Volumetric concentration factor (VCF), 272
diafiltration, 34–35 VP processes, 75
VRF, see Volume reduction factor
U VRR, see Volume reduction ratio
UF, see Ultrafiltration W

UF-RO, see Ultrafiltration-reverse osmosis
Ultra-high temperature (UHT), 103 “Wastes”, 300
Ultrafiltration-reverse osmosis (UF-RO), 270 Waste valorization by membrane bioreactor,
Ultrafiltration (UF), 4, 5, 7, 17–18, 43, 56, 84, 344–348
94, 131–133, 162–165, 197, 199, 216, Wastewater, 189
317, 318, 348; see also Microfiltration treatment, 94
(MF); Nanofiltration (NF); in wineries, 189
Pervaporation (PV) Water, 67, 176
biodiesel production using UF membrane flux, 177
separation technology, 276–281 juice extraction by, 198
modeling UF in absence of fouling, 47–50 recovery of process, 121
modeling UF in presence of fouling, 50–54 vapor transport, 83
unit, 305 water-soluble substances, 131
UNIFAC method, 70 Water-in-oil-in-water emulsions (W/O/W
Uniform transmembrane pressure (UTP), 95, 100 emulsions), 291
UNIQUAC method, 70 Water-in-oil emulsion (W/O emulsion), 281, 284
UTP, see Uniform transmembrane pressure production, 288–289
Watermelon, 221
V Wheat starch effluents treatment, 257
Wheat starch processing, 255–257
Vaccinium macrocarpon Ait., see Cranberry juice treatment of wheat starch effluents, 257
Vaccinium myrtillus L, see Bilberries Whey
Vacuum freeze drying, 84 acid, 97
Vacuum membrane distillation (VMD), 82, 83 characteristics, 96–98
Valorization of waste by membrane bioreactor, concentration, 114–115
344–348 ideal, 111
van’t Hoff’s equation, 21–22 sweet, 97
Vapor–liquid interface, 80 Whey and derivates, membrane separations to, 114
Vapor pressure, 22, 80 concentration, 114–115
VCF, see Volumetric concentration factor concentration of serum proteins, 117–118
VCR, see Volume concentration ratio demineralization, 115–117
Vegetable juice processing and concentration, fractionation of peptides, 119–120
232–234 fractionation of serum proteins, 118–119
Vegetable oil production Whey processing, MBRs in, 312
membrane emulsification and encapsulation hydrolysis of milk fat, 320–321
in food industry, 281–294 lactic acid production, 315–317
membrane filtration in vegetable oil lactose hydrolysis, 314–315
purification, 270–281 protein functional groups, 313
Vermouths, 187 protein hydrolysis, 317–320
Versatile microbial lipases, 331 Whey protein concentrates (WPCs), 106, 117
Virgin olive oil, 281 Whey protein isolates (WPI), 111
Vitamin C, 200 Whey proteins, see Serum proteins
Vitis vinifera (V. vinifera), 187 White grape, 186
VMD, see Vacuum membrane distillation White wines, 155, 160
VOC, see Volatile organic carbon Wine-making process, MBR systems in, 339
Volatile acidity reduction, 163 Wine(s)
Volatile fraction, 179 components, 165
Volatile organic carbon (VOC), 227 concentrate, 181
Volume concentration ratio (VCR), 33 consumption, 169
Volume reduction factor (VRF), 199 ingredients content by RO, 184–186
376 Index
Wine(s) (Continued) membranes in wine making, 162

maker, 161 MF, 164, 166, 167
making, 150 pervaporation for aroma recovery, 180
modern, 169 phenolic compounds, 154
modern method for ethanol reduction of, 170 polyphenol contents, 155
Porto, Madeira, Malaga, Marsala wines, 187 proposed membrane processes, 163
Portuguese, 152 resveratrol enhanced wine, 187
production, 164 sherry wines, 187
vigor, 155 special wine products, by-products, 186
wine-making industry, 162 spirits from wine, 188
Wine clarification, 162, 164 Tokay wine, 186
combined MF + NF system, 168 TPC and TAC, 152
components of crude and centrifuged traditional methods and modern method for
wines, 165 ethanol reduction of wines, 170
MF, 164, 166, 167 traditional wine making, 159–162
Winemaking, bioreactors in, 340 vermouths, 187
Wine production using membranes vitamins, anions, and cations in wines, 151
anthocyanin contents, 156 wastewater in wineries, 189
application of grape seeds, skins, and lees, wine clarification, sterilization, and
188–189 stabilization, 164
by-products in wineries, 188 wine from dried grape, 186–187
champagne and sparkling wine, 187–188 wine history, 150
chemical components of wine, 150 wine ingredients content by RO, 184–186
chemical substances in wine, 151 Wineries, 189
combined MF + NF system, 168 W/O emulsion, see Water-in-oil emulsion
commercial spanish wines, 153 W/O/W emulsions, see Water-in-oil-in-water
components of crude and centrifuged emulsions
wines, 165 WPCs, see Whey protein concentrates
concentration of wine, increase of valuable WPI, see Whey protein isolates
components’ content, 181
concentration with NF, 181–184 X
dealcoholization by combined method, 180
dealcoholization by liquid emulsion XN45 Trisep membrane, 181
membrane, 179
dealcoholization by OD, 176–179 Y
dealcoholization by pervaporation, 174–176
dealcoholization by RO and NF, 171–174 Yeast, 160, 165, 288
dry wine, 187 deposit, 167
ED, 169 Yolk, 126
ice wine, 186 Younger wines, 154
low-alcohol wine production, 169
medical effects of wine, 157–159 Z
membrane methods for ethanol reduction in
wines, 170–171 Zirconium oxide, 168

(Contemporary Food Engineering) Robert W. Field, Erika Bekassy-Molnar, Frank Lipnizki, Gyula Vatai - Engineering Aspects of Membrane Separation and Application in Food Processing-CRC Press (2017)

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(Contemporary Food Engineering) Robert W. Field, Erika Bekassy-Molnar, Frank Lipnizki, Gyula Vatai - Engineering Aspects of Membrane Separation and Application in Food Processing-CRC Press (2017)

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Engineering Aspects of

© 2017 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4200-8363-7 (Hardback)

Library of Congress Cataloging-in-Publication Data

Names: Field, Robert W., editor. | Bekassy-Molnar, Erika - editor. |

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

Section I Basic Principles of Membrane Processes

Chapter 1 Membrane Separation Processes: An Overview................................... 3

Chapter 2 Concentration Polarization, Fouling, and Its Mitigation..................... 41

Chapter 3 Activity-Driven Membrane Processes................................................. 67

Chapter 5 Wine Production Using Membranes................................................. 149

Chapter 6 Fruit and Vegetable Juice Processing Applications.......................... 195

Chapter 7 Membrane Processes for Sugar and Starch Processing.................... 241

Chapter 8 Vegetable Oil Production: Emulsification......................................... 269

Chapter 9 Food Applications of Membrane Bioreactors................................... 299

Erika Bekassy-Molnar expresses her gratitude to Professor Zsolt Fonyo at the

Erika Bekassy-Molnar graduated from the Technical University of Budapest

a­ ssociated R&D manager at Alfa Laval—Business Centre Membranes, Denmark

Gyula Vatai qualified as a chemical engineer, with specialization in process

Robert Field Edit Marki

1.8.4 Membrane Process Design.................................................................. 37

1.2 INTRODUCTORY REMARKS

a disadvantage) and solvents (putting extraction at a disadvantage). Many advantages

1.3 MEMBRANE PROCESSES

1.3.1 A Chemical Engineering Perspective

1.3.2 Basic Concept of Membrane Processes

a For UF and MF membranes, separation performance is determined by size exclusion mechanism.

Solubility Solvent extraction

Clarifier gravity sedimentations

Particle size 10–4 10–3 10–2 10–1 1.0 10 102 103

Approximate 100 200 20,000 500,000

Processes. John Wiley, New York.)

FIGURE 1.4 Membrane separation mechanisms: sieving mechanism (1), solution-diffusion

Based on the solution-diffusion mechanism, molecules of equal size or larger

1.3.3 Basic Modes of Operation

(1) Feed (2)

Filter cake Membrane Permeate

In pressure-driven membrane separation, the driving force is of course the pres-

1.4 MEMBRANE CLASSIFICATION

MF membranes are given an absolute rating typically based on the diameter of

1.4.7 Nonporous Membrane Processes

1.4.8 Activity-Driven Nonwetted Membrane Processes

1.5 MEMBRANE-RELATED ASPECTS OF PHYSICAL CHEMISTRY

Solution 2 Solution 1 Solution 2 Solution 1

the fruit juice, wine, sugar, and honey industries.

where idj is the degree of dissociation of component j expressed as the number of

idj = αm + (1 − α ) = 1 + α(m − 1) (1.12)

Substantial deviations from van’t Hoff’s equation occur at high concentrations

1.6 MEMBRANE MATERIALS, TYPE, AND STRUCTURES

selectivity/sieving characteristics, good mechanical stability, and good chemical sta-

Synthetic Biological Origin

Organic Inorganic Material

Dense Porous Morphology

Phase inversion Composite Phase inversion

FIGURE 1.7 Classification of membranes. (Modified after Rautenbach, R. and Albrecht, R.

1.6.3 Polymeric Membranes

1. Molecular weight and number of repeating units

1.6.3.1 Chemical Structure of Polymers

(1) Homogenous polymer

(2) Block polymer

(3) Random polymer

a ssociated R&D manager at Alfa Laval—Business Centre Membranes, Denmark

m f ⋅ dw = −(a ⋅ win + b)dA (1.22)

2.5 FOULING: ITS NATURE AND KEY INFLUENCES

To plot fn(J,n) versus (V − J nt ) requires an estimate of J n but an alternative is