c81e7PROCESS INTENSIFICATION

RE-ENGINEERING
THE CHEMICflL
PROCESSING PMNT
Process Intensification
edited by
flndrzej ftankiewicz
DSM Research
Geleen, and
Delft University of Technology
Delft, The Netherlands
Jacob fl.Moulijn
Delft University of Technology
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
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Preface
The book you are about to read will introduce you to modern ways of reengineering the chemical processing plant by means of Process Intensication (PI).
The story behind this book had begun with the paper Process Intensication:
Transforming Chemical Engineering, which we published in the millennium issue
of Chemical Engineering Progress (January 2000). After a pretty enthusiastic
response to our paper by the chemical engineering community, Marcel Dekker
proposed to us writing a book on that subject. After some discussions we came to
the conclusion that it was not a good idea to write the entire book ourselves
because, as you will see next, Process Intensication is a very broad discipline and
includes many diverse expertise elds. So, instead of writing all chapters on our
own, we have invited a number of prominent experts in various areas of Process
Intensication, both from industry and from academia, to contribute to what now
has become the worlds rst book on that subject.
The principal aim of this highly practice-oriented book is to illustrate the
current developments and the frontline research in the area of Process
Intensication. The book is primarily intended for engineers, technologists and
researchers in chemical, biochemical and engineering companies, who are
involved in process design and development and are interested in learning more
about equipment and techniques that may bring quantum-leap improvements to
their technologies. Also for others working in the forefront of process design and
development it is intended to be inspiring, in particular for the chemical engineering community in the universities and the National Laboratories. We hope
that it will contribute to a better image of the chemical industry and even play a
role in attracting more high-quality, motivated students to the discipline. The
book may also be benecial to R&D managerial personnel who wish to have a
broader understanding of the principles and methodology of Process
Intensication and gain the up-to-date knowledge of the emerging novel equipment and processing methods that could help to achieve technological breakthroughs in the processes at their companies.
The book has a certain logical structure that can be inferred from scanning
the individual chapter headings. Chapter 1 introduces the reader into the genesis,
philosophy and principles of Process Intensication and discusses its dimension
and structure. It provides general information on process-intensifying equipment
and methods and gives some examples of their application on the commercial
scale. The three subsequent chapters describe selected types of the PI-equipment.
Most of that equipment have already been successfully implemented on the commercial scale or is ready for implementation. Chapters 2 and 3 are devoted to the
rotating equipment, rotating packed beds and spinning disk reactors, in which the
use of high gravity elds leads to spectacular miniaturization of the processing
units. Chapter 4 in turn describes the technology, design and application of compact and multifunctional heat exchangers. The next three chapters show how
bringing certain structures in various scales of chemical processing environment
can boost process efciency, by dramatically improving mixing, heat and mass
transfer. Various types and scales of such structuring are presented: microreactors
in Chapter 5, large-scale structured catalysts and reactors in Chapter 6 and
inline mixing equipment in Chapter 7. Following that hardware part of the
book, its next four chapters focus on some important methods that can be used for
intensication of chemical processes. Chapter 8 presents the application aspects
of functional integration of reaction and separation into reactive separation systems, or integration of different separative techniques into hybrid separations. In
Chapter 9 the modeling issues of the reactive separation systems are discussed.
Chapter 10 discusses some aspects of the integration of reaction and heat transfer
in multifunctional reactors, while Chapter 11 focuses on the application of process synthesis principles to the optimal design of integrated chemical processing
plants. The nal three chapters of the book address more general issues of Process Intensication. Chapter 12, based on the experiences within DSM, shows
how the PI-principles can be applied in the industrial environment for redesigning and development of process-intensive chemical plants, while Chapters
13 and 14 focus respectively on safety and sustainability aspects of PI.
The chemical industry skyline in the 21st Century is changing. New highly
efcient devices have already begun replacing the tens-of-meters high reactors and
separation columns. In the still denser populated world inhabited by the still more
educated and environment-conscious society, there will be no room (literally and

guratively) for the huge, inefcient chemical factories of today, generating tens
of tons of waste per each ton of the useful product. As a part of the society-driven
changes miniaturization and, in general, intensication of chemical and biochemical plants, will become inevitable.
We are well aware that the present book does not cover all developments in
the eld of Process Intensication. It has not had such ambitions. With this collection of contributions by the leading experts in the eld, we have tried to focus
on the main developments and main issues only, hoping that they will give the
reader sufcient avor of PI and will encourage him/her to further studies on how
to re-engineer a chemical processing plant basing on the smaller-cheaper-saferslicker principles of Process Intensication. Both contributors and editors will
be very glad to hear from the reader if we indeed have succeeded. Also suggestions for a possible next edition are welcome!
Andrzej Stankiewicz
Jacob A. Moulijn
Contents
Preface
Contributors
1. Process Intensication: History, Philosophy, Principles
Andrzej Stankiewicz and A. A. H. Drinkenburg
2. Chemical Processing in High-Gravity Fields
David L. Trent
3. The Spinning Disc Reactor
C. Ramshaw
4. Compact Multifunctional Heat Exchangers: A Pathway to
Process Intensication
B. Thonon and P. Tochon
5. Process Intensication Through Microreaction Technology
Wolfgang Ehrfeld
6. Structured Catalysts and Reactors: A Contribution to
Jacob A. Moulijn, Freek Kapteijn, and Andrzej Stankiewicz
7. Inline and High-Intensity Mixers

Andrew Green
8. Reactive and Hybrid Separations: Incentives, Applications,
Barriers
Andrzej Stankiewicz
9. Reactive Separations in Fluid Systems
E. Y. Kenig, A. Grak, and H.-J. Bart
10. Multifunctional Reactors: Integration of Reaction and Heat
Transfer
David W. Agar
11. Process Synthesis/Integration
Patrick Linke, Antonis Kokossis, and Henk van den Berg
12. Process Intensication in Industrial Practice: Methodology and
Application
Remko A. Bakker
13. Process Intensication for Safety
Dennis C. Hendershot
14. Process Intensication Contributions to Sustainable Development
G. Jan Harmsen, Gijsbert Korevaar, and Saul M. Lemkowitz
Contributors
David W. Agar Lehrstuhl fr Technische Chemie B, University of Dortmund,

Dortmund, Germany
Remko A. Bakker DSM Fine Chemicals Austria, Linz, Austria
H.-J. Bart Institute of Thermal Process Engineering, University of Kaiserslautern,
Kaiserslautern, Germany
A. A. H. Drinkenberg DSM Research, Geleen, The Netherlands
Wolfgang Erhfeld Ehrfeld Mikrotechnik AG, Wendelsheim, Germany
A. Grak Lehrstuhl fr Thermische Verfahrenstechnik, University of Dortmund,
Germany
Andrew Green BHR Group Limited, Craneld, England
G. Jan Harmsen Delft University of Technology, Delft, The Netherlands
Dennis C. Hendershot Rohm and Haas Company, Bristol, Pennsylvania, U.S.A.
Freek Kapteijn Delft University of Technology, Delft, The Netherlands

E. Y. Kenig Lehrstuhl fr Thermische Verfahrenstechnik, University of Dortmund,
Dortmund, Germany
Antonis Kokossis University of Surrey, Surrey, England
Gijsbert Korevaar Delft University of Technology, Delft, The Netherlands
Saul M. Lemkowitz Delft University of Technology, Delft, The Netherlands
Patrick Linke University of Surrey, Surrey, England
Jacob A. Moulijn Delft University of Technology, Delft, The Netherlands
C. Ramshaw Department of Chemical and Process Engineering, University of
Newcastle upon Tyne, Newcastle upon Tyne, England
Andrzej Stankiewicz DSM Research, Geleen, and Delft University of Technology,
B. Thonon
P. Tochon
Greth, CEAGrenoble, Grenoble, France

David L. Trent
The Dow Chemical Company, Freeport, Texas, U.S.A.
Henk van den Berg Faculty of Chemical Technology, University of Twente,

Enschede, The Netherlands, and Ghent University, Ghent, Belgium
1
Process Intensication:
History, Philosophy, Principles
Andrzej Stankiewicz and
A. A. H. Drinkenburg
DSM Research, Geleen, The Netherlands
1.
INTRODUCTION
Process intensication (PI) is currently one of the most signicant trends in chemical engineering and process technology. It is attracting more and more of the
attention of the research world. Four international conferences, several smaller
symposia/workshops every year, and a number of dedicated issues of professional
journals are clear proof of it. A number of commercial-scale applications of the
PI principles have already taken place. But how did it all begin?
2.
A BIT OF HISTORY
According to Miriam-Websters Collegiate Dictionary, the word intensive has probably its origins somewhere in 15th century. And it was not many years later, right
at the peak of the Renaissance, when Georgius Agricola published his famous book
De Re Metallica (1), the book that is commonly regarded as the rst comprehensive textbook on the engineering of mining and metallurgy. De Re Metallica is
richly illustrated with woodcuts showing equipment and processing methods used
in the times of Agricola. In many of those woodcuts clear elements of process
intensicationoriented thinking can be found. One example is shown in Figure 1,
FIGURE 1 Sixteenth century technology of gold retrieval from gold ore. (From
Ref. 1.)
which illustrates the process of retrieving gold from gold ore. The technology is
pretty simple. The ore is crushed by the stamp, C, ground in the mill, F, and
mixed with mercury in vessels O. Gold is extracted from the ore by mercury and
is later separated from it by pressing the mixture through a leather or cloth lter
bag (not shown in the drawing). Taking a closer look at the woodcut, one notices
that the stamp, the mill and the stirrers for mixing the ore with mercury are all
driven by the same water wheel, A, via the common axle, B, and a number of
various gears. Speaking the language of the 21st century, one could say, A marvelous example of a green, energy-based, highly integrated processing plant! (One
dare not, however, call it a sustainable technology. Not only are the gold reserves
unsustainable, but the operations involving mercury are not environmentally
friendly, as we all know today.)
Yet there is another aspect to Agricolas woodcut. As one may have noticed,
some of the equipment shown (OS) exhibits a striking resemblance to the
equipment used in the chemical process industry almost 450 years later (see
Figure 2). Were the contemporaries of Agricola so ingenious, or are we merely
satised with the inventions of past centuries? At the dawn of the third millennium,
in-series stirred tanks still remain the most common chemical processing system.
An attempt to break this domination of the stirred-tank technology by the invention
and introduction of the static mixer (2,3), is one of the nest and earliest modern
examples of process intensication. Here, the technological leap was achieved
not by the improvement of the stirring itself but, quite the opposite, by abandoning
the mechanical stirring as a method of mixing uids! This reveals one of the most
important features of PIthe changes it brings are drastic in nature, revolutionary
rather than evolutionary.
In the scientic literature, the term process intensication started to appear
in the mid-1960s and early 70s, mostly in East European publications concerning
FIGURE 2 Four and half centuries have passed, yet almost no fundamental
differences can be seen between the technology of 1556 and that of 2002.
metallurgical processing (4 7) (an interesting coincidence, considering that

Agricolas book was also on metallurgy, not on chemical processing). Of course,
all of those papers understood process intensication as simply equivalent to
process improvement. Also, in the rst chemical industryoriented articles (all of
East European origin, by the way), the term process intensication had that same
meaning (810).
The birth of process intensication as a chemical engineering discipline came
several years later in the United Kingdom and was marked by the paper published
in 1983 by Colin Ramshaw from the ICI New Science Group, who described their
studies on the application of centrifugal elds (so-called HiGee) in distillation
processes (11). A few months later the Annual Research Meeting, entitled
Process Intensication, was held at UMIST, Manchester (12). Interestingly, the
rst paper presented at that meeting concerned processing of gold ore using
intensive methodsa strange coincidence, indeed.
Both in the paper by Ramshaw and in the report from the UMIST conference,
first denitions (or rather descriptions) of process intensication can be found.
Ramshaw (11) describes PI as devising an exceedingly compact plant which
reduces both the main plant item and the installations costs, while according
to Heggs (12) PI is concerned with order-of-magnitude reductions in process
plant and equipment. In one of his subsequent papers, Ramshaw writes about typical equipment volume reduction by two or three orders of magnitude (13).
Until the early 1990s, process intensication was mainly a British discipline
and was focused primarily on four areas: the use of centrifugal forces, compact heat
transfer, intensive mixing, and combined technologies (14). It was also the Brits
who organized the rst international conference on PI (15). By that time, however,
process intensication had already become an international business, for many
research centers in different countries had entered the eld. In Holland, for instance,
Delft University of Technology, together with DSM, carried out research on
structured reactors (16). Another group in Delft investigated centrifugal adsorption technology (17). In France, Greth CEN institute in Grenoble carried out
extensive studies on compact heat exchange equipment (18). In Germany, research
on microtechnology ourished in the Institut fr Mikrotechnik Mainz (19), while
in China a special center at Beijing University was established to carry out R&D
activities in the area of high-gravity processing (20). In the United States a number
of research institutes started PI-related studies too, e.g., Pacic Northwest National
Laboratory in the eld of microchannel heat exchangers (21) and MIT in the eld
of microreactors (22). Also early on, a number of chemical companies got involved
in process intensication. This involvement resulted in the rst successful
commercial-scale applications, such as the methyl acetate process of Eastman
Chemical (23), the hydrogen peroxide distillation system of Sulzer (24), and the
hypochlorous acid process of Dow Chemical (25).
The end of the 20th century and the beginning of the 21st have seen a fast
growth in PI-related activities in both industry and academia. In the UK the Process
Intensication Network was launched, gathering a large number of industrial and
academic participants; a similar network has been established in the Netherlands.
Four international conferences and several smaller symposia on PI have been
organized so far. Process Intensication, traditionally tied up with the commodity
chemicals sector, has begun entering new areas, such as bioprocessing and fermentation (2628) and, quite recently, ne chemistry (29). The denition of process
intensication has changed accordingly. It is no longer exclusively regarded as
drastically smaller equipment/plants (although equipment compactness remains
its most obvious feature). Process intensication, as it is widely understood nowadays, comprises novel equipment, processing techniques, and process development
methods that, compared to conventional ones, offer substantial improvements in
(bio)chemical manufacturing and processing (30).
The question may arise why it took so long for PI to come into the picture.
One possible answer is the enormous expansion of the process industry in the
third quarter of the 20th century, expansion in market size but certainly also in
plant scale. There were very few incentives at that time for the very risky introduction of new technologies. In the fourth quarter of the century, much effort was
spent on modeling, optimization, and control, resulting, among other things, in
the well-known onionskin methodologies of process development (e.g., Ref. 31).
Although very worthwhile at the time, these sequential, onionskin methodologies
(rst the reactor, then separation/purication, then heat integration, then process
control, safety, etc.) hindered the thinking in terms of integrated equipment. More
incentives were found in environmental engineering, also a topic of the second
half of the 20th century, that developed from the end-of-pipe solutions to problems to the integrated process solutions backsourcing the problems.
3. THE PHILOSOPHY AND OPPORTUNITIES
OF PROCESS INTENSIFICATION
The philosophy of process intensication has been traditionally characterized by
four words: smaller, cheaper, safer, slicker. And indeed, equipment size, land use
costs, and process safety are among the most important PI incentives. But process
intensication can (and should) also be placed in a broader contextthe context
of sustainable technological development. Several years ago DSM published a
picture symbolizing its own vision of process intensication (32), in which skyscraping distillation towers of the naphtha-cracking unit are replaced by a compact,
clean, and tidy indoor plant (see Figure 3). The importance of PI for sustainable
development and its role in the companys responsible business has been further
stressed in a recent publication by the companys CEO, Peter Elverding (33). Here,
FIGURE 3 DSMs vision of process intensication.
process intensication was the highest-rated activity of DSM within the known
Triple-P (protplanetpeople) triangle, as shown in Table 1.
From this general philosophy of process intensication follow concrete
opportunities that PI offers to chemical enterprises, as shown in Figure 4. These
opportunities exist primarily in four areas: costs, safety, time to market, and company image.
TABLE 1 Process Intensication in the ProtPlanetPeople
Triangle of DSM
Triple P
Process intensication
Green routes
Recycling
Energy efciency
Prot
Planet
People
Source: Ref. 32.
FIGURE 4 Main benets from process intensication.
3.1.
Costs
Process intensication leads to substantially cheaper processes, particularly in

terms of:
Land costs, resulting from much higher production capacity and/or number
of products per unit of manufacturing area
Other investment costs, resulting from cheaper, compact equipment, reduced
piping, reduced civic works, integrated processing units, etc.
Costs of raw materials, due to higher yields/selectivities
Costs of utilities, in particular costs of energy, due to higher energy efciency
Costs of waste processing (less waste generated in process-intensive plants)
Figure 5 shows the estimated savings in some DSM technologies, after applying
the PI principles (grass-roots situation).
3.2.
Safety
Process intensication drastically increases the safety of chemical processes. It

is obvious that smaller is safer. In Table 2 some of the more severe chemical
disasters of the past century are listed. The table shows clearly how disastrous
consequences may arise from the large inventories when something goes wrong.
And of course, one may not claim that process intensication would have prevented
all those tragedies. Yet a study done at AIChE showed that methyl isocyanate (MIC),
FIGURE 5 Estimated savings in some DSM technologies, achieved by applying PI principles to process and plant design (grass-roots situation).
the poisonous intermediate that was released at Bhopal, could be generated and
immediately converted to nal products in continuous reactors that contained a
total inventory of less than 10 kg of MIC (34)! But process intensication offers
not only smaller equipment but also much better possibilities for keeping processes
under control, for instance, via extremely efcient heat removal from exothermic
reactions (one speaks about heat transfer coefcients exceeding 20,000 W/m2K)
or via fully controlled gasliquid ow in structured catalysts that prevents liquid
maldistribution and hot-spot formation. Furthermore, intensication of the processing plant often leads to elimination of one or more of its components, which
also has a direct advantageous effect on process safety (What you do not have
cannot leak).
3.3.
Time to Market
Process intensication also offers substantial improvements to those sectors of

the chemical industry in which time to market plays a crucial role, e.g., the ne
chemical and pharmaceutical sectors. Ramshaw (35) discussed how process
intensication could shorten the time to market in case of a low-tonnage pharmaceutical process. The idea consists in developing a continuous lab-scale process
and using it directly as the commercial-scale process. One must not forget that
liquid ow of only 1 milliliter per second means, in continuous operation, circa
30 tons per year, which is quite a reasonable capacity for many pharmaceuticals.
TABLE 2 Some 20th Century Disasters in the Chemical Industry

Place
Date
Chemicals
Estimated
amount
Casualties
4,500 tons exploded
ca. 600 dead, 1500 injured

28 dead, 89 injured
Oppau/
Ludwigshafen
Flixborough
September 21,
1921
June 1, 1974
Ammonium sulfate,
ammonium nitrate
Cyclohexane
Beek
Propylene (mainly)
Seveso
November 7,
1975
July 10, 1976
2,4,5 Trichlorophenol,
dioxin
400-ton inventory,
40-ton escaped
10,000-m3 inventory,
5.5 tons escaped
7-ton inventory,
3 tons escaped
San Juan,
Mexico City
November 19,
1984
LPG
10,000-m3 inventory
Bhopal
December 3,
1984
October 23,
1989
Methyl isocyanate
41 tons released
Ethylene, isobutane,
hexene, hydrogen
33 tons escaped
Pasadena
14 dead, 107 injured

No direct casualties,
ca. 37,000 people
exposed
ca. 500 dead, 7000
injured (mainly
outside the plant)
ca. 3,800 dead, 2720
permanently disabled
23 dead, 130300 injured
The advantages of such an approach over the conventional one, based on the
scale-up philosophy of stirred tank bigger stirred tank even bigger stirred
tank, always batch are twofold:
Process development takes place only once, with no scale-up via a pilot
plant to the industrial scale. The scale-up of a batch process in stirred
tanks is not straightforward, especially in the case of reactions with a
large heat effect or a strong viscosity effect, and therefore can be troublesome and time-consuming.
All the administrative (FDA) procedures involved in the legal approval of
the production technology of the drug take place only once: The labscale technology is the commercial-scale technology.
In consequence, the start of commercial production can be greatly speeded up,
in some cases even by several years. Time to market will be shortened and the patent
lifetime of the drug will be much more effectively utilized (read: utilized longer).
3.4.
Company Image
More and more chemical companies do recognize the fact that their image, their
reputation, plays a very important role in successful business. A proper image of
the company is necessary to ensure public support for its activities. A study done
in the United States showed that only the tobacco industry and the nuclear energy
sector had a worse reputation than the chemical industry. The situation in Europe
is probably not very much different. On the other hand, process intensication,
deeply anchored in the philosophy of sustainable development, in safe and environmentally friendly processing, presents perhaps the simplest, the most obvious
key to the improved image of the chemical industry.
4. TECHNOLOGICAL BREAKTHROUGHS
AND CREATION OF SHAREHOLDER VALUE
In the reality of the global markets of the 21st century, not only do chemical companies compete with each other, they also have to compete with other sectors of
the economy by proving to their shareholders that the revenues they receive from
the chemical business are as good as or better than from other fast-growing sectors, such as software and servicing. But the chemical process industry struggles
to create value for its shareholders. As John Goldhill of Arthur D. Little Inc.
wrote, the chemical industry has lagged other industries in creating value for
shareholders for at least the past 10 years (36). And indeed, when looking at
stock index developments in various types of enterprises in the period 19972002
(Figure 6), one notices that the value of chemical shares grew substantially slower
than in other sectors. The strategy of growth in the chemical process industry at
FIGURE 6 History of the Standard & Poor stock index in the chemical sector
and other selected sectors of the economy, 19972002. (From: www.
bloomberg.com.)
the present time is based mainly on mergers, splits, takeovers, and modifying the
structure of the product portfolio. It is basically a strategy of growth via trade, not
via technological innovation. In most chemical companies nowadays, opportunities are sought in cost reductions via optimization of the primary business work
processes (e.g., operational excellence) and via opening up bottle necks in the
existing production facilities.
Unfortunately, neither of these activities can make a company very attractive to shareholders. In the optimization of work processes, a critical limit in cost
reductions will soon be reached, and competitors will also follow more or less the
same path, so the companys competitive advantage will only be temporary unless
a shakeout takes place. Opening up bottlenecks, squeezing out yet another few
percent from existing plants, is also not the way to convince investors that the
company is capable of delivering an adequate growth in earnings. One of the most
obvious solutions to that problem lies in innovations and technological breakthroughs, because only innovations and technological breakthroughs can ensure
a sustainable technological advantage, cost leadership, and growth potential.
Innovations and technological breakthroughs are what process intensication is
all about.
5.
PROCESS INTENSIFICATION TOOLBOX
The toolbox for process intensication is schematically shown in Figure 7. It

includes process-intensifying equipment (PI hardware) and process-intensifying
methods (PI software). Obviously, in many cases overlap between these two
domains can be observed as new methods may require novel types of equipment
to be developed and, vice versa, novel apparatuses already developed sometimes
make use of new, unconventional processing methods. In Figure 7, examples of
both PI hardware and PI software are shown. Many of them will be discussed in
detail in other chapters of this book. Here, we give only a brief overview of the
more important PI items.
5.1.
Process-Intensifying Equipment
As already mentioned, one classic example of technological breakthroughs in

process engineering was the invention and commercialization of static (motionless) mixers, examples of which are shown in Figure 8. Nowadays, static mixers
not only offer a more size- and energy-efcient method for mixing or contacting
uids. In the SMR static mixer reactor by Sulzer, mixing elements are made of
FIGURE 7 Process intensication toolbox.
FIGURE 8 Various types of static mixers. (Courtesy: Koch-Glitsch.)
heat transfer tubes (Figure 9). Thanks to that, the SMR units can successfully be
applied in processes in which simultaneous mixing and intensive heat removal/
supply are necessary, e.g., in nitration, neutralization, and polymerization reactions.
For the cases when efcient mixing has to be coupled with a solid-catalyzed
reaction a whole family of open-crossow-structure catalysts has been developed. The best known of them are the so-called KATAPAKs, commercialized by
Sulzer. One of them, KATAPAK-M is shown in Figure 10. It has good mixing
properties and can simultaneously be used as the support for catalytic material.
FIGURE 9 Static mixer reactor developed by Sulzer. (Courtesy: Sulzer

Chemtech.)
FIGURE 10 Sulzers KATAPAK-M. (Courtesy: Sulzer Chemtech.)
KATAPAKs are applied in catalytic distillation and in some gas-phase exothermic

oxidation processes traditionally carried out in xed beds. In these processes
KATAPAKs exhibit very good radial heat transfer characteristics (37).
In nonreactive distillation processes structured packings are also widely
used. One of the most recent and most promising types is the Super X-Pack developed by Nagaoka International Corporation, shown in Figure 11. This wire-based
packing is claimed to be able to reduce the height of a distillation column by a
factor of 5 compared to a conventional tray design, as shown in Figure 12 (38).
Also, the Super X-Pack can save up to 80% energy due to a substantially lower
pressure drop.
Heterogeneous catalytic processes can often be intensied by the use of
monolithic catalysts (39). These are metallic or nonmetallic bodies forming a
multitude of straight, narrow channels of dened uniform cross-sectional shapes
(Figure 13). In order to ensure sufcient porosity and to enhance the catalytically
active surface, the inner walls of the monolith channels are usually covered with a
thin layer of washcoat, which acts as the support for the catalytically active species.
The most important features of the monoliths are:
Very low pressure drop in single- and two-phase ow, one to two orders of
magnitude lower than in conventional packed-bed systems
FIGURE 11 Super X-Pack, developed by Nagaoka International Corp.

(Courtesy: Nagaoka International Corp.)
FIGURE 12 Height reduction of a distillation column claimed by Super X-Pack. (Courtesy: Nagaoka International
Corp.)
FIGURE 13 Monolithic catalysts.
High geometrical areas per reactor volume, typically 1.5 4 times higher
than in the reactors with particulate catalysts
Very high catalytic efciency, practically 100%, due to very short diffusion
paths in thin washcoat layer
Stankiewicz (40) gives a spectacular example of reactor size reduction by a factor of ca. 100, as a result of replacement of the conventional system with a monolithic reactor operated horizontally in a pipeline.
For highly exothermic reactions the so-called HEX reactors present a very
promising option. The basic common feature of all HEX reactors is much more
favorable heat transfer conditions in comparison with conventional reactors (heat
transfer coefcients typically 35007500 W/m2K, heat transfer areas up to
2200 m2/m3). A HEX reactor developed by BHR Group Ltd. (Figure 14) was able
to decrease the by-product formation in one of ICI Acrylics processes by 75%
(41) and to decrease the processing time in a Hickson & Welch ne chemical
process from 18 hours to 15 minutes, saving 98.6% of batch time (42).
Even higher values of heat transfer coefcients than those in the HEX reactors can be achieved in microreactors. Here, values up to 20,000 W/m2K are reported (43). Microreactors (Figure 15) are chemical reactors of extremely small
dimensions that usually have a sandwich-like structure, consisting of a number of
slices (layers) with micromachined channels (10100 m in diameter). The layers
perform various functions, from mixing to catalytic reaction, heat exchange, or separation. Integration of these various functions within a single unit is one of the most
important advantages of microreactors. The very high heat transfer rates achievable
in microreactors allow for isothermal operation of highly exothermic processes (also
important in carrying out kinetic studies). The very low reaction-volume-to-surfacearea ratios make microreactors potentially attractive for carrying out reactions
involving poisonous or explosive reactants (think about partial oxidation reactions).
FIGURE 14 HEX reactor developed by the BHR Group. (Courtesy: BHR Group
Ltd.)
Also, microchannel heat exchangers have channel sizes around or lower than
1 mm and are fabricated via silicon micromachining, deep X-ray lithography, or
nonlithographic micromachining. The reported values of heat transfer coefcients
in the microchannel heat exchangers range from ca. 10,000 to ca. 35,000 W/m2K
(21,44).
High heat transfer coefcients, though not as high as in the previous case,
are also achievable in spinning disk reactors (Figure 16). This type of reactor has
been developed by Ramshaws group at Newcastle University and is primarily
applied to fast and very fast liquidliquid reactions with large heat effect, such
as nitrations, sulphonations, and polymerizations. At very short residence times
(typically 0.1 s), heat is efciently removed from the reacting liquid at heat transfer rates reaching 10,000 W/m2K. The spinning disk reactor investigated in one
of SmithKline Beechams processes offered a 99.9% reduction in reaction time,
99% reduction in inventory, and 93% reduction in impurity level (45).
Rotational movement and centrifugal forces are used not only in spinning
disk reactors. The earlier-mentioned high-gravity (HiGee) technology, started at
ICIs New Science Group in the late 1970s as a spinoff of a NASA research project in deep space (microgravity environment), has developed into one of the most
promising branches of process intensication. It consists of intensifying the mass
transfer operations by carrying them in rotating packed beds, in which high centrifugal forces (typically 1000 g) occur. This way, not only mass transfer but also
heat and momentum transfer can be intensied. The rotating bed equipment, originally dedicated to separation processes (such as absorption, extraction, distillation), can also be applied to reacting systems (especially those mass transfer
limited). It can potentially be applied not only to gasliquid combinations but also
to other phase combinations, including three-phase gasliquidsolid systems. The
HiGee technology has already been successfully applied on a commercial scale,
for deaeration of ood water in Chinese oil elds (20), where conventional vacuum
towers of ca. 30-m height have been replaced by the rotating machines of ca. 1-m
diameter. The earlier-mentioned hypochlorous acid technology of Dow Chemical
presents another example of a successful application of rotating packed beds (25).
Also, successes have been achieved in the crystallization of nanoparticles. In the
group of Chong Zheng, very uniform 15- to 30-nm crystals of CaCO3 are made
in a rotating crystallizer at processing times 410 times shorter than in the conventional stirred-tank process (46).
Another interesting example of process-intensifying equipment, also undergoing commercialization, is the centrifugal adsorber. This is a new continuous
device for carrying out ion exchange and adsorption processes. By using a centrifugal eld for establishing countercurrent ow between the liquid phase and
the adsorbent, very small adsorbent particles (1050 m) can be used. This allows
for extremely compact separation equipment (see Figure 17) with very short contact times and high capacities (typically 10 50 m3/h, (17)).
FIGURE 15 An example of a microreactor. (Courtesy: Institut fr Mikrotechnik

Mainz.)
FIGURE 16 Spinning disk reactor.
Other examples of interesting PI hardware include the supersonic gas

liquid reactor developed at Praxair Inc. (47) and the jet impingement reactor of
NORAM Engineering and Constructors (Hauptmann et al. (48)). The former is
based on using a supersonic shock wave to disperse gas into very tiny bubbles in
a supersonic inline mixing device, while the latter uses a system of specially congured jets and bafes in order to divide and remix liquid streams with high
intensity. Also, rotor/stator mixers (49) are dedicated for processes requiring very
fast mixing on the micro scale. They contain a high-speed rotor spinning close to
a motionless stator. Fluid passes through the region where rotor and stator interact and experiences highly pulsating ow and shear. Inline rotor/stator mixers
resemble centrifugal pumps and therefore may simultaneously contribute to
pumping the liquids.
5.2.
Process-Intensifying Methods
As seen in Figure 7, three well-dened categories of PI software can be distinguished:

Novel processing methods, such as integration of reaction and one or more
unit operations in so-called multifunctional reactors and integration of
two or more separation techniques in hybrid separations
Use of alternative forms and sources of energy for chemical processing
Novel methods of process/plant development and operation
Multifunctional reactors can be described as reactors that, alongside chemical conversion (and for the sake of it), integrate at least one more function (usually unit operation) that conventionally would have to be performed in a separate
piece of equipment. A pretty widely known example of the integration of reaction and heat transfer in a multifunctional unit are reverse-ow reactors (50).
Also, a number of interesting reactor concepts for combining endo- and exothermic reactions have been developed (51,52).
Reactive separations present probably the most signicant class of multifunctional reactors, of which reactive distillation is one of the better-known and
commercially applied examples. The multifunctional reactor is in this case a
packed distillation column, in which the packing material acts simultaneously as
the catalyst carrier. Chemicals are converted on the catalyst and reaction products
are continuously separated by fractionation (thus overcoming equilibrium limitations). Besides the continuous removal of the reaction products and higher yields
due to the equilibrium shift, the advantages of catalytic distillation units consist
mainly in lower energy requirements and lower capital investment (53). Currently,
numerous studies are being carried out in the eld of reactive distillation modeling,
as reviewed recently by Taylor and Krishna (54). Also, research on new internals
for catalytic distillation columns attracts a lot of attention. Reactive distillation
originates from and nds most applications in the hydrocarbon processing. Recently,
interesting papers on the application of reactive distillation in ne chemistry began
to emerge (55). The reverse process to the reactive distillation, i.e., reactive condensation, has also been studied (56).
Reactive extraction processes involve simultaneous reaction and liquidliquid
phase separation and can be effectively utilized to obtain signicant improvements
in yields of desired products and selectivities to desired products in multireaction
systems, thereby reducing recycle ows and waste formation. The combination of
FIGURE 17 Progress in size reduction of adsorption equipment, up to the

most recent centrifugal adsorption technology. (From Ref. 118.)
reaction with liquidliquid extraction can also be used for separation of waste byproducts that are hard to separate using conventional techniques (57,58). Reactive
extraction can also be used for selective separation of amino acids (59).
Reactive crystallization, or precipitation, has been investigated by numerous research groups. Processes of industrial relevance include liquid-phase oxidation of para-xylene to terephthalic acid, the acidic hydrolysis of sodium
salicylate to salicylic acid, and the absorption of ammonia in aqueous sulfuric
acid to form ammonium sulfate (60). A very special type of reactive crystallization is diastereomeric crystallization, widely applied in the pharmaceutical industry for the resolution of enantiomers (61). Another ne example of reactive
precipitation is the earlier-described production of nano-size particles of CaCO3
in high-gravity elds (46).
Reactive absorption is probably the most widely applied type of a reactive
separation process. It is used for production purposes in a number of classical
bulk-chemical technologies, such as nitric or sulfuric acid. It is also often employed
in gas purication processes, e.g., to remove carbon dioxide or hydrogen sulde.
Other interesting areas of application include olen/parafn separations, where
reactive absorption with reversible chemical complexation appears to be a promising alternative to the cryogenic distillation (62).
Numerous investigations are being carried out in reactive adsorption processes, for instance, in chromatographic reactors, which integrate continuous
countercurrent chromatographic separation with chemical reaction (63,64), and in
periodic separating reactors, which are a combination of a pressure swing adsorber with a periodic ow-forced packed-bed reactor (65). This allows achieving
higher conversions and better yield by separating educts and products of an equilibrium reaction from each other. In the simulated moving bed reactor (SMBR), the
movement of the bed with regard to the reactant inlets/outlets is usually realized
in a rotating system. One of the more interesting developments here is the rotating cylindrical annulus chromatographic reactor, shown in Figure 18 (66). In this
design the inlets of the mobile phase are uniformly distributed along the annular
bed entrance, while the feed stream is stationary and conned to one sector. As a
result of the rotation of the reactor, the selectively adsorbed species take different
helical paths through the bed and can be continuously collected at xed locations.
Another interesting example of reactive adsorption is the so-called gas
solidsolid trickle ow reactor, in which adsorbent trickles through the xed bed
of catalyst, removing selectively in situ one or more of the products from the reaction zone. In the case of methanol synthesis this led to conversions signicantly
exceeding the equilibrium conversions under the given conditions (67).
A huge research effort is devoted nowadays to membrane reactors. The
membrane can play various functions in the reactor systems (68); it can, for
instance, be used for selective in situ separation of the reaction products, as a
result of which an advantageous equilibrium shift can be achieved. It can also be
FIGURE 18 Rotating cylindrical annulus chromatographic reactor.
applied for a controlled distributed feed of some of the reacting species, either to
increase the overall yield/selectivity of the process or to facilitate the mass transfer (e.g., direct bubble-free oxygen supply/dissolution in the liquid phase via
hollow-ber membranes (69)). The membrane can also be used for the in situ
separation of catalyst particles and even homogeneous catalysts from the reaction
products (70). Finally, the membrane can incorporate catalytic material, thus
becoming itself a highly selective reaction-separation system. Membranes are
more and more frequently employed in the life sciences sector, in manufacturing
of pharmaceuticals, in combination with a bioreactor in which enzymatic reaction
takes place (71).
Multifunctional reactors may also combine reaction and phase transition. A
well-known example of such a combination is reactive extrusion. Reactive extruders have been used increasingly in polymer industries. They enable reactive processing of highly viscous materials without a need for using large amounts of
solvents, as is the case in stirred-tank reactors. Most of the reactions carried out
in extruders are single- or two-phase reactions. Recently, however, new types of
extruders have been investigated with catalyst immobilized on the surface of the
screws, which enables carrying out three-phase catalytic reactions (72).
Fuel cells present another widely investigated type of multifunctional reactors, in which chemical reaction is integrated with the generation of electric
power (73). Simultaneous gassolid reaction and comminution in a multifunctional reactor has also been investigated (74).
Among hybrid separations, the integration of membranes with another separation technique presents the most important category. In membrane absorption
and stripping the membrane is used as a permeable barrier between the gas and
liquid phases. By using hollow-ber membrane modules, large mass transfer
areas can be created, which results in compact equipment. Besides, absorption
membranes offer operation independent of gas- and liquid-ow rates, with no
entrainment, ooding, channeling, or foaming (75,76).
In membrane distillation, two liquids (usually two aqueous solutions) held
at different temperatures are mechanically separated by a hydrophobic membrane. Vapors are transported via the membrane from the hot solution to the cold
one. The most important (potential) applications of membrane distillation are in
water desalination and water decontamination (7779). Other possible elds of
application include recovery of alcohols (e.g., ethanol, 2,3-butanediol) from fermentation broths (80), concentration of oilwater emulsions (81), and removal of
water from azeotropic mixtures (82). Membrane (pervaporation) units can also be
coupled with conventional distillation columns, for instance, in esterications or
in production of olens, to split the azeotrope (83,84).
Membrane chromatography systems include microporous or macroporous
membranes that contain functional ligands attached to their inner pore structure,
which act as adsorbents. In this sense, membrane chromatography is a hybrid
combination of liquid chromatography and membrane ltration. Its most important potential applications include separations of biomolecules, such as proteins,
polypeptides, and nucleic acids (85,86).
Among hybrid separations not involving membranes, adsorptive distillation (87) offers interesting advantages over conventional methods. In this technique a selective adsorbent is added to a distillation mixture. This increases
separation ability and may present an attractive option in the separation of
azeotropes or close-boiling components. Adsorptive distillation can be used, for
instance, for the removal of trace impurities in the manufacturing of ne chemicals (it may allow for switching some ne chemical processes from batchwise to
continuous operation).
Several unconventional processing techniques using alternative forms and
sources of energy have been investigated thus far and are of importance for
process intensication. The use of the centrifugal elds instead of gravitational
ones was discussed earlier in this chapter. On the other hand, the formation of
microbubbles (cavities) in the liquid reaction medium as a result of ultrasound
waves has opened new possibilities for chemical syntheses. These cavities can be
thought of as high-energy microreactors. By their collapse, microimplosions
take place with very high local energy release (temperature rises up to 5000 K,
and negative pressures up to 10,000 bar are reported (88)). This may have various
effects on the reacting species, from homolytic bond breakage with free radicals
formation, to the fragmentation of the polymer chains by the shock wave in the
liquid surrounding the collapsing bubble. In case of solid-catalyzed (slurry) systems, the collapsing cavities can additionally affect the catalyst surfacethis can,
for example, be used for in situ catalyst cleaning/rejuvenation (89). Sonochemistry
has also been investigated in combination with other techniques, e.g., electrolysis,
in the case of the oxidation of phenol in wastewater (90).
The use of solar energy in chemical processing has also been investigated.
Studies describe, for example, the cycloaddition reaction of a carbonyl compound to
an olen carried out in a solar furnace reactor (91) or oxidation of 4-chlorophenol
in a solar-powered ber-optic cable reactor (92). The concept of using solar light
for the synthesis of -caprolactam was evaluated, and it was shown that the return
on investment was better than for the conventional technology (93). Solar reactors can also be used advantageously in water treatment plants (94).
The use of microwave dielectric heating offers signicant advantages for
chemical synthesis (9597). Microwave heating was shown to enable some organic
syntheses to proceed up to 1240 times faster than by conventional techniques (98).
The employment of electric elds to augment process rates and to control
droplet size is known for a range of processes, including paint spraying, crop
spraying, and coating processes. In these processes the electrically charged
droplets exhibit much better adhesion properties. Electric elds can also enhance
processes involving liquid/liquid mixtures, in particular liquidliquid extraction,
where rate enhancements of 200300% were reported (99). Bioseparations (e.g.,
DNA separation) present another area in which electric elds can be advantageously applied (100).
Interesting results have been reported concerning the so-called gliding arc
technology, i.e., the use of plasma generated by the formation of gliding electric
discharges (101103). In this technology, gliding electrical discharges are produced between electrodes placed in the fast gas ow. They offer a low-energy
alternative for conventional high-energy-consuming high-temperature processes.
The applications tested so far in the laboratory and on industrial scale include:
methane transformation to acetylene and hydrogen, destruction of N2O, reforming of heavy petroleum residues, CO2 dissociation, activation of organic bers, air
purication from volatile compounds, natural gas conversion to syngas, and SO2
reduction to elementary sulfur.
A number of other methods, not falling within any of the earlier-mentioned
categories, may prove useful for process intensication. Some of them, such
as supercritical uids, are already known and have been applied in other industries (104,105). Because of their unique properties, especially the high diffusion
coefcient, supercritical uids are attractive media for mass transfer operations,
FIGURE 19 Process intensication via process synthesis: methyl acetate plant of Eastman Chemical.
e.g., extraction (106), and for chemical reactions (107,108). On the other hand,
cryogenic techniques (distillation or distillation combined with adsorption (109)),
nowadays almost exclusively used for production of industrial gases, may in the
future prove attractive for some specic separations in manufacturing of bulk or
ne chemicals.
Among novel methods of process/plant operation, the use of unsteady-state
(periodic) operation of chemical reactors has been studied for more than three
decades (110). In many processes studied on the lab scale, the intentional pulsing of ows or concentrations led to a clear improvement of product yields/
selectivities (111). Purposeful pulsing of the feed in trickle-bed reactors has been
shown to bring signicant improvement in mass transfer rates, in catalyst wetting,
and in the radial uniformity of liquid ow (112). The commercial-scale applications of the periodic operation are scarce and are practically limited to the reverseow reactors discussed earlier. One of the main reasons is that a stationary process
has the advantage of providing constant production and product purity, without the
need for additional investments to synchronize nonstationary with stationary parts
of the process. Further developments in the eld of advanced process control may
denitely change this picture, especially where the time constant of the pulsing
mode is smallsynchronizing will not be problematic.
Finally, in order to get a more or less complete picture of the process intensication toolbox, the PI-oriented methods for process/plant development must
be mentioned. Among them, process synthesis (PS) denitely plays the most
important role (113115). Process synthesis is in some sense a sister discipline of
process intensication that aims at the development of a cost-optimal process
concept based on the required functionalities. It includes diverse levels of activities, starting from basic conceptual plant design (often based on the out-of-thebox approach), through the selection of optimal pieces of equipment and optimal
interconnections between them (plant integration), up to cost estimates. Process
synthesis permits early assessment and evaluation of the manufacturability of
products resulting from potential new chemistries. A textbook example of a commercial application of process synthesis is the methyl acetate plant of Eastman
Chemical (23), in which a task-oriented integration of reaction and separation in
a multifunctional reactor reduced the number of pieces of equipment from 28 to 3
(see Figure 19). In recent years, process synthesis has gone beyond its traditional
field of applications and has entered new sectors, such as bioprocessing and pharmaceuticals manufacturing (116,117).
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2
Chemical Processing in High-Gravity Fields
David L. Trent
The Dow Chemical Company, Freeport, Texas, U.S.A.
1.
INTRODUCTION
The use of high-gravity, or centrifugal, elds for chemical processing has generated
much interest in recent years. Fluid acceleration creates an environment in which
mass transfer rates are two to three orders of magnitude higher than rates
achieved in more conventional equipment, such as packed towers and stirred
tanks. Heat transfer is also enhanced. Short contact time and fast transfer rates
allow a reduction in equipment size and in-process inventory. Many chemical
processes could benet from these unique properties by reducing the cost of construction, reducing working capital, improving safety, producing less waste, etc.
In addition, the use of high-gravity elds may provide solutions to processing
problems more effectively and more economically than conventional equipment.
Before exploring the wide range of applications, a brief review of the history of development, a discussion of the process fundamentals, and an introduction to mechanical design issues will help to set the boundaries for use of
high-gravity elds in chemical processing.
2.
HISTORICAL DEVELOPMENT
The use of centrifugal elds in chemical processing dates to the beginning of the
industry with such physical transport operations as pumping, compression, and
solid/liquid separations. Extending this use into mass and heat transport operations
such as liquid/liquid extraction, gas/liquid interactions, reactions, crystallization,

and heat transfer, however, is a much more recent development. Although the
commercial application of high-gravity elds has been limited in these recent
areas of interest, the potential to improve existing chemical processes and develop
new processes remains high.
The extension of the use of centrifugal elds into the commonplace of
chemical processing had its start in 1945 with the commercial application of a
centrifugal liquid extractor to the recovery of penicillin (1). The liquid extractor,
based on earlier patents by Podbielniak (2), employed perforated concentric
plates for contacting the two countercurrent liquid streams.
Pilo and Dahlbeck (3) introduced an apparatus employing a variety of rotor
internals and liquid distributors for countercurrent contact of two uids having
different specic gravities in their 1960 U.S. patent. Although the authors suggest
use of the apparatus for gas scrubbing, distillation, heat exchange, and reactions,
commercial application was not exploited. In 1966 Podbielniak (4) described a
centrifugal device with concentric perforated plates for gas/liquid contact. Todd
(5) extended the concepts of Pilo and Podbielniak to a multistage device in 1969.
In 1981 Ramshaw and Mallinson (6) provided for lling the rotor with a
high-surface-area material such as glass beads or wire gauze in order to effect
improved mass transfer. They also described a rotor for distillation, complete with
vapor/liquid contacting, condenser, and boiler. Following this patent, considerable academic interest developed in an attempt to exploit the high mass and heat
transfer rates, high-throughput capability, and short contact times afforded by
countercurrent uid contact using centrifugal elds.
Sustained commercial application, however, did not occur until 1997, when
Zheng et al. (7) described the successful stripping of oxygen from water used in
secondary oil eld recovery. In 1999 Trent et al. (8,9) introduced the rst commercial application involving simultaneous absorption, reaction, and stripping. Both of
these involve gas/liquid contact using a woven wire screen for the rotor internals.
3.
PROCESS FUNDAMENTALS
In order to fully appreciate the application opportunities available from use of

high-gravity elds, an understanding of what happens within the rotor would be
helpful. Since many of the models used to describe chemical processes in more
conventional equipment do not apply to high gravity, much of the information
available is empirical. However, where possible the traditional models are being
modied to match the observed behavior. The process fundamentals of interest
here are mass transfer, heat transfer, uid distribution and holdup, ooding, pressure drop, power requirements, and rotor internals. Although this last item could
be considered with the mechanical design discussion, it is included here because
the rotor internals can have a signicant impact on the other process variables.
FIGURE 1 Schematic of gas continuous operation of a rotating packed-bed gas/

liquid contactor.
Before addressing these process fundamentals, however, a description of

the basic process equipment would be helpful. Figure 1 shows a schematic of a
simplied rotating packed-bed (RPB) contactor. This RPB illustrates countercurrent gas/liquid operation. Liquid enters at the eye of the rotor, being distributed
on the rotor packing at the inside diameter. The centrifugal force of the spinning
rotor accelerates the liquid radially outward. Gas enters the stationary housing
and passes through the rotor from outside to inside. The gas exits at the eye of the
rotor, while liquid drains from the housing. Seals on the drive shaft and on the
rotor ensure that the gas moves through the rotor.
Figure 1 shows a gas continuous conguration. A liquid continuous arrangement is also possible (10). For liquid/liquid extraction the preceding description
applies if we consider the liquid to be the heavy phase and the gas to be the light
phase (11). In both of these scenarios the light phase enters through the drive shaft
and channels radially in the rotor end plate to the outer periphery of the rotor for
distribution into the heavy phase (see Figure 2).
3.1.
Hydrodynamics
Understanding the ow of liquid and gas through a rotating packed bed is important to understand the performance results achieved. Liquid ow involves two
FIGURE 2 Schematic of liquid continuous operation of a rotating packed bed

for gas/liquid and liquid/liquid contacting.
components, liquid introduction to the packing and ow through the packing. Flow
through the packing occurs in the radial direction with very little tangential or axial
spreading (see Figure 3). A slight curvature in the radial ow results from the
direction of rotation. The degree of curvature and spreading is primarily a function
of rotor speed and liquid viscosity and less a function of packing type and liquid
ow rate (12,13). Gas ow does not impact liquid ow through the rotor (14).
The ow pattern described results in incomplete wetting of the packing at
the outer diameter of the rotor (13). Thus, not all of the packing surface area is
utilized for mass transfer operations. For maximum use of the packing surface
area, the ratio of the outside diameter to the inside diameter should be minimized.
Scale-up from small-diameter to large-diameter rotors typically provides more
efcient use of the packing. In spite of this incomplete wetting of the packing,
very high mass transfer rates are achieved.
Enhanced mass transfer performance results from the initial contact of the liquid feed with the rotor. Studies at the Higravitec Center of Beijing University of
Chemical Technology (HCBUCT), using a video camera attached to the rotor,
revealed a breakup of the liquid feed into smaller droplets that lled the void spaces
of the packing. This effectively increases the interfacial surface area of the liquid
beyond that of the surface area of the packing. At a packing depth of about 710 mm,
most of the liquid has been accelerated to the rotor speed and wets the packing.
Liquid ow continues mostly along the packing surface, but some additional
droplets y across the void spaces in the packing. The most intense mixing and mass
transfer occur in the inlet zone of the packing. The degree of mass transfer enhancement at the inlet is a function of the type of packing (porosity, shape of packing structure, etc.), rotor speed, method of liquid distribution, and liquid properties (15).
Liquid distribution on the rotor affects the initial contact zone performance.
Some of the variables to consider include angle of impingement, velocity of the
liquid spray, and acceleration of the liquid via rotation. Optimum performance
requires full axial wetting of the packing, whereas full tangential wetting is not necessary. The use of nozzles rotating in the same direction and at the same speed as the
rotor gave poor results for a hypochlorous acid process due to little surface area or
liquid-side mass transfer enhancement (8). Although nozzles rotating in the opposing direction of the rotor would be expected to provide the best mass transfer performance, the increased cost of manufacture of the equipment may not be justied.
Gas distribution in the rotor has not been studied as thoroughly as that of the
liquid. Gas entering the rotor at the outside diameter accelerates radially inward
due to the reducing diameter. Gas tangential velocity relative to that of the rotor
varies depending on the rotor packing. With parallel at plates the low frictional
drag (high slippage) makes the gas spiral inward with a path length much longer
than the radial thickness of the packing (Figure 4a). The gas path length approaches
the radial thickness of the packing as the packing surface area increases and the
FIGURE 3 General ow pattern of liquid in a gas continuous rotor.
FIGURE 4 Relative path of gas (a) in a rotor of low resistance (e.g. parallel at
plates), and (b) in a rotor of high resistance (low porosity, high surface area).
porosity decreases, due to the increased drag of the rotor on the gas (Figure 4b).
This behavior signicantly impacts gas-side mass transfer performance (16).
The thickness of the liquid lm on the rotor packing helps determine mass
transfer rates. Film thickness can be shown to be inversely proportional to rotor
speed to the 0.8 power (17). Visual measurements using a video camera attached
to the rotor show a water lm thickness of 2080 microns on foam metal packing
and 10 microns on wire gauze packing (15). Theoretical models estimate similar
lm thickness values (13,18,19). Film ow is expected to be laminar. In addition
to rotor speed, liquid ow rate and uid properties affect the lm thickness (14).
The foregoing discussion focuses on gas continuous operations, in which

the bulk of the rotor volume is lled with gas. Liquid continuous operation can
be accomplished by collecting the liquid at the outside diameter of the rotor and
channeling it back for discharge at a diameter slightly larger than the feed radial
position, as illustrated in Figure 2 (20). Gas introduced into the liquid pool at the
outer diameter moves countercurrent to the liquid inside the packing of the rotor.
Because of the hydraulic pressure of the liquid from the centrifugal force, the gas
bubbles start out small and steadily expand. Contact of the bubbles with the rotor
packing results in breakup of the bubbles, to maintain a high interfacial surface
area. References 21 and 22 illustrate this approach for water deaeration and a centrifugal eld bioreactor, respectively.
Liquidliquid contact in an RPB involves introduction of the heavy liquid
at the inside diameter of the rotor and the light phase at the outside diameter. The
two liquid phases move countercurrent to one another within the rotor packing.
Centrifugal force causes the heavy liquid to move radially outward. This displaces the light liquid, which moves radially inward. The design of the rotor packing inuences the contact between the two liquid phases (23,24).
3.2.
Flooding
Rotating packed-bed devices handle high volumes of uids in a small equipment

volume, compared to packed towers, due to the acceleration of gravity. The
Sherwood ooding correlation for packed towers (25) is expressed as a plot of
UG2 a p G 0.2
L
g 3 L
versus
L G

G L
0.5
Early RPB researchers discovered that this ooding correlation for packed towers applied equally well to RPBs when the gravity term (g) was replaced by centrifugal acceleration (r2). As acceleration increases, the gas ooding velocity
(UG) increases in order to maintain the same value of the rst term. Since the ratio
of liquid (L) to gas (G) ow remains constant, liquid ow increases commensurately with gas ow. Most researchers observed higher gas velocities before the
onset of ooding than predicted by the Sherwood correlation (17,26,27).
Measurement of ooding by traditional means of observing a sharp pressure increase as gas rates increase is not effective with the RPB (28). Flooding
can be determined experimentally by adjusting rotor speed and holding gas and
liquid rates constant. Flooding will occur at the point of maximum pressure drop
over a range of rotor speeds (28) or by observing the increased pressure drop
change (inection point) as a function of decreased rotor speed (27,29).
In liquidliquid contact, two types of ooding can occur. The design of the
centrifugal contactor denes the throughput capability before ooding occurs.
The second type of ooding relates to the principal interface moving into either
the light-phase or heavy-phase takeoff. The movement of the principal interface

is controlled by the back pressure of the light-phase takeoff, which is a function
of the rotor speed and phase density difference (24).
3.3.
Residence Time
Liquid residence time in the packed rotor varies as a function of packing depth,
packing type, rotor speed, and liquid properties (26). Two basic approaches have
been applied to the measurement of liquid in the rotor. The rst measure is the
average residence time of the liquid within the rotor, and the second is the liquid
holdup on the packing. Due to the ow patterns described previously, not all of
the rotor packing is wetted and not all of the liquid resides on the packing surface. As a result, average residence time and liquid holdup are distinct measures
of liquid ow, contrary to the experience with packed towers.
Tracer methods, both visual and electrical conductivity sensors, have been
applied to measure the residence time of the liquid in the rotor (15,26). Measured
liquid residence time ranges from about 0.2 seconds to about 1.8 seconds. Time
decreases as the rotor speed increases, as liquid ow rate increases, and as the
radial position increases. Gas ow rate and liquid viscosity (narrow test range)
have little impact on residence time (15,19,26).
Since liquid does not completely wet the packing and since lm thickness
varies with radial position, classical lm-ow theory does not explain liquid ow
behavior, nor does it predict liquid holdup (30). Electrical resistance measurements have been used for liquid holdup, assuming liquid ows as rivulets in the
radial direction with little or no axial and transverse movement. These data can
then be empirically t to lm-ow, pore-ow, or droplet-ow models (14,19).
The real ow behavior is likely a complex combination of these different ow
models, that is, a function of the packing used, the operating parameters, and uid
properties. Incorporating calculations for wetted surface area with the lm-ow
model allows prediction of liquid holdup within 20% of experimental values (18).
Liquid holdup in liquidliquid extractors must be dened for both the
heavy and light phases. The light-phase outlet pressure is used to control the relative liquid holdup of the two phases. Higher light-phase outlet pressure increases
the light-phase holdup. This pressure has been correlated with the phase density
difference, rotor speed, and rotor dimensions (24). In addition, packing characteristics of volumetric surface area and porosity inuence liquid holdup and
throughout capability (23).
3.4.
Mass Transfer
Developing correlations to describe mass transfer in rotating packed beds has

proven to be a challenge. Penetration theory (31), lm-ow theory (32), and modied surface-renewal theory (12) are some examples of leveraging previous work
to the rotating packed bed. At issue is the need to include a multiplicity of variables
as well as to understand the hydrodynamics of gas/liquid contact within the rotor.
Each modeling approach compared experimental data to the models, with reasonable t. However, these expressions have not yet been validated on multiple-RPB
designs and operating conditions. A key to developing a generalized model for
mass transfer performance is the proper understanding and treatment of the uid
ows within the rotor, as discussed previously in Section 3.1.
The combination of high surface area, high velocities, thin lms, and
intense mixing in the packing provides an environment for intensive mass transfer, resulting in values for height of transfer unit (HTU) of 1.54 cm (26). Mass
transfer has been described using HTU, number of transfer units (NTU), mass
transfer coefcient (kL, kG), and volumetric mass transfer coefcient (kLa, kGa,
k S a). To accommodate the variation in packing surface wetting with radial distance,
an area transfer unit (ATU) has been proposed (33). Another proposed method of
evaluation uses a volume transfer unit (VTU) to account for the entire volume of
the packed rotor (34). Although the ATU and VTU methods may have merit in
evaluating RPB performance, these methods make comparison with other transfer devices based on HTU more difcult.
The possible physical design parameters affecting mass transfer include
packing and packing supports. Atomization of the liquid as it impacts the spinning rotor packing creates high-surface-area liquid drops, in addition to the lm
wetting of the high-surface-area packing. This atomization results in signicant
mass transfer apart from the packing surface. As a result, low-surface-area packings produce equivalent, if not better, volumetric mass transfer coefcients than
do high-surface-area packings (35,36). This implies that low-surface-area packing with high porosity can effectively replace high-surface-area packing, contrary
to the experience with packed towers. The result is lower-cost packing, reduced
pressure drop, and higher throughput. Packing supports at the inside diameter of
the rotor generally provide a positive effect on mass transfer (36). Due to the
atomization of liquid exiting the rotor, additional mass transfer occurs in the
space between the rotor and the housing (37).
Operational parameters of importance to mass transfer include rotor speed,
liquid rates, and gas/liquid ratios. Mass transfer increases proportionately to rotor
speed, decreases with increasing liquid ow, and increases with gas/liquid ratio
(17,26,36). Although most references present rotor speed as revolutions per
minute (rpm), expression as either tangential velocity (r) or multiples of gravity
(r2) provides a better basis for comparison among the different rotor designs and
for scale-up.
Gas-side mass transfer in rotating packed beds does not show the same
level of enhanced performance as liquid-side mass transfer. Average volumetric
gas mass transfer values for a wire screen packing increased with gas ow rate
but decreased with increased rotor speed. Compared to a packed tower, the RPB
mass transfer coefcient (18 s1) was similar when operated at similar supercial gas velocities (1 m/s). However, when gas velocities were increased
(412 m/s) in studies with parallel at plates as the rotor, the mass transfer coefficient also increased, to a high of 45 s1 (16). In a commercial-scale RPB, average
volumetric gas-side mass transfer coefcients of 4050 s1 were achieved using
a wire screen packing and gas velocities of 45 m/s (9). The factors affecting gasside mass transfer are less understood than those of liquid-side mass transfer.
Liquidliquid mass transfer in centrifugal extraction contactors shows similar trends on performance as the gasliquid contactors. Mass transfer improves at
higher rotor speeds, higher solvent ratio, and higher phase density difference.
Since the light-phase outlet pressure controls the liquid holdup of both phases,
decreasing the light-phase outlet pressure decreases the light-phase holdup and
increases the number of transfer units (24). Packing characteristics of pore size,
porosity, and volumetric surface area also play a role in performance (23). Single
centrifugal extractors have achieved up to 10 theoretical stages of extraction (38),
but they could achieve up to 20 stages with suitable rotor design (11).
Liquidsolid mass transfer has also been studied, on a limited basis.
Application to systems with catalytic surfaces or electrodes would benet from
such studies. The theoretical equations have been proposed based on lm-ow
theory (32) and surface-renewal theory (39). Using an electrochemical cell with
rotating screen disks, liquidsolid mass transfer was shown to increase with rotor
speed and increased spacing between disks but to decrease with the addition of
more disks (39). Water ow over naphthalene pellets provided 46 times higher
volumetric mass transfer coefcients compared to gravity ow and similar supercial liquid velocities (17).
3.5.
Pressure Drop
Gas pressure drop through the RPB rotor is an important consideration when
comparing the performance of the RPB with other mass transfer devices, such as
a packed tower. Numerous studies on pressure drop in RPB rotors employing a
variety of packings have yielded some surprising differences from conventional
packed towers. For example, lower pressure drop for wetted packing compared to
dry packing has been reported (26,40,41). Not all researchers observed this phenomena, because pressure drop was found to be a function of packing type, rotor
design, gas rates, liquid rates, and rotor speed (41).
Pressure drop has been reported for a number of rotor internals, including
corrugated structured packing (28), foam metal (26,40,42), rectangular and elliptical cylinder plastic grains randomly packed (41), wire screen (43), and glass
beads (17). In spite of the variation in porosity from 0.38 to 0.95 and in volumetric surface area from 500 to 4000 m2/m3, all of these studies showed similarities
of increased pressure drop as rotor speed increased and gas rates increased.
In addition to the differences in packing type and characteristics, these studies also had a variety of rotor and housing designs for the gas and liquid inlet and
outlet. All of them measured a gas pressure drop from the inlet gas piping or
housing to the outlet gas pipe. In an effort to develop models of the pressure drop,
most have attributed the pressure drop to centrifugal and frictional forces in the
rotor, using a lm-ow model (43). Pressure drop is proportional to the square of
rotor speed (26,42). Compared to conventional packed towers, the pressure drop
is lower per NTU (26) and about 15 times higher at ooding conditions (28).
To account for the differences in machine conguration and to better
explain the pressure-drop observations (e.g., lower pressure drop with onset of
liquid ow), a model based on conservation of mass and momentum, in particular gas angular momentum, was developed (40). This model divided the pressure
drop into four increments that included the gas inlet to the machine housing, the
rotor, the eye of the rotor, and the gas exit nozzle from the machine.
Although the models for pressure drop have a basis in theory, all are t
empirically to data generated from specic equipment. Application of these
models may not be relevant to machines of different congurations and packing
types (9).
In liquidliquid contactors, pressure drop is dened by the light phase. The
heavy phase enters at near atmospheric pressure and is accelerated by the rotor to
its discharge pressure. The pressure drop of the light phase is a function of phase
density difference, rotor speed, rotor diameter, and location of the principal phase
interface (24).
3.6.
Heat Transfer
Most of the experimental work on heat transfer in centrifugal elds has been done
on spinning discs, which is the subject Chapter 3 in this book. A brief review of
the enhanced heat transfer rates is relevant here. Studies on a smooth, at spinning disc show heat transfer coefcients as high as about 20 kW/m2K. The coefcient is highest at the inlet to the disc, due to disturbances as the liquid is
accelerated to the angular velocity of the disc. The heat transfer coefcient
increases with increased rotor speed but decreases with increased radial position.
Higher-viscosity uids decrease the heat transfer rate. Heat transfer is generally
higher than predicted from lm or penetration theory (44).
Modifying the surface of the disc allows enhancement of the heat transfer
by introducing liquid lm instabilities (waves). Best results come from the combination of thin lms and large instabilities as revealed from the study of four surface geometries: smooth, sprayed metal, and two types of concentric grooves. In
general, increased rotor speed gives higher heat transfer. However, with the
grooved disc, high speeds cause liquid separation from the disc, resulting in lower
heat transfer (45).
Heat transfer involving non-Newtonian uids has not been studied in rotating devices. Models have been developed for gravity-driven heat transfer for
power-law uids (46). These models may be useful as a starting point to evaluate
performance in higher-gravity elds.
Another method of introducing heat to uids in rotating devices involves
the generation of eddy currents by rotation through a stationary magnetic
field. This approach was successfully used in a polymer devolatilization
process (47).
3.7.
Power
Estimating power consumption in rotating systems depends on several factors,

including acceleration of the liquid, windage effect of gas drag on the rotor, friction in the bearings and seals, and gas pressure drop (33,48). As would be expected from power consumption in such devices as centrifugal pumps, the largest
power component involves acceleration of the liquid to the angular velocity of
the rotor at the outer diameter. Gas pressure drop actually decreases power
consumption in the rotor. Frictional losses are dened by the design of the rotor,
bearings, and seals.
3.8.
Rotor Internals
The rotor packing has an impact on all of the previously mentioned process fundamentals. Hydrodynamics, especially at the liquid inlet to the packing, is a function of packing porosity and volumetric surface area (12,13). These same packing
properties inuence pressure drop, residence time, and ooding velocity (26).
Liquid-side mass transfer performance is best with wire gauze as compared to
glass beads or parallel at plates (8). Gas-side mass transfer is better with parallel at plates than in wire gauze (16). Flat plates provide the best medium for heat
transfer (34).
4.
MECHANICAL DESIGN
Since the development of high-gravity elds requires rotating equipment, the

mechanical design is very important when considering operating performance,
cost of design and fabrication, ease of maintenance, and overall reliability.
Although most public reports on RPB studies describe the particular RPB design
used in the reported studies, very little information has been published on the
mechanical design principles. Original equipment manufacturers of rotating equipment provide an effective resource for proper design and fabrication of RPBs. The
following discussion outlines some of the basic issues to be considered in the
machine design. Overriding all of the following discussion is the need to design a
stable rotor with minimal vibration under the desired operating conditions.
4.1.
Cantilevered Versus Centerhung Rotor
Once the rotor dimensions of inside diameter, outside diameter, and axial height
have been determined from the operating performance requirements, the rotor
orientation on the shaft must be determined. Two options are available, cantilevered, also called overhung, and centerhung. These relate to the position of the
rotor relative to the shaft and the support bearings. The cantilever design places
the rotor at the end of the shaft, while the centerhung design positions the rotor
in the middle of the shaft, with bearings on either side of the rotor. Often the
determining factor for selection is the ratio of axial height (AH) to outside rotor
diameter (OD). The conservative approach limits cantilever selection to AH/OD
0.5, though designs with ratios up to about 0.85 are possible. Numerous examples
of rotating equipment, such as pumps, compressors, and centrifuges, can be found
for each design conguration. Figure 5 illustrates the vertical-shaft cantilever
design; Figure 6 illustrates the horizontal-shaft cantilever design; and Figure 7
illustrates the horizontal-shaft centerhung design.
In addition to the rotor dimensions, other considerations for selection of
rotor shaft position include impact on operating performance, cost of manufacture,
maintenance, and number and type of seals. The operating performance is not
expected to deviate signicantly based on rotor position. The possible considerations include rotor imbalance due to ooding of the housing and liquid distribution
on the rotor. In general the centerhung design is considered more stable, but it has
a slightly higher cost of manufacture due to the split case housing, is more difcult to maintain, and requires two shaft seals instead of one. Standard equations for
fatigue and rigidity are used to determine shaft diameter for both orientations.
4.2.
Horizontal Versus Vertical Shaft Orientation
The centerhung design is restricted to a horizontal shaft orientation. A verticalshaft cantilever design is expected to have slightly lower maintenance costs than
the horizontal-cantilever design. Both cantilever options should have similar
design and fabrication costs. Flooding of the housing due to insufcient liquid
drainage would be less of a problem with the vertical-shaft arrangement with
respect to rotor imbalance. Liquid distribution on the rotor can be inuenced by
gravity more on the vertical shaft, but the effect should be minimal. Reference 7
illustrates both the centerhung and cantilever horizontal-shaft arrangements and
discusses an application for use of the vertical-shaft cantilever design.
4.3.
Seals
Two types of seals are needed to prevent uid leakage from the housing and to
ensure that gas passes through the rotor countercurrent to the liquid. Seals on the
shaft as it passes through the housing can be of a design appropriate for the uids
FIGURE 5 Pilot-scale RPB illustrating the vertical-shaft cantilever design with

direct motor drive. (Photo courtesy of The Dow Chemical Company.)
FIGURE 6 Pilot-scale RPB illustrating the horizontal-shaft cantilever design

with direct motor drive. (Photo courtesy of Higravitec Center of Beijing University of Chemical Technology.)
being handled. Mechanical seals, lip seals, and packing glands are some suitable
examples. As mentioned previously, a centerhung rotor requires two shaft seals,
whereas the cantilever rotor requires only one. To seal the rotor to prevent gas
bypassing, labyrinth seals and liquid ring seals are options. Figure 1 shows the
position of seals for a vertical-shaft cantilever design.
FIGURE 7 Commercial water deaeration RPB using the horizontal-shaft centerhung design and direct motor drive. (Photo courtesy of Higravitec Center
of Beijing University of Chemical Technology.)
4.4.
Power Train
Options for connecting the motor drive to the shaft depend on the shaft orientation. A vertical-shaft cantilever design would prefer a belt drive to reduce the cost
of manufacture of the support structure and to facilitate maintenance. A horizontal shaft has the additional option of direct coupling. Variable speed can be
accomplished through a gearbox or preferably through variable frequency control
on the motor. In addition to the power requirements discussed previously, the
startup power to overcome the torque of the rotor must be considered. This startup power is related to the time required to reach the desired rotor speed.
4.5.
Liquid Distribution
As discussed previously, proper liquid distribution on the rotor is critical to performance, but it is also important to prevent rotor imbalance. Rotor imbalance
from liquid maldistribution is especially a problem with high-viscosity uids.

Liquid distributor pipes extending the axial length of the rotor, depending on
the pipe diameter and number, can be a source of additional gas pressure drop.
Gas ow around the distributor pipes can also be a source of vibration. In the case
of a vertical-shaft arrangement, the liquid head in the vertical distributor pipe
must be considered to ensure equal liquid distribution on the axial length of
the rotor.
The rotor can be used to assist liquid distribution either by attaching the distributor pipes to the rotor or by introducing the liquid onto the rotor and allowing
the centrifugal force to move the liquid to the packing. In the former option the
liquid must enter the RPB through the shaft, requiring machining of a channel in the
shaft and an additional seal. In the case of liquidliquid extraction, the shaft must
have at least one channel for introduction of one of the liquid phases (see Figure 2).
4.6.
Rotor Packing
The selection of the type of rotor packing depends largely on the performance
requirements. However, there are some mechanical design considerations. Examples
of packing include woven wire screen, pellets randomly packed, foam metal, and
structured packing. The materials of construction must have physical properties sufcient to withstand the hydraulic forces created by the accelerating liquid. The packing must be dimensionally stable during operation to avoid rotor imbalance issues.
Some packing materials may require supports to keep them in place. Proper
design of the supports will consider porosity to prevent ooding, strength, impact
on uid distribution, and pressure drop.
4.7.
Multiple Rotors
Several designs involving multiple rotors have been proposed. To accommodate

the need of additional transfer units in countercurrent gas/liquid contact, a vertical shaft with at least two rotors and appropriate internals to conduct the gas from
the bottom to the top and liquid from top to bottom can be built (5). Another variation allows for heat transfer in addition to the mass transfer. By providing rotors
for condensation and for boiling and multiple packed rotors for gas/liquid contacting, a self-contained distillation column on a single shaft is envisioned (6).
Obviously, these multiple-rotor devices are more complex from a mechanical
design and construction perspective. However, they offer some interesting possibilities for reducing plant size by combining multiple unit operations and additional stages of separation in one piece of equipment.
5.
APPLICATIONS
The operating and design principles given previously provide a basis for understanding the performance enhancement available to a wide variety of applications.
These include standard mass transfer operations, such as absorption and stripping, but also include reaction systems. The following section highlights some of
the applications for which data are available and suggests other opportunities for
exploitation of the intensied mass and heat transfer capabilities.
5.1.
Absorption
Absorption of a component of a gas stream into a liquid is a common practice in

the chemical industry to affect cleanup of vent gases, conduct chemical reactions,
purify products, or to recover products from process streams. The enhanced mass
transfer capability of RPBs provides the opportunity to perform absorption processes in smaller equipment, to lower inventories, to shorten startup and shutdown
times, and to lower pressure drop (48). Figure 8 provides a visual comparison of
the size of a conventional absorber tower next to three RPBs that handle the
equivalent gas and liquid ows (9).
An example of industrial relevance is the removal of sulfur dioxide (SO2)
from vent gases by absorption into water or a lime slurry (48). In the water
absorption process, both gas-lm and liquid-lm resistance to mass transfer
occurs. As a result the overall mass transfer rate is proportional to gas-ow rate
and acceleration but inversely proportional to liquid-ow rate. Due to the fast
reaction of SO2 with lime, this system is only gas-lm diffusion limited. The
overall mass transfer rate is largely unaffected by gas- or liquid-ow rate and is
proportional to acceleration, but to a lesser extent than the water absorption
process. In both cases the overall mass transfer rate is reportedly much higher
than the corresponding conventional packed towers.
In another study of gas-side mass transferlimited absorption involving
SO2 absorption into a sodium hydroxide solution using a wire screen packing, the
overall mass transfer coefcient was found to be lower than reported data for
packed towers (16). Replacing the wire screen packing with two parallel rotating
plates signicantly enhanced the mass transfer performance.
Absorption of hypochlorous acid into water, a liquid-side mass transfer
limited process, showed HTU values as low as 4 cm, with a strong dependence
on liquid-ow rate. Heat of absorption removal was identied as a potential issue
with absorption in rotating beds (9).
5.2.
Stripping
Removal of volatile components from the liquid phase to a gas phase has been the
object of much study in RPB devices. One of the early successful applications
was oxygen removal from water for use in secondary oil eld recovery and boiler
water feed (7). The oil eld application demonstrated oxygen removal from 614
ppm to less than 50 ppb in both 50-T/h and 300-T/h RPBs using natural gas for
stripping. The packing had 92% porosity and 500-m2/m3 volumetric surface area
FIGURE 8 Commercial use of RPB technology in HOCl process. (Photo courtesy of The Dow Chemical Company.)
and was constructed of wire mesh. Comparison with conventional vacuum desorption in a packed tower combined with chemical reduction agents showed
lower cost and equipment size for the RPB approach. The proposed application
on oil platforms promises further advantages of weight reduction over conventional process equipment.
The boiler feed water deaerator reduced oxygen content to less than 7 ppb
by the use of exhaust steam (low pressure). This system operated at lower temperature (110C), used lower-pressure steam (0.05-MPa gauge), and achieved the
oxygen specication without the use of chemical reducing agents as compared to
conventional thermal desorption in a packed tower (7).
The preceding approaches to water deaeration used a gas continuous
process in the RPB. A liquid continuous RPB has been designed and tested for
this application as well (21). The liquid continuous process allows design of the
RPB for reduced power requirements, but it does require higher-pressure gas to
overcome the hydraulic head of the liquid. The schematic in Figure 2 shows the
liquid takeoff near the eye (inside diameter) of the rotor, thus recovering the
power needed to accelerate the liquid. In the case of oil platform water deaeration
using produced methane gas, boosting the pressure of the available gas would not
be necessary. As with the gas continuous process, mass transfer is enhanced by
increasing rotor speed and increasing gas-ow rate. Sampling at various radial
positions in the polyurethane foam packing revealed the possibility of liquid
back-mixing within the rotor that reduced the mass transfer efciency, i.e., fewer
transfer units than expected (21). Further work on the hydrodynamics of the gas
and liquid interaction may be warranted in order to realize the full potential of this
energy-saving approach for stripping (49).
A novel example of stripping in rotating packed beds is the stripping of
residual monomer and solvent from polymers (47). In polystyrene production,
conventional vacuum desorption achieves residuals reduction to about 500 ppm.
Steam-stripping technology is available to reduce residuals to about 200 ppm.
Compared to steam stripping, the RPB technology is expected to reduce capital
cost, energy costs, and equipment size and to eliminate the potential for side reactions of steam with the polymer. A pilot-scale devolatilizer, called an Accelerator,
and a larger demonstration unit showed the viability of this approach. Data collected at 510 mm Hg pressure followed the equilibrium curve for residual
styrene and solvent. This indicates that the mass transfer capability is more than
adequate to achieve equilibrium conditions in the short residence time in the
rotor. As a further effort to minimize process costs, the devolatilization rotating
packed bed was combined with a centrifugal pelletizer. Heating of the rotor and
polymer was accomplished by eddy currents generated by placing magnets on either
side of the rotor. Since the high viscosity of the polymer melt requires higher
g-force to achieve thin-lm ow over the packing compared to earlier gas/liquid
applications, the packing must have sufcient compressive strength to withstand
the generated forces. A reticulated foam metal packing of high porosity (90%)
and high surface area (500 m2/m3) was used (47).
Air stripping of volatile organic compounds from groundwater shows the
possibility of using RPB technology for either continuous operation or intermittent
remedial operation. Since a wide variety of processes (membranes, air stripping,
biological activity, chemical oxidation, and carbon adsorption) are available to
remove volatile organics from water, the selection of RPBs will depend on
the performance requirements and the relative cost compared to the alternatives.
Tests on air stripping of jet fuel components from groundwater show the viability
of RPB use (33). Both a wire gauze packing and a reticulated foam metal
packing proved effective in removing compounds such as benzene, o-xylene,
toluene, 1,2,4-trimethylbenzene, and naphthalene. A demonstrated number of transfer units as high as 12 gave corresponding height-of-transfer-unit values of 23 cm.
Another stripping application actually involves absorption and reaction as
well. Chlorine gas absorbs into sodium hydroxide aqueous solution, reacts to produce hypochlorous acid (HOCl), and is then stripped using excess chlorine gas.
The primary measure of performance of this operation is the recovery of stripped
HOCl. This study showed the importance of liquid distribution (type of spray
nozzle), gas/liquid ratio, and type of packing (wire gauze preferred over glass
beads or at plates). Above a minimal g-force, little performance improvement
was seen. Low-surface-area wire gauze packing (660 m2/m3) was just as effective
as high-surface-area (2800 m2/m3) packing (8). Scale-up to commercial operation
of this process showed a doubling of the HTU for this gas-side mass transfer
limited stripping. The actual pressure drop in the commercial scale RPB was half
the expected value. This same correlation, empirically based on centrifugal and
frictional factors of lm ow, effectively modeled the pilot RPB (9).
5.3.
Distillation
Distillation combines absorption and stripping in one device. Rotating packed

beds perform distillation by use of external condensers and reboilers, as in conventional towers (29), or by use of internal heat exchangers as part of the rotor (6).
Up to 20 theoretical plates were demonstrated in a rotor of 800-mm diameter (50).
Distillation was demonstrated on a 3-tons/h pilot plant separating an ethanol/
propanol mixture at total reux. The pilot plant consisted of two RPBs, one for
stripping and one for rectication, along with external reboiler and condenser,
respectively (51). Retrot of existing distillation towers with an RPB has been
proposed as a means to adding separation stages (52).
Another pilot distillation study employed only one RPB along with external condenser and reboiler. The cyclohexane/n-heptane mixture was separated at
rates up to 9 tons/h at total reux. The system provided up to 6 transfer units
(NTU) of separation in a 21-cm packing depth. The primary variable affecting
separation was rotor speed. Two operating pressures and a range of gas loading
(reboiler duty) provided additional data for analysis (29,42).
5.4.
Heat Transfer
Heat input or removal in rotating systems is best accomplished using plates to

separate the heat transfer uids from the process uids (45). Since spinning disc
technology is discussed in Chapter 3 of this book, this section will cover only the
application of heat transfer in conjunction with rotating packed beds and some of
the issues related to further development needs.
In the 1950s Hickman developed a centrifugal vapor compression evaporator for seawater desalination (53). This device consisted of multiple spinning
discs. Seawater sprayed on one side of the disc evaporated, while the centrifugal
force removed the residue from the plate surface. The vapor was compressed and
returned to the opposite side of the plate, where condensation provided the heat
for evaporation and the desired freshwater for recovery. Overall heat transfer
coefcients of 18 kW/m2-K are about three times higher than those achieved in
steam turbine condensers.
A high-intensity heat pump, called Rotex, has been developed taking
advantage of the enhanced heat and mass transfer performance of rotating discs
(44). This single device carries out the processes of evaporation, condensation,
absorption, and heat transfer to a working uid.
The higher heat transfer coefcients experienced by Hickman led to the
concept of placing a peripheral reboiler and core condenser on either side of a
rotating packed bed (50). This concept would be useful for distillation applications that need reux and boilup. The internal exchangers as part of the rotor
would decrease the required heat transfer surface area but would involve additional design and fabrication complexity.
Although heat exchangers on either end of a packed rotor are an option for
replacing external heat exchangers for distillation, the problem of heat transfer
within a porous packed bed remains. Heat input can be achieved by use of eddy
currents (47), microwaves, or sonic energy. Thus operations such as evaporation,
stripping, and endothermic reactions can be envisioned. Heat removal, however,
is more problematic. Exothermic reactions must be conducted adiabatically within the rotor, unless a suitable means of extracting the heat of reaction can be
developed. One approach could be alternating packing and heat transfer plates.
This raises the complexity of design and fabrication but could provide the needed
cooling to approach isothermal operation. A simpler method of evaporative cooling is possible if the evaporation is compatible with the chemical process.
5.5.
Adsorption
Centrifugal adsorption technology (CAT) allows the use of very small adsorbent
particles (microns) to increase the mass transfer efciency. Application to ion
exchange, volatile organic removal from water, recovery of pharmaceutical proteins, and production of ne chemicals are examples of potential commercial
interest. Process advantages include low inventory, low contact time, steady-state
operation, and relatively small equipment (54).
The CAT mode of operation involves introduction of the adsorbent near the
axis of the rotor, allowing the centrifugal force to move the particles radially outward. Liquid introduced at the outer periphery of the rotor moves countercurrent
to the adsorbent and is removed at the axis of the rotor. Adsorbent slurry collects
at the periphery and is conducted to the rotor axis for discharge. Experiments
using activated carbon to adsorb n-butanol from water revealed that the degree of
back-mixing is the dominant factor in performance. Back-mixing is a function of
rotor speed, density difference between the phases, and the particle diameter (54).
The hydrodynamics of two-phase ow in CAT were compared to two-phase
ow under gravity using a large-diameter (1.3-mm) particle in water with a small
density difference and a small-diameter (81.8-micron) particle in water with a
large density difference. The throughput capacity of the CAT was higher than predicted from the homogeneous-ow model, though the model works well for the
gravity-ow column. Pressure drop estimates were used to predict void fractions
in the range of 0.70.8. Higher rotor speeds resulted in higher void fraction (55).
5.6.
LiquidLiquid Extraction
The use of centrifugal elds for liquidliquid extraction was perhaps the rst
commercially successful application of rotating packed beds. Podbielniak modied a patented vaporliquid contactor (2), using a perforated spiral passageway
as the rotor packing, to solve problems with penicillin recovery in 1945 (1).
Penicillin broth forms stable emulsions that require centrifugal force to break.
Solvent extraction was effective only at low pH, which caused penicillin degradation. Multiple stages were needed to affect the necessary concentration. In
addition, the fermentation liquor varied signicantly from batch to batch and plant
to plant. Conventional countercurrent solvent extraction, mixer-settlers, and mixercentrifuge combinations could not effectively solve these problems without product loss. The centrifugal solvent extractor achieved 98% product recovery by taking
advantage of its low liquid holdup, short residence time, high centrifugal force,
and multistage countercurrent contacting.
Continuous glycerin washing of soap produced by saponication has been
demonstrated in a countercurrent centrifugal extractor (38). The device achieves
phase separation with as little as 0.02 specic gravity difference and accomplishes
up to 10 theoretical stages of extraction. Some of the advantages over prior operations reportedly include exibility in feed, low holdup, less waste due to more
efcient separation, simple operation, rapid startup, and small space requirements.
Rotors lled with ceramic foam instead of perforated cylinders have been
tested for liquid extraction of trace contaminants from water (23). The test solution
used a C12 alkene to extract 1,2-dichloroethane from water. Flow patterns are similar to the previous applications, with the heavy phase introduced at the inner
diameter of the rotor and the light phase at the outer diameter. Countercurrent
ow is achieved as the heavy phase moves outward, displacing the light phase
inward. The results indicate an optimum pore size for the ceramic foam, decreasing height of transfer unit with increasing rotor speed, and increasing holdup with
increasing dispersed phase ow.
The ability of the centrifugal extractor to solve difcult liquidliquid separation problems, as illustrated in the previous examples, has allowed its use in a
wide range of extraction applications. The long history of use has given it a general acceptance in chemical manufacturingan acceptance not shared by the
broader application of gasliquid interactions.
5.7.
Crystallization
In the reactive precipitation process of reacting CO2 with Ca(OH)2 slurry to produce nanoparticles of CaCO3, the controlling steps of the process are absorption
of CO2 and dissolution of solid Ca(OH)2. The degree of supersaturation depends
on the reaction rate and controls the nucleation rate and, therefore, the particle
size. The intense mass transfer and micromixing capability of the rotating packed
bed provides the environment to produce CaCO3 particles of size 1530 nm with
a narrow size distribution. Reaction time reduces 4- to 10-fold, compared to
stirred-tank reactors. Rotor speed, gasliquid ratio, and initial calcium hydroxide
concentration inuence reaction rate. An increase in rotor speed reduces the average particle size. Addition of growth inhibitors also helps to control particle size
and size distribution (56).
High-gravity reactive precipitation (HGRP) has been extended to the production of aluminum hydroxide and strontium carbonate (57). Aluminum hydroxide
fibrils precipitate from the reaction of sodium meta-aluminate (NaAlO2), water,
and carbon dioxide and are formed in diameters of 110 nm and lengths of
50300 nm. Rotor speed, gas- and liquid-ow rates, and initial reactant concentrations control particle size. Strontium carbonate particles of 40-nm mean diameter and narrow size distribution have been produced from the liquidliquid
reaction of strontium nitrate and sodium carbonate.
Crystallization that occurs during evaporation can potentially be intensied
by use of vapor recompression and spinning discs. In this scenario, the evaporated vapor is compressed and then condensed on the bottom of the discs to heat
the crystallizing uid (58). This approach may permit operation at higher temperatures, lower surface area, and less time.
Recrystallization of an active pharmaceutical ingredient on a spinning disc,
employing a solvent/antisolvent approach to induce rapid precipitation, results in
the desired small particles (115 microns) and narrow particle size distribution (59).
5.8.
Reactions
A signicant number of chemical reactions of commercial interest have reaction

rates limited by heat or mass transfer rather than the intrinsic chemical kinetics.
Many of these processes could be intensied by application of the RPB or spinning disc technology. Indeed, application of centrifugal elds to reacting systems
may represent its greatest potential. Improved yield performance may also be
possible (50). Spinning disc technology provides the advantage of heat transfer
capability. Thus, temperature control of exothermic reactions such as styrene
polymerization and intense mixing allow reduction in reaction time compared to
conventional batch reactors, especially in the latter stages of reaction, where viscosity is higher (60,61).
Polycondensation reactions that are equilibrium controlled, such as polyesters, could benet from the thin lms generated in the RPB or spinning disc. In
these reactions, removal of the coproduct of polymerization, e.g., ethylene glycol,
is necessary in order to advance the polymerization, a task that becomes increasingly difcult as the reaction proceeds. The thin lms and short residence time of
high-gravity devices aid the evaporation and may permit operation at higher temperatures than conventional reactors (50).
As mentioned previously, RPB and spinning disc technology may provide
benets for reactions that are mass or heat transfer limited, i.e., for fast kinetic
reactions. Unfortunately, the true chemical kinetics are often unknown. A smallscale RPB or spinning disc may prove to be a useful screening tool to determine
the intrinsic chemical kinetics. In one such study, six different reactions of interest in the manufacture of pharmaceuticals were screened using a spinning disc
reactor (59). Three of the six reactions were found to be limited by liquidliquid
mixing. These include a phase-transfer-catalyzed Darzens reaction, a crystallization, and a highly exothermic condensation reaction. In the Darzens reaction the
reactant inventory was reduced 99% and the impurity level decreased 93% as
compared to the conventional reactor. Crystallization achieved mean crystal size
of 3 microns, with a narrow size distribution. The highly exothermic reaction had
excellent temperature control.
A lab-scale RPB has also been used to investigate reactions that are mass
transfer constrained in conventional reactors. Testing a reaction that involves
release of a volatile organic as part of molecular weight buildup revealed overall
process reaction rates equivalent to conventional reactors in time frames more
than two orders of magnitude lower. Here the high surface area and surface
renewal capability of the RPB helped to overcome the transfer limitations across
the liquid boundary. Similar results were seen on other reaction processes that
were constrained by a liquidsurface interaction (62).
Reactions can be combined with other unit operations, as in the example of
reactive stripping in the production of hypochlorous acid (HOCl). An RPB was
used to absorb chlorine gas into an aqueous sodium hydroxide solution (caustic)
where reaction to HOCl occurs. Since HOCl is unstable in the presence of the
coproduct sodium chloride, stripping of the HOCl into the gas phase is necessary
to recover a stable product. The reaction of chlorine with caustic is essentially
instantaneous: therefore the process reaction rate is liquid-side mass transfer controlled. Stripping of HOCl, on the other hand, is believed to be gas-side mass
transfer controlled. The intense mass transfer capability of the RPB allowed 10%
higher yields while using less than half the stripping gas as compared to conventional spray tower operation. This study showed low-surface-area, high-porosity
wire screen packing to perform better than glass beads or parallel at plates.
Packing support design and liquid distributor type inuenced performance.
Operating parameters of importance included rotor speed and the gasliquid ratio
(8). Scale-up issues and performance of the commercial HOCl operation (9) are
discussed in Section 6.
Fermentation reactions are often limited by oxygen transfer rates. The
enhanced mass transfer achieved in centrifugal elds applied to bioreactions should
be expected to increase productivity. A centrifugal eld bioreactor (CFBR) demonstrated higher productivity in the overproduction of lipase with Staphylococcus
carnosus as compared to conventional fermenters (22). Both batch and semibatch
fermentation in the CFBR showed no inuence on the biological activity of
growth or exoprotein synthesis. Lipase productivity rates were proportional to
oxygen transfer rates, which were 10 times higher than in shaken cultures. The
CFBR process involved feed of air and liquid to the outer diameter of the rotor,
with takeoff at the center. Air was dispersed in the liquid by either a sieve drum
or a multilayer-sintered screen. The inward radial movement of the gas helped to
suspend the bacteria in the culture against the centrifugal force. An external circulation loop for the liquid allowed heat exchange and product analysis. Since
many fermentation reactions are characterized by foaming, the CFBR was
equipped with a foam breakera stator with needles positioned at the inside
diameter of the rotor.
5.9.
Other Applications
Centrifugal elds in an electrochemical cell facilitate the removal of gas bubbles

from the electrodes, thus reducing the voltage requirement. A rotating chlorine cell
showed a drop in voltage from 3.17 V to about 2.8 V at 3-kA/m2 current density
when accelerated to 200 g (50). Demonstration of a rotating air cathode provided
greater voltage drop at higher current density as compared to a stationary cell (50).
Dedusting or demisting in rotating devices provides opportunity to remove
small particles at very high throughput. A mop-fan built with exible bers in
a conventional fan housing effectively removes 50% of two-micron particles
of slaked lime dust in conjunction with water spray on the rotor. Inline rotary
demisters employing reticulated metal foam are used for oil separation from air
on turbines (50).
6.
SCALE-UP AND COMMERCIAL USE
Although considerable studies on the use of centrifugal elds in chemical processing have been reported for lab- and pilot-scale operations, little information
is public on scale-up criteria for either performance parameters or equipment
design. Three examples of commercial use of centrifugal elds are available for
review. These include liquidliquid extraction, water deaeration, and reactive
stripping for hypochlorous acid production.
Commercial application of centrifugal elds encounters considerable
resistance from both the technical and business communities due to both real and
perceived risks. The real risks involve reliable mechanical design of rotating
equipment, which includes seals, bearings, and rotor stability. Perceived risks
on process performance may derive from a lack of understanding of the process
fundamentals and how performance may change with the scale of operation.
Overcoming the tendency to use what we know and understand represents a
challenge that goes beyond the effort at technology development.
Convincing the technical community to accept the risk of rotating equipment for chemical processing may be easier on applications with clear performance advantages over conventional process equipment. A good example is the
liquidliquid solvent extraction of penicillin (1), in which the low residence time
and ability to handle emulsions and solids allowed 98% product recovery. The
10% higher yields and 50% reduction in stripping gas for the HOCl reactive stripping process provides another example of performance advantage (8).
In addition to the lower operating costs associated with enhanced performance, the business community is interested in lower capital investment and assurance that the process will reliably perform as designed in terms of product
capacity, on-stream time, and product quality. The smaller size of the centrifugal
equipment may satisfy the capital investment question. This was the primary
driver for implementation of water deaeration in China (7). Lower capital is also
a driver for the polymer devolatilization application (47). The question of reliable
performance is best addressed through convincing the technical community and
leveraging the considerable industry experience with design and manufacture of
rotating equipment, such as pumps, compressors, and centrifuges.
6.1.
Scale-Up Criteria
A number of parameters can be considered for scale-up of rotating packed beds,

including rotor packing, liquid distribution, ooding, pressure drop, rotor speed,
HTU, NTU, temperature, and pressure. Since the same packing material (same
porosity and volumetric surface area) is used on scale-up as in the pilot equipment, HTU is expected to scale directly. Results from water deaeration (7) and
HOCl production (9) indicate this may be true for liquid-side mass transfer
controlled operations but not for gas-side mass transfercontrolled operations.
Flooding of the rotor in gas continuous operations would be expected at the
same gas velocities as in the pilot RPB. Flooding normally occurs at the inside
diameter of the rotor due to the lower cross-sectional area and higher velocities.
However, a check of the porosity of the outer packing support may be necessary
to ensure that no ooding occurs. If scale-up of rotor speed is based on constant
rotor tangential velocity instead of constant g-force, then the gas velocity at ooding will be lower with larger-diameter rotors. Throughput capability and backpressure control of the light-phase takeoff (24) control ooding in liquidliquid
or gas-dispersed systems.
Using a pressure drop model based only on centrifugal acceleration and
frictional drag, the HOCl scale-up overpredicted the pressure drop of the commercial RPB by a factor of 2 (9). A more rigorous approach to pressure drop calculation that takes into account the conservation of angular momentum and the
inlet and outlet zones of the rotor and housing (40) should provide more predictable scale-up performance.
Rotor speed has an impact on mass transfer performance, ooding, and
pressure drop. Rotor speed on scale-up can be determined based on maintaining
constant tangential velocity (r) or constant acceleration (r2). Rotor speed will
be higher for constant-acceleration scale-up. Impact on both process performance
and equipment design must be understood in making this determination. Scale-up
based on constant acceleration is conservative for mass transfer and ooding performance, while constant tangential velocity is conservative for pressure drop.
Liquid distribution may be an important parameter, as demonstrated in the
HOCl process, where different liquid distributors provided signicantly different
results (8). The initial contact of the liquid with the rotor inuences the mass
transfer performance of the RPB in gas continuous operations (15). Although the
use of a packing support at the inside diameter of the rotor would be expected to
impact this initial liquid contact with the rotor, experiments did not show any
reduced mass transfer performance (36).
As mentioned earlier, the same rotor internals used in pilot tests should be
used upon scale-up. The rotor dimensions of inner diameter and axial height
are determined by maintaining a constant supercial gas velocity at the rotor eye.
The radial packing depth, and thus the outer diameter, is based on the number of
transfer units required. Adjustments in packing depth and packing type may be
necessary to achieve the desired liquid holdup or residence time, e.g., for chemical reaction (26).
As with any chemical operation, the physical properties of the uids, such
as density, viscosity, and heat capacity, must be known. If chemical reaction is
involved, then the intrinsic kinetics must be understood. Of particular relevance

is the inuence of mass transfer rates on overall reaction rates.
6.2.
Scale-Up Design
Once the rotor dimensions have been determined along with the operating conditions, attention shifts to the mechanical design of the RPB. The major concern
with rotating equipment is maintaining stable operation, i.e., limiting vibration.
Excessive vibration results in premature seal and bearing failure, poor process
performance, metal fatigue, and increased maintenance costs and downtime.
Proper mechanical design principles determine the option of cantilevered or
centerhung rotor, the shaft diameter, the type and position of bearings, and seal
design. The drive train, whether belt driven or direct coupled, is determined by
the power requirements and the shaft orientation. The housing must be sufcient
to contain the temperature and pressure of the operation and to provide adequate
inlet and outlet nozzles for the process uids.
6.3.
Commercial Examples
Two commercial examples of rotating packed-bed operation are water deaeration

for the Chinese oil elds (7) and HOCl reactive stripping in the United States (9).
These two cases illustrate nicely the range of process conditions and design
features available for successful scale-up. Water deaeration (Figure 7) uses a
direct-coupled drive on a horizontal-shaft centerhung rotor to process a low gasto-liquid operation (3 : 1 vol/vol). The HOCl process (Figure 9) employs a beltdriven, vertical-shaft cantilever rotor to contact a high gas-to-liquid ratio.
The water deaeration process employed a staged scale-up program. From
the lab operations, a 50 tons/hour (T/h) pilot RPB was built and tested in the oil
eld. Using natural gas for stripping at a gas/liquid ratio of over 2, the desired
oxygen content in the exit liquid of less than 50 ppb was demonstrated. This successful demonstration led to the installation of a full-scale commercial RPB to
process 300 T/h. This unit has rotor dimensions of 600-mm ID, 1000-mm OD, and
700-mm AH. The wire screen packing has high porosity (92%) and low surface area
(500 m2/m3). The rotor spins at a modest 750 rpm. Performance matched that of the
lab and pilot units, achieving a typical 30-ppb oxygen content. Two 250-T/h units
have been designed for installation on an oil platform to process seawater, providing advantages in size and weight as compared to conventional technology (7).
Figure 9 shows the commercial-scale RPB for the reactive stripping process
for HOCl production. Figure 8 provides a visual impression of the process intensication that occurs using RPBs. The three RPBs shown in the lower left of the
picture process the same volume of gas and liquid as the tall absorber tower to the
right. The scale-up factor from the pilot unit of over 400 : 1 yielded a rotor of
slightly less than 2 m in diameter. Performance of product yield from raw materials
FIGURE 9 Commercial RPB for HOCl production using the vertical-shaft

cantilever design with belt drive. (Photo courtesy of The Dow Chemical
Company.)
met or exceeded that of the pilot unit. Pressure drop half of that expected implies
the need for better predictive correlations. Due to the higher gas-handling capability and the conservative scale-up design, much higher capacities are anticipated
as compared to the design. The liquid-side mass transfer performance as measured by chlorate formation showed performance equivalent to or better than that
of the pilot RPB. However, the gas-side mass transfer, as represented by HOCl
stripping, showed a doubling of the HTU to about 8 cm. The mechanical reliability after two years of operation indicates no issues due to RPB operation. The
RPB is very easy to start up and shut down (9).
These two successful commercial applications of rotating packed beds
prove that scale-up from pilot-scale equipment can achieve the desired process
performance in commercial-scale operations. In addition, the mechanical reliability of the rotating equipment is in line with the experience with other rotating
devices. Thus, the risk concerns of performance and reliability can be managed
acceptably. Both the technical and business communities can have condence
that future applications will meet expectations of process performance and onstream time.
7.
FUTURE
Extension of the use of centrifugal elds into chemical processing, beyond the
physical movement of uids, has shown limited niche application in the past, in
spite of considerable research activity. Specialty application of centrifugal elds
to liquidliquid extraction has enjoyed success for more than 50 years. Advantages stem from operation at low density differences, breaking of emulsions,
short contact times, and higher efciencies as compared to other liquidliquid
extractors.
The commercial use of rotating equipment for the broader eld of gas
liquid operations has only a ve-year history. Numerous examples of possibilities
in the areas of absorption, adsorption, stripping, distillation, reactions, crystallization, and other operations have been referenced. The chief objections to the use of
centrifugal elds have been associated with the risks of scale-up and the operation
of rotating equipment. The two commercial applications of water deaeration and
HOCl reactive stripping demonstrate the ability to reliably scale up processes
involving a wide range of gasliquid loadings. Process performance in both cases
met or exceeded design criteria, with good operating reliability.
Further application will likely require signicant cost or performance
advantages over more conventional process technology. Considerable commercial experience will be needed before centrifugal elds will enjoy common
acceptance among both technical and business interests in the chemical industry.
To gain that status, projects must be selected carefully to ensure that advantages
are realized over alternative technologies.
The most likely opportunities for exploitation will come from mass transfer
limited reactions and the combination of unit operations in one device. Examples
of reactions mentioned earlier include polymerization, condensation reactions,
crystallization, and heterogeneous catalysis. Combined unit operations are illustrated by reactive distillation, polymer devolatilization with pelletization, and the
use of heat exchangers (reboilers and condensers) with distillation.
In addition to research on process applications, research to dene the fundamental performance characterizations is needed. A number of empirical correlations have been developed for pressure drop, residence time, power, ooding,
etc. More generalized theoretical expressions for these parameters that accurately predict performance on a wide range of rotor designs and sizes would be very
benecial to condently scale-up the technology.
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3
The Spinning Disc Reactor
C. Ramshaw
University of Newcastle upon Tyne, Newcastle upon Tyne,
England
1.
INTRODUCTION
When considering the options for intensifying reactions that involve multiple
uids, it is helpful to identify the shortcomings of the conventional equipment
that is currently in use. In this context, perhaps the most frequently used item is
the stirred vessel tted with a cooling jacket, shown in Figure 1. A turbine impeller
generates a circulation comprising two toroidal vortices, and the turbine torque is
normally prevented from driving a free vortex by the use of wall bafes, as
shown. If a gasliquid reaction is involved, then the gas is usually injected directly
below the impeller via a suitable sparging arrangement. The popularity of the
stirred vessel is due to its perceived simplicity and adaptability, coupled with the
fact that it is supercially straightforward to scale-up from the laboratory beaker
that was used when the process was being developed. Unfortunately, it suffers
from several serious problems, as indicated later.
In the normal case of a geometrically similar scale-up, it can be readily
shown that the surface area per unit volume varies inversely with the vessel diameter. Thus larger vessels are more difcult to cool, since the heat generated by
a reaction in a potential runaway situation is proportional to the vessel volume,
whereas the surface area available to dissipate a given heat output is decreased.
Vigorous reactions may require the reactor to be detuned by operating with
more dilute feedstock in order to reduce the full-scale reaction intensity. This
FIGURE 1 Stirred vessel showing circulation pattern.
could inuence the reaction temperature trajectory and compromise the yield and
selectivity.
A further unfortunate characteristic of the stirred vessel is that its mixing
capability is also a strong function of its size. Scale-up usually proceeds on the
basis of a constant impeller tip speed, and since the mean circulation speed in the
vortices is broadly proportional to the tip speed chosen, the circulation time is
proportional to the vessel diameter. Thus the turnover time of the vessel contents
increases at the larger scale and the macro mixing performance deteriorates.
These fundamental shortcomings of the stirred vessel have generated a considerable degree of uncertainty when ne chemical or pharmaceutical processes
are being developed for full-scale operation. This has led the relevant regulating
authorities, e.g., the U.S. Food and Drug Administration, to insist on a process
validation at laboratory, pilot, and full scale. Since each validation entails signicant administration and delay, the procedure can hold up the implementation of
commercial production by several years. Because a new metabolically active
molecule will be patented as soon as possible and certainly before clinical trials
and process development, this delay signicantly erodes the time available under
patent cover to recoup a companys R&D expenditure and make a prot from a
potential blockbuster drug.
1.1.
The Desktop Continuous Process
The predominant culture that prevails for the production of ne chemicals/drugs,

with an output of up to (say) 500 tons per year, is to operate batchwise. As already
noted, this stems from the fact that the process is almost always developed from
a batch-operated beaker or ask. However, it is worth observing that an output of
500 tons/year of active substance corresponds to a continuous process ow rate
of around only 70 mL/second. This allows various items of intensied equipment
to be assembled and operated continuously literally on a desktop to meet the

production demand. The decision to switch from batch to continuous processing
immediately confers an intensication benet because the peak batch process
loads (e.g., heat output, liquid removal, etc.) are distributed in time, so equipment
size can be reduced. Thus with a new process, the laboratory scale becomes the
full scale when allowed to run continuously and the scale-up delays described
earlier are largely avoided. This strategy is generating considerable industrial
interest as the commercial pressure to bring new molecules to market rapidly continues to increase.
A further factor that favors continuous desktop manufacture is its potential impact on the overall business process of making and marketing ne chemicals. Thus it goes without saying that with very short process residence times, the
operation can be much more responsive so that grade changes can be effected in
seconds rather than hours. This facilitates just-in-time manufacture, which can
lead to dramatic reductions in the capital costs associated with the multiple grades
of stock that may be needed rapidly to satisfy demanding customers.
1.2.
Exploitation of Centrifugal Fields
Approximately two-thirds of the unit operations performed in process engineering involve multiphase contact (e.g., distillation, gas/liquid reaction, boiling). In
the absence of an imposed acceleration eld, the system uid dynamics are dominated by surface forces so that the interfacial area developed is relatively small,
and, with no buoyancy force, there can be no countercurrent interfacial motion.
When these conditions prevail, the intensity of the operation is very low, with little if any process performance (e.g., reaction, separation, heat transfer) being
exhibited. This scenario leads naturally to the suggestion that a high-acceleration
eld would stimulate the generation of smaller bubbles, higher ooding velocities, and more intense shear stresses.
This Higee strategy has been championed over many years because of its
profound and benecial impact upon many important multiphase operations:
Absorption
Distillation
Boiling
Condensation
Liquid extraction
Particle disengagement
Heat pumps
Etc.
One particular embodiment of this approach is the rotating packed bed,
which was originally conceived as the Higee equivalent of a packed column (1),
FIGURE 2 The Higee contactor (continuous gas phase).
shown schematically in Figure 2. The equivalent stage height within the toroidal
packing is about 1.5 cm for a gas lmlimited system, compared with about
60 cm in a conventional packed column. Equivalent ooding velocities may
be estimated from the Sherwood plot and can be very high, even for packing with
a specic surface area exceeding 1000 m1. Since the Higee duty was originally envisioned as being purely orientated to mass transfer, no specic heat
transfer capability was provided. However, the spinning disc reactor (SDR) may
be regarded as an alternative to the Higee rotor. It can act as a mass transfer/
contacting device (possibly with multiple discs) or as a particularly intense
gasliquid reactor (when tted with heating/cooling provision). Its attraction lies
in the high heat and mass transfer rates that can be stimulated between the disc
and the thin liquid lm generated on its surface, and between the lm and the
adjacent gas. The performance and applications of the SDR are considered in
detail later.
As might be expected, the enhanced acceleration eld is established on a
permanent basis within a rotor that receives and discharges the working uid. The
alternative approach, which relies upon a permanent vortex eld, i.e., a cyclone,
will not be considered here, primarily because the uid residence time within a
vortex cannot be easily controlled independent of the desired acceleration. At this
juncture it is helpful to consider the basic physics of motion in a rotating system.
1.3.
Free Motion of a Particle Around an Axis
Consider the free (frictionless) motion of a particle P of mass m rotating around

a xed axis O on a smooth surface, as shown in Figure 3. The particle is constrained to move in a circular trajectory by a light string that exerts an inward tension T and generates a corresponding acceleration. This can be estimated as
follows: In time t, P moves along an arc that subtends an angle to the axis.
The angular velocity of P is given by ddt and its speed is v r, where
r is the length of the string. During the time t the change of velocity of P is
v v sin () and as 0, v is directed along the radius toward O.
The acceleration is
dv v sin ( d )

v as 0
dt
dt
Hence,
acceleration r2
and the string tension needed to maintain this is
T m2r
FIGURE 3 The free motion of a particle around an axis.
FIGURE 4 Spiral trajectory as a particle moves toward the center of rotation.
If the string is broken, then the acceleration ceases and the particle leaves its circular trajectory and continues along a tangent at a velocity v.
If the string is slowly shortened then:
1. The particle moves toward O in a spiral trajectory involving many turns.
2. Work must be done in order to overcome the string tension T.
For the proposed frictionless system, this work input results in an increase
in the particles kinetic energy. Conversely, if the string were lengthened, the particles velocity would decrease. Figure 4 shows the spiral trajectory of the particle and the corresponding velocity diagram. The radial and tangential velocity
components are drdt, v, respectively, giving a resultant VR that is a tangent to the
spiral trajectory.
Noting that drdt << v, the angle between v and VR is , where
tan (drdt)v. As the particle moves inward towards O, the component of T
along the spiral trajectory is responsible for increasing its speed.
Hence, with an inward tension deemed to be negative we have:
m
dv
v 2 dr 1
T sin m
dt
r dt v
(as 0)
or
dv
dr v

dt
dt r
(1)
This conrms that v increases for an inward spiral trajectory (i.e., when
drdt is negative). From Eq. (1) we have
dv
dr

v
r
and integration from v1r1 to v2r2 gives
ln
v2
r1
ln
v1
r2
i.e.,
v2 r2 v1r1
(2)
This is an important result because it shows that in a frictionless or free situation,

angular momentum is conserved.
The same conclusion can be reached from energy considerations, noting
that the work done by the string tension as r is reduced is equal to the gain in particle kinetic energy, i.e.,
T dr m
v2
v2
dr d m mv dv
r
2
Hence
v
dr dv
r
leading again to Eq. (2).
The practical consequence of Eq. (2) for rotational uid ow can be quite
dramatic, as demonstrated by the high wind speeds that may be generated near
the center of free vortex owse.g., tornadoes and typhoons.
1.4.
Flow Over a Rotating Surface
If we now consider the behavior of a liquid lm on a rotating disc, the motion is

no longer free, because the lm is inuenced by the disc via the shear force
generated at the solid/liquid interface. Liquid supplied to the inner region of the
disc is rst brought up to the discs rotational velocity by the tangential shear
force and then moves radially outward, to be discharged from the disc periphery.
In a stationary frame of reference, the liquid trajectory is therefore a spiral with
arms separated by a radial distance given by
2
dr
dt
In a rotating frame of reference (i.e., that of an observer anchored to the disc),
the trajectory is nearly radial. Since this reference frame is most relevant when
we consider the disc/uid interaction, it is helpful to evaluate the ow on this
basis.
We shall assume that frictionless ow occurs through a closed radial channel that is xed to the rotating disc. Thus as the uid moves outward, the only
interaction with the disc/channel is via a tangential force. In a time dt, the change
per unit mass in the uid angular momentum as it moves a distance dr is
dM d (rr ) 2r dr
(3)
Note that since the uid is forced to rotate at the disc speed, is constant.
The change in angular momentum given by Eq. (3) is brought about by the torque
generated by a tangential force F exerted on the uid at the radius r by the radial
channel and acting for a time dt. Since dM Fr dt, the tangential acceleration
imposed by the channel on the uid as it moves radially is
F 1 dM
dr

2
m r dt
dt
(4)
This is the Coriolis acceleration, which is imposed on particles moving in a rotating reference framee.g., liquids on a rotating surface or winds in the earths
atmosphere. The resultant acceleration experienced by a particle is a combination of the radial and tangential components, making an angle to the radius,
where
tan 2
dr
2
2 r
dt
v
dr

dt
In general
dr
<< v
dt
and the unconstrained ow will be largely radial. This can be readily conrmed
during the operation of a spinning disc reactor or a rotating packed bed, because
any deposits from the uid ow lie close to the radius vector.
2.
THE SPINNING DISC REACTOR
As pointed out earlier, a spinning disc, or more generally a rotating surface of revolution, is an alternative to the Higee rotating packed bed. It is particularly effective when high heat uxes or viscous liquids are involved. The object is to
generate a highly sheared liquid lm when a liquid is supplied to the unit at or
near its center. The lm is initially accelerated tangentially by the shear stresses
established at the disc/liquid surface. This causes the liquid to approach the discs
angular velocity and then move outward as a thinning/diverging lm under the
prevailing centrifugal acceleration. The phenomenon was studied in detail by
Woods (2), who photographed the behavior of a fully wetting dilute lm of ink as
it traveled over a spinning glass disc. Care was taken to supply the liquid from a
central axisymmetric distributor in a particularly uniform manner. After calibration,
the local lm thickness was inferred from the density of the photographic image
at that point.
Even when great care was taken to ensure that the liquid feed was introduced to the disc in an axisymmetric manner with the minimum disturbance, the
smooth inner lm always broke down into an array of spiral ripples, as shown in
Figures 5 and 6. These spiral structures then broke down further until the wave
pattern became utterly chaotic, provided that the disc was big enough. It is known
that liquid lm ow over a surface is intrinsically unstable, and the phenomenon
has been studied by several workers (37). It appears to be qualitatively equivalent to the breakdown of a smoke plume rising from a lighted cigarette, where a
chaotic zone is generated about 20 cm above the source. The behavior can also be
observed when a liquid lm ows over a stationary surface such as a windowpane
or a dam spillway.
Woods concluded that two types of wave existed: nearly two-dimensional
(2D) and three-dimensional (3D). The amplitude of the two-dimensional spiral
waves grew rapidly, and therefore a theory based on the assumption of small amplitude is not valid across the whole disc. A transition from 2D to 3D waves occurred
once their amplitude reached about three to four times the local lm mean thickness. Higher liquid ow rates stimulated a more rapid breakup of the wavelets.
Only about 1% increase in liquid surface area was ascribed to the presence of
waves. Thus any improvement in mass/heat transfer performance generated by
the waves is due to the additional shear they induce. It will be appreciated that
even in the absence of ripples, highly sheared thin liquid lms, such as those that
can be readily generated on a spinning surface, provide an ideal uid dynamic
environment for the rapid transmission of heat, matter, and momentum. This is
due to the short diffusion path length involved for transfer between the adjacent
gas phase to the liquid lm and thence to the disc surface. These characteristics
of a spinning disc (or more generally a rotating surface of revolution) make it
ideal for performing any intrinsically rapid physical or chemical transformation
in a liquid, even if it is viscous. Typical examples include polymerization, precipitations, and rapid exothermic organic reactions. Some of these are described
in more detail later.
2.1.
The Nusselt-Flow Model
While the uid dynamics of the actual lm-ow process across the disc is dauntingly complex, a very approximate interim ow model may be based upon
Nusselts treatment of the ow of a condensate lm. This assumes that the ow is
stable (i.e., ripple free), that there is no circumferential slip at the disc/liquid surface, and that there is no shear at the gas/liquid interface. The treatment is based
FIGURE 5 Liquid lm behavior on a rotating disc, with Q 19 cm3/s and

(a) 100, (b) 200, (c) 300, (d) 400, (e) 500, (f) 600 rpm.
FIGURE 5 (cont.)
FIGURE 5 (cont.)
FIGURE 6 Local liquid lm behavior on a rotating disc, with (a) Q 19 cm3/s,

100 rpm; (b) Q 19 cm3/s, 200 rpm; (c) Q 13 cm3/s, 400 rpm;
(d) Q 19 cm3/s, 500 rpm; (e) Q 19 cm3/s, 600 rpm; (f) Q 19 cm3/s,
600 rpm.
FIGURE 6 (cont.)
FIGURE 6 (cont.)
FIGURE 7 (a) Sketch of a liquid lm on a rotating disc. (b) Detail of a liquid

lm on a rotating disc.
on the schematic representation given in Figure 7. Part b represents the local lm

at a radius r. The shear stress on the annular plane at a distance y from the disc
provides the radial acceleration for the uid lying between y y and y s. Thus a
force balance on the lm lying between r r and r r dr, with zero shear
stress at the gasliquid interface, gives
2 r ( s y)
du
dy
(5)
The boundary conditions are:

1. u 0 at y 0 since there is no uid slip at the disc/liquid interface.
2. dudy 0 at y s since there is no shear stress at the gas/liquid
interface.
Hence
2 r
y2
sy

2
u
(6)
The average lm velocity is given by

Uav
1
s
u dy
w 2 rs 2
3
The maximum lm velocity (at y s) is

Umax
w 2 rs 2
1.5 Uav
2
(7)
Referring to Figure 7a, the liquid is supplied to the disc at a radius ri and a
mass ow rate M. It is deemed to instantaneously acquire and maintain the disc
angular velocity as it moves over the disc to be discharged at its periphery. At a
radius r the mass ow rate is given by
M Uav s2r
(8)
Eliminating Uav from Eqs. (7) and (8) gives

3M
s
2
w 2 2
1/ 3
r 2 / 3
(9)
Inserting Eq. (9) into Eq. (8) gives

Uav
w 2 r 3M
3 2
r 2 w 2 2
M 2w2

12
2
2/3
1/ 3
r 1/ 3
(10)
Hence the average time required for the liquid to travel from ri to ro is
t
R0
Ri
dr 3 12 2

Uo 4 M 2 2
1/ 3
(ro
4/3
ri4 / 3
(11)
If we consider a typical example of water owing over a disc under the following conditions:
M 3 102 kg/s
103 N-s/m 2
10 3 kg/m 3
ri 5 102 m
ro 0.25 m
100 s1 (955 rpm)
then from Eq. (11) the average liquid transit time on the disc is 0.25 s, and from
Eq. (9) the lm thickness at the disc edge (provided that the lm does not break
up into rivulets) is 28 microns. A more viscous liquid, such as a polymer (say,
10 N-s/m2), would have a thickness at the disc periphery of 600 microns and
a transit time of about 5 seconds.
As already noted, the foregoing calculations must be regarded as a guide
only, since the lms are intrinsically unstable, with waves being amplied as the
liquid proceeds to the edge of the disc. It will be appreciated that this process proceeds more rapidly with relatively inviscid liquids.
2.1.1.
Mass Transfer
A conservative estimate of the discs mass transfer performance may be obtained

from the Nusselt model, assuming that there is no lm mixing as it proceeds to
the edge of the disc. For unsteady diffusion into a nite stagnant slab, the plot
shown in Figure 8 from (8) gives the relative concentration distribution within the
slab at various times, with a zero initial concentration and a surface concentration
C0 imposed at time t 0. The parameter on the curves is the Fourier number, Fo,
where
Fo
Dte
s2
(12)
and
D solute diffusivity within the lm
te exposure time of the lm surface
s lm thickness
As can be seen from Figure 8, if Fo 0.02, the concentration changes
within the lm are conned largely to the surface layer and the local mass transfer coefcient is given by the Higbie penetration theory (9) as
D
kL

te
1/ 2
(13)
For the previous example of a polymer owing over the disc, a typical
Fourier number may be calculated from:
D 109 m 2 /s
te 5 s
s 6 104 m
FIGURE 8 Concentration distribution at various times in a slab x for

zero initial concentration and surface concentration C0.
Thus Fo 0.014.
Equation (7) shows that the lm surface velocity is given by
9 M 2 2
Umax 1.5 Uav 2
32
1/ 3
r 1/ 3
Hence from Eq. (11),

32
2
te
2 2
9 M
1/ 3
3 4/3
r r14 / 3
4
(14)
Inserting this into Eq. (13) gives

D
kL
1/ 2
2 M 2 2
2
3

1/ 6
(r
1
4/3
r14 / 3
(15)
1/ 2
However, it must be noted that as the lm ows over the disc, the lm thickness progressively decreases, provided the liquid fully wets the disc. As this
occurs, the concentration proles normal to the disc plane are compressed, thereby causing a proportionate enhancement of the solute diffusion rate beyond that
predicted by penetration theory. Thus the local value of kL can be corrected to
account approximately for the steepened concentration gradients by multiplying
by a factor s1s, where s1 is the lm thickness at a radius r1 as given by Eq. (9).
The corrected local value of kL is then
D
kL
1/ 2
2 M 2 2
2
3

1/ 6
r

r1
2/3
(r
1
4/3
r14 / 3
1/ 2
(16)
At the point of lm formation, where r r1, Eq. (16) shows that kL .

However, the average value of kL over the disc surface is given by
k Lav
1
2
r2 r12
r2
2
k L r dr
(17)
r1
This requires numerical integration. As pointed out at the outset, these estimates
of the mass transfer performance are likely to be conservative as the disturbance
of the lm by ripples has been neglected. This will reduce the exposure time signicantly, particularly with inviscid liquids.
2.1.2.
Heat Transfer
The Nusselt model was originally developed to correlate the performance of

vapor condensers. In this case, the latent heat of condensation is discharged at
the gasliquid interface and subsequently conducted through the draining condensate lm, the conduction path length being the local lm thickness. When a
liquid lm is heated or cooled on a spinning disc, the conduction path length is
less (about 50% of the thickness) because all of the sensible heat does not have
to be conducted through the entire lm. Since the thermal diffusivity of most
liquids is typically of the order of 107 m2/s, compared with a mass diffusivity of
around 109 m2/s, the Fourier numbers involved in the heat transfer version of
Figure 8 are approximately 100 times their mass transfer equivalent. This implies
that the heat transfer process involves the whole liquid lm rather than merely
a thin layer near the disc surface. The Higbie model for heat transfer is therefore
inappropriate.
For the larger Fourier numbers involved in the heat transfer it is reasonable
to represent the lm temperature prole approximately by a quadratic expression:
T A By Cy 2
(18)
A, B, and C are constants determined by these boundary conditions:

1. T Tw at y 0
2. T Ts at y s
3. dTdy 0 at y s
It can be shown that
y
y2
T Tw 2(Tw Ts ) (Tw Ts ) 2
s
s
(19)
dT 2(Tw Ts )

dy
s
(20)
and
y 1
s
Since the lm temperature gradient perpendicular to the disc will be much

greater than that in the radial direction, the local heat ux (Q) into the lm will
be controlled by the value of dTdy at the disc surface. Hence
dT
2k
Q k
(Tw Ts )
s
dy y 0
Thus the effective lm coefcient is
h
Q
2k

s
Tw Ts
(21)
For our earlier example with water on a 0.5-m-diameter disc, Eq. (21)
implies that the heat transfer lm coefcient at the periphery is 43 kW/m2k, with
the predicted lm thickness of 28 microns. For this estimate to be realistic it is
essential that the lm wet the disc and not break up into rivulets. This depends
upon a force balance at an incipient dry-out point, as indicated in Figure 9. At
the lm stagnation point the lm momentum is potentially destroyed by the action
of the component of the surface forces parallel to the disc. Thus for an average lm
velocity Uav we must satisfy the following condition for rivulet maintenance:
2
T (1 cos ) Uav
s
FIGURE 9 Schematic showing liquid lm dry-out on a rotating disc.
where T is the surface tension per unit length, is the contact angle, is the liquid density, and s is the local lm thickness.
Coherent lms are less likely as they become thinner and their velocity
decreases. An inspection of Eqs. (9) and (10) reveals that U 2av s is proportional to
2/3M5/3. Hence the tendency to form rivulets is less at higher disc speeds and liquid ow rates and increases with large T and small .
2.1.3.
Film-Flow Instability
The existence of the wave structure within the lm is of major practical interest, as
was highlighted by some elegant experimental work conducted by Brauner
and Maron (7). They monitored the instantaneous local lm thickness of a
liquid owing down a stationary inclined plane using a capacitance technique.
Simultaneously the local mass transfer coefcient was measured between the disc
and the liquid, using the limiting electrolytic current method. Their plots are reproduced in Figure 10. It was clear that the passage of a ripple was associated with a
signicant enhancement of the mass transfer coefcient, as a consequence of the
ow eld associated with ripple propagation. An analogous phenomenon may be
observed when sand particles are disturbed by wavelets in shallow seaside pools.
While the phenomenon has considerable theoretical interest, its immediate practical implication is very important because it suggests that the disc heat and mass
transfer performance could be enhanced still further by appropriately engineering
the disc surface prole. Some experimental results are discussed next.
FIGURE 10 Simultaneous time traces of local instantaneous lm thickness

and transfer rate.
2.2.
Heat/Mass Transfer Performance
An early application of the SDR to heat transfer duty was developed by Hickman
(10), who was interested in the desalination of brackish water using a vapour
compression evaporator. A sketch of his initial arrangement is shown in Figure 11,
where brackish water owing on one side of a rotating disc assembly was evaporated by condensing steam on the other. The very high overall heat transfer coefcients that could be achieved (up to 45 kW/m2K) ensured that the pressure ratio
demanded from the vapor compressor was minimal, thereby establishing very
efcient operation. In a further development of the idea (11), a series of disc
assemblies was mounted on one vertical shaft that was enclosed within a tower,
as shown in Figure 12. It is signicant that Hickman did not report any problems
associated with the deposition of crystal scale, even though his experimental runs
lasted for several hundreds of hours. Radial rather than spiral stains were, however, exhibited, which suggested that the inuence of the Coriolis acceleration
was minimal. Since the temperature difference between the condensate and the
evaporating brackish water was only 12C, it is presumed that the equivalent
supersaturation was insufcient to cause signicant crystal nucleation.
The ability of the spinning disc to operate with very small driving temperature and concentration differences can improve the thermodynamic efciency of
the overall process system. This is clearly the case with the Hickman vapor compression evaporator, and it is also exemplied in the applications described next.
In general, the power needed to rotate the spinning disc assembly is a small fraction of that saved by virtue of the establishment of an intensied uid dynamic
environment.
2.2.1.
The Rotating Electrolytic Cell
A laboratory-scale rotating chlor-alkali membrane cell was constructed and tested

some years ago in ICI. The electrodes comprised closely spaced catalyzed discs that
were separated by a Naon membrane. The anolyte and catholyte concentrations
corresponded to those in the brine and sodium hydroxide solutions used in the
standard (FM21) industrial version of the membrane cell. As can be seen from
Figure 13 (taken from Ref. 12), while the industrial cell voltage at a current density
of 3 kA/m2 was 3.17 V, that of the rotating unit was a function of the applied acceleration, falling to about 2.75 V at 100 g. At a higher current density, the benets
of enhanced acceleration were even more marked. It will be recognized that
the enhanced buoyancy forces generated by the high acceleration can eliminate
the polarization effects associated with bubbles that adhere to the electrodes/
membranes or remain in the electrolytes. In principle a compact rotor comprising
a bipolar cell assembly of closely spaced discs is capable of an exceptionally high
chlorine production rate while operating at exceedingly competitive voltage.
FIGURE 11 Schematic of the single-element Hickman still.
FIGURE 12 (a) Schematic of the multiple-disc Hickman still. (b) Full-scale

Hickman still.
2.2.2.
The Rotex Absorption Heat Pump
The main factor that has been responsible for the slow adoption of absorption heat
pumps for heating and air conditioning duties has been their high capital cost
compared with that of vapor compression equivalents. This is due largely to the
cycle complexity, as shown in Figure 14, which displays the four principal cycle
elements, all of which involve vaporliquid systems:
1.
2.
3.
4.
Condenser
Evaporator
Generator/boiler
Absorber
FIGURE 12 (cont.)
FIGURE 13 Voltage characteristics of a rotating chlorine cell.
The only single-phase item involved is the solution heat exchanger, which
is intensied by the use of laminar ow in a matrix of ne channels. A sketch of
the single-effect Rotex (13) design is shown in Figure 15, where it can be seen
that a hermetically sealed rotating disc assembly fullls the four functions listed.
The working uid consists of a water solution of either mixed alkali metal
hydroxides or lithium bromide.
The evaporator receives low-grade heat from the circulating ambient air and
vaporizes the refrigerant at low pressure, the vapor being promptly absorbed at
the absorber disc immediately opposite. Working uid from the absorber sump,
now rich in refrigerant, is returned to the generator via a solution pump and a
solution heat exchanger. The latter consists of a matrix of closely spaced metal
foil, which, as discussed earlier, gives very efcient heat transfer in a small volume. The heat of condensation and absorption is removed from the condenser/
absorber disc assembly by circulating water that enters and leaves via a mechanical seal. The working uid is pumped around the cycle by a pitot tube assembly,
with the tubes dipping into a peripheral liquid trough. Since the Rotex machine
operates with a horizontal axis, the pitot tube arm is counterweighted to resist the
frictional torque exerted by the trough.
Information recently released (14) shows that the double effect air conditioning version of Rotex has achieved a coefcient of performance of 1.0 at a temperature lift of 35C using lithium bromide solution. This unit is about to enter
eld trials. Its high performance is entirely due to the intensity of the heat and
mass transfer environment generated on the liquid lm owing over the discs.
It is also worth noting that Alfa Laval has developed a process evaporator
for fruit juice and milk concentration using a nested stack of cones. Figure 16
shows the arrangement, in which steam is caused to condense outside the cones
while the process uid is concentrated on the lm owing on the inside surface.
In this context it may be observed that the disc and the cone are specic examples of the general case of a rotating surface of revolution. The acceleration causing the outward movement of the liquid lm is the resolved component of 2r
along the surface in question.
Koerfer (15) performed an interesting study with a series of perforated and
smooth rotating discs 600 mm in diameter at speeds up to 600 rpm. The mass
transfer performance was measured using the oxygen/water system, with the
results shown in Figure 17. Very good performance was recorded with the perforated discs, and this was attributed partly to the short exposure time of the lm as
it negotiated each perforation and partly to the extra lm area created.
Interestingly, the lm behavior was much more predictable when it owed
over the disc surface containing the raised lips arising from the punching operation. Film ow on the alternate side tended to leak through the disc, particularly at lower liquid ows, presumably due to the Coanda effect as liquid
negotiated the rounded edge of the holes.
As part of a general development to use spinning discs in an intensied
absorption heat pump, Aoune and Ramshaw (16) measured both the local and
average heat transfer performance on smooth rotating surfaces. The disc surface
FIGURE 14 Single-effect absorption heat pump cycle.
temperature was estimated by extrapolating the values given by the digitized output from thermocouples embedded at depths of 1 mm and 9 mm in a brass disc.
The local lm temperature was measured by a thermistor contained in a stylus
that could be traversed over the disc surface.
Using water, the heat transfer coefcient on the 50-cm-diameter disc regularly exhibited a minimum value at a radius of about 17 cm. On the other hand,
with the use of a water/60% monopropylene glycol mixture, no minimum was
observed and the absolute performance was much poorer than that obtained with
water. This behavior is attributed to the tangential uid slip generated as the feed
liquid is brought up to the rotors angular velocity. This slip appears to be more
marked with low-viscosity liquids, which seems intuitively reasonable.
FIGURE 15 (a) Rotex design concept. (b) Rotex prototype.
FIGURE 15 (cont.)
Mass transfer studies were then performed, based upon the aeration of liquid
that had been previously stripped. The local liquid oxygen concentration was established by carefully abstracting a lm sample via a quill that could be traversed over
the disc. An Orbisphere oxygen analyzer was used. Rather poor agreement was
obtained between the experimental results for water (kL 4 10 m/s 104) and
the Higbie predictions (approx 1 m/s 104) based upon total exposure time of
liquid on the disc. Clearly, liquid mixing within the lm generates exposure times
that are much shorter than the liquid residence time on the disc.
Another study, by Jachuck and Ramshaw (17), explored the inuence of
surface prole upon the heat transfer performance of a spinning disc. Using a
smooth disc as a benchmark it was shown that disc surfaces disrupted with metal
powder or grooves gave a signicantly improved performancepresumably due
to the better lm mixing. The best performance at modest disc speeds was
obtained with undercut grooves (Figure 18), which were originally conceived
as a technique for improving the circumferential distribution of any radial
rivulets. At higher disc speeds, the lm radial velocity was such that liquid was
projected off the disc, thereby compromising the heat transfer process.
FIGURE 16 Alfa Laval concentrator.
2.3.
2.3.1.
Reactor Applications
Strategic Considerations
At the most basic level, the SDR is an extremely effective gasliquid contacting
device. This makes it ideal for performing many intensied heat or mass transfer
operations and, as will be discussed later, it may be deployed as an evaporator or
an aerator/desorber. However, its principal application in the process industry is
likely to be as a very high-performance reactor. Since the reactor is the heart of
FIGURE 17 Mass transfer performance of a rotating disc (O2/H2O system).
FIGURE 18
Types of disc grooves tested.
any process, the SDR can radically improve the economics and efciency of
many key processes, both in the commodity and in the ne chemical area.
In order to exert full control over the progress of a chemical reaction or physical transformation, the uid dynamic environment must be sufciently intense so
as to ensure that the mixing and heat transfer rates are faster than the intrinsic
chemical kinetics. This concept is shown diagrammatically in Figure 19, which
illustrates the progress of a reaction represented simply as A B C, with the
reactants A, B traveling in plug ow along a tubular reactor. When the interdiffusion of A, B is slow compared with the reaction rate, then C is produced near the
original plane of AB separation. This represents a total loss of control on two
counts:
1. The AB stoichiometric ratio varies wildly across the reactor diameter.
Therefore the selectivity for the desired product C is likely to be compromised because a more realistic reaction scheme will usually include
many side reactions.
2. Most of the reaction to C occurs in the immediate neighborhood of the

plane of AB separation. Thus only a small fraction of the available
reactor volume is utilized and an opportunity for intensication is lost.
On the other hand, when mixing is fast, the AB ratio is uniform and control over the product spectrum can be maintained. All the reactor space is used to
maximum effect. Since the intrinsic kinetics are allowed free rein, the reactor
is able to operate at the maximum intensity permitted by the specic chemical
system.
While it should be self-evident that a rational reactor design demands a
knowledge of both the uid dynamic environment and the detailed process kinetics, the latter are rarely available. In many instances this leads to the severe limitation of many important reactions by an inadequate uid dynamic intensity.
Some of these are known to be fast, e.g., liquid-phase nitrations, while others are
(incorrectly) assumed to be slow, e.g., most polymerizations. In these circumstances the pragmatic approach is to use a high-intensity reactor for each system
and then to assess the impact upon the spacetime productivity. Obviously, an
intrinsically slow system is resistant to further acceleration and this will rapidly
become evident. One signicant qualication of this contention involves the very
FIGURE 19 The inuence of mixing and reaction rates on reactor behavior.
short residence time in the SDR compared with its conventional counterparts. In
certain reactions the process temperature is restricted to one that avoids product
breakdown in the time available. Since the residence time in the SDR when performing a polymerization reaction is up to 10 seconds rather than the several
hours involved in a conventional stirred vessel, we must re-examine the processs
temperature trajectory. A higher operating temperature may well be acceptable
because the undesired breakdown components may not have time to be generated.
However, the higher temperature will reduce the liquid viscosity and accelerate
the reaction. The lower viscosity will reduce the residence time still further.
Therefore the SDR can exploit a process operating envelope that is much larger
than what is accessible to conventional technology.
With regard to the processing of viscous liquids, by far the most important
application relates to the manufacture of polymers. The key processes are:
1.
2.
3.
Condensation reactions
Radical reactions
Devolatilization
The progress of a condensation reaction is controlled by an equilibrium

with a volatile product, which, if continuously removed, drives the reaction forward. Unfortunately, as polymerization proceeds, the liquid viscosity increases,
rendering the removal of the volatile component much more difcult. The batch
stirred vessel, which is conventionally used for polymer manufacture, has a limited ability to remove a volatile component from the increasingly viscous polymer
melt. On the other hand, the SDR can maintain effective mass transfer and, as will
be shown in Section 2.3.2, can achieve in one pass (taking several seconds) the
same increment in polymerization as would conventionally require tens of minutes. The SDR with one or more discs on the same shaft is therefore capable of
performing polycondensation extremely rapidly. The short residence time also
facilitates rapid changes of product grade with minimum wastage.
The rate of a polymerization that proceeds via a series of radical reactions is
controlled by the micromixing environment within the polymer melt. Once again
the stirred vessel is a poor means to achieve the high desired intensity, whereas the
SDR has an impressive capability in this respect. It is well known that UV radiation is a very effective means of radical generation, and this technique has been
proposed in the past for stimulating certain radical polymerizations. However, the
radiation extinction distance in a polymer melt is only a few millimeters, so a polymerization reactor comprising a stirred vessel having a diameter of several meters
is not a rational option. On the other hand, the thin polymer lms that can be created and maintained on the SDR allow all of the polymer to receive a continuous,
uniformly high radiation dose and thereby maintain a very high reaction intensity,
as described later for the manufacture of butyl acrylate.
FIGURE 20 Schematic of an SDR styrene polymerizer.
The industrial manufacture of polymers is rarely taken to completion, and

this requires unreacted monomer to be removed from the productwhen its viscosity is highest. This devolatilization procedure is notoriously difcult because
it usually involves the vacuum stripping of a stirred vessels contents for many
hours. Just as the SDR promotes the removal of the volatile component of a condensation reaction, it is also effective in dramatically accelerating the
devolatilization process.
2.3.2.
Polymerization
Polystyrene. The manufacture of polystyrene from various grades of prepolymer has been performed (18,19) on a 36-cm brass SDR using the arrangement
shown in Figure 20. A series of concentric grooves was machined in the disc surface in order to improve liquid mixing within the lm. The reaction operates via
free radicals, which were initiated in this case using benzoyl peroxide. In the rst
instance a series of batch runs was performed in a conventional laboratory-scale
stirred vessel in order to produce a calibration curve (Figure 21) of conversion
FIGURE 21 Free-radical polymerization of styrene.
versus time. This vessel was then used to produce about 200 mL of prepolymer
at a range of conversions that was supplied to the inner spinning disc surface over
a period of about 30 seconds. The SDR was heated from below by a stationary
radiant ring, and the polymer produced was collected in a cooled annular trough
surrounding the disc. The styrene was diluted with about 16% w/w toluene in order
to reduce the viscosity.
Figure 21 also shows the increment in polymer conversion in one pass over
the disc as a function of the initial conversion in the preliminary batch. It can be
seen that the equivalent batch time that can be ascribed to one pass on the disc
increases (up to 58 minutes) as the initial conversion increases to 63%. This
implies that the benets of the SDR become more marked as the polymer viscosity increases. It is envisaged that the process can be scaled up either by using a
larger disc or by mounting several discs on one shaft. The latter approach (i.e.,
several discs in series) does, however, involve the problem of transferring polymer from the peripheral collection trough to the center of the next disc. An alternative may be to operate discs on one shaft in parallel. For the experiments just
described, the feed rate was roughly 510 mL/s, which is equivalent to an output
of up to 250 tons/year on a continuous basis, though at this early stage this should
not be considered the ultimate limitation.
The fundamental reasons for the high performance of the SDR are still a
matter for debate. The signicance of micromixing and the consequent improved
probability of radical interaction has already been mentioned. However, another
factor is expected to be the divergent character of the ow on the disc. This may
be expected to align the polymer molecules and thereby encourage the juxtaposition of the reactive groups.
Polycondensation. The reaction between maleic anhydride and ethylene
glycol has been studied as an example of polycondensation (19). Since the reaction proceeds on an equilibrium basis, in order to drive it to completion the water
produced must be eliminated from the increasingly viscous polymer melt. The
grooved brass 36-cm disc described earlier for the polystyrene experiments was
used at a temperature of 200C and a disc speed of 1000 rpm. As before, the
experimental procedure involved the establishment of a benchmark batch calibration against which the subsequent disc runs could be compared. A typical acid
number plot versus batch time is presented in Figure 22. As the acid number
decreases, the conversion to polymer increases. The water of reaction was removed
from the polymer lm by maintaining a large nitrogen purge to the vapor space.
This technique, rather than the application of a vacuum, was the preferred method
for reducing the water vapor partial pressure.
It can be seen that the increment in polymerization following one pass in
the SDR corresponds to many minutes of reaction in the small batch reactor used
as a reference. This is particularly encouraging because the mass transfer intensity
in the laboratory stirred reactor is likely to be much greater than its industrial-scale
FIGURE 22 Time savings in the SDR for polyestirication.
equivalent, and it therefore provides a demanding benchmark for the spinning

disc performance.
2.3.3.
Fine Chemical Manufacture
The intense heat and mass transfer environment that can be established within the
liquid lm owing over the disc allows high selectivities and conversions to be
achieved when fast liquid-phase reactions are performed. Very encouraging results
were achieved in an industrial study of a phase-transfer-catalyzed (p-t-c) Darzens
reaction to produce a drug intermediate (20). In comparison with the currently used
batch processes, the ptc reaction on the SDR had a 99.9% reduced reaction time, a
99% reduced inventory, and a 93% reduced impurity level. A more recent study has
involved a 20-cm-diameter SDR with a catalytically activated surface to perform
the rearrangement of -pinene oxide to campholenic aldehyde (21), which is an
important intermediate used in the fragrance industry. The comparative performance of the batch reactor and the SDR is shown in Table 1. For equivalent conversion and selectivity, the unoptimized SDR gave a much higher throughput than the
equivalent batch reactor and avoided the need to separate a catalyst slurry from the
product. Figure 23 shows the variation of selectivity as a function of disc speed and
feed ow rate; Figure 24 gives the conversion levels achieved. While conversion
falls from 100% at the higher ows and speeds, presumably due to the reduced liquid residence time on the disc, the selectivity increases. Thus it might be
expected that a larger disc (or a sequence of small discs) could combine high conversion and high selectivity. The batch reactor performance is summarized in
Figure 25, where it can be seen that 100% conversion requires 5 minutes ( 1 second on the disc) and a maximum selectivity of 65% is reached.
2.3.4.
Precipitation/Crystallization
The operation of crystallizers and precipitators is critically dependent upon the

supersaturation environment prevailing within the crystal magma because this
inuences both the nucleation of new particles and the growth of those that
TABLE 1 Comparison of the Best SDR Runs with Batch Results for
Conversion of -Pinene Oxide to Campholenic Aldehyde
Batch process
Process time (s)
Processed feed
Conversion (%)
Selectivity (%)
Note
300
1.2 kg/h
100
64
Catalyst separated from
the product mixture
SDR (continuous)
1
209 kg/h
100
62
No loss of
catalyst
FIGURE 23 Selectivity towards campholenic aldehyde at 85C at various feed rates.
FIGURE 24 Conversion of -pinene oxide at 85C and various disc speeds.
FIGURE 25 Batch reaction: conversion and selectivity towards campholenic aldehyde.
already exist. In general, the growth rate has a rst-order dependence on supersaturation for diffusion-limited systems and 1.5- to second-order where the surface
integration resistance is signicant (22). On the other hand, the nucleation rate,
whether primary or secondary, has a higher-order dependence on supersaturation,
typically in the range 29 (23), with the lower values being obtained mainly with
low-molecular-weight solutes. Hence it will be recognized that high supersaturation can be readily achieved on SDRs. This feature makes them attractive for
producing very small or nanosized particles, which are currently of intense industrial interest.
Supersaturation can be generated in several ways. Perhaps the simplest
technique is merely to cool a solution saturated at a higher temperature.
Alternatively, supersaturation can be created by removing the solvent or adding
an antisolvent for systems where the solubility is only a weak function of temperature. Finally, supersaturation can be created by reactionbetween either two
liquids or a liquid and a gas. In all these cases the intense environment created
within an initially crystal-free liquid lm moving in plug ow over the disc can
generate very high supersaturation and consequently small and fairly uniform
crystals. This characteristic of the SDR may be attractive in several industries
(e.g., pharmaceuticals and coatings), where the product quality is intimately related to the neness of the crystals and the tightness of the size distribution. The
concept has recently been tested (24) in a spinning cone precipitator (Figure 26),
which shares most of the characteristics of a spinning disc except that the centrifugal acceleration vector is not aligned to the cone surface. Barium sulfate was
generated by mixing equimolar solutions of BaCl2 and Na2SO4 in a central reservoir. A thin liquid/slurry lm owed to the cone rim, from where it was collected
and subsequently analyzed in a Malvern Mastersizer. Equivalent batch experiments were performed, for the purpose of comparison, in a 50-mL agitated
beaker. At a supersaturation of 500, dened as
Molar concentration of Na 2 SO 4 or BaCl 2
Molar solubility of BaSO4
the cone produced crystals at 6000 rpm that had a Sauter mean diameter of
3.2 microns, compared to 6.85 microns from the batch runs. However, at a
supersaturation of 5000, the batch yielded a Sauter mean diameter of 0.75 microns,
compared with 0.180.32 microns from the disc. The particle size distributions
reproduced in Figure 27 highlight the cone behavior at 8000 rpm more starkly,
with a decided shift to 0.11 microns, compared with 110 microns in the batch.
Thus it can be seen that for many systems, spinning precipitators hold out
the prospect of generating the crystal size distributions that have considerable
industrial interest. This view is further reinforced by some earlier work by
SmithKline Beecham (20), which crystallized an unnamed product (API) on a
FIGURE 26 Spinning cone reactor layout.
15-cm spinning disc. Figure 28, reproduced from their work, compares the product size distribution from the SDR with that of the standard industrial material.
Crystallization was induced by adding an antisolvent, and it can be seen that a
very signicant impact could be made on the normal product size distribution,
which was smaller and narrower on the disc. The stainless steel disc was subject
to crystal scaling after a few runs. However, a thin layer of PTFE suppressed this
without signicantly impairing the discs heat transfer performance.
2.4.
Comparative Spinning Disc Reactor Costs
It should be borne in mind that the SDR is most effectively exploited when it is run
on a continuous basis. The industrial units constructed to date have had disc diameters up to 30 cm and have been capable of processing around 30 g/s of feedstock.
This corresponds to a continuous annual output of (e.g., polymer) 1000 tons/year.
For a typical pharmaceutical product, a 15-cm disc could process about 7 g/s,
equivalent to an annual output of 200 tons. With conventional stirred-vessel technology, a roughly equivalent unit to the 30-cm SDR is a 2000-L batch reactor
FIGURE 27 BaSO4 size distribution for a supersaturation of 5000.
fabricated in 316 stainless steel, complete with computer control and a service
unit delivering a disc temperature in the range 20C150C. The cost of such a
reactor is estimated to be 250,000 with a range of 200400K.
Comparative SDR costs have been supplied by the most experienced manufacturers (Triton Chemical Systems Ltd), which has been collaborating closely
with Newcastle University during the last 5 years of SDR development.
2.4.1.
Spinning Disc Reactor Layout/Specication
The SDR system is available as a desktop or a oor-standing unit. The latter

is easier to use at pressure and is more versatile for use with ancillaries such as
feed units. The desktop system is restricted to the core system shown within the
circle in Figure 29, which is a schematic representation of the oor standing
arrangement. Experience has shown that SDR design and manufacturing details
are very important in ensuring that the unit operates satisfactorily over its full performance range. Thus care must be taken with respect to the feed arrangements
to ensure that instantaneous stoichiometric ratios are held constant and that feed
liquids are mixed exceedingly rapidly on the disc. A sophisticated feed system is
provided to ensure that the delivery of two liquid feeds is accurate. If this level of
complexity is not required, then there may be a signicant cost saving. As shown
in Figure 29, feed liquids are supplied by means of two ram injectors accurately
driven by precision step motors. Product is drained from the disc casing into a
lower receiving vessel, which can be isolated during SDR operation. This allows
product removal without interfering with the progress of the reaction.
Specications for all systems include:
a. Constructed with 316L stainless steel contact parts for the reactor
(other materials are available).
b. Constructed with a vessel to take 3-atm pressure or vacuum (other pressures available). Vessel has twin-wall construction to allow heating or
cooling of the jacket.
c. Supplied complete with:
i. Temperature measurements at the disc.
ii. Electronics and interfaces for:
1. Up to 8 measurements of temperature.
2. Up to 8 measurements of pressure etc.
iii. An advanced computer control and data-logging system.
The main variables on a specic spinning disc reactor are:
d. The material of construction.
e. The range of ambient conditions under which the reaction take place
(temperature and pressure).
f. The range of disc speeds available.
g. The degree of instrumentation required.
FIGURE 28 Recrystallization of an API: comparison of size distributions.
2.4.2.
Prices
These prices are for the spinning disc reactor as just dened in points a to c, including advanced control and data-logging software with computer and at screen. The
following ancillaries are usually necessary for the system, and these may exist, or
Triton can recommend units or can supply them integrated into the system.
a. Feed systems
b. Heat transfer uid system(s) for the disc/vessel/feeders
c. Reaction atmosphere control systems, e.g., pressure/vacuum/gas feed
Example prices are given in Table 2. As can be seen from the table, the cost
of the SDR system is signicantly less than that for a stirred vessel with a similar productive capacity. However, cost considerations are likely to be much less
signicant than the competitive edge that SDR technology is likely to bring in
terms of improved selectivity and product quality.
FIGURE 29 Schematic of the SDR manufactured by Triton.
TABLE 2 Spinning Disc Reactor Costs

M/C type
Type K-01
Type P-01
Description
Small benchtop system, speeds from 100 to

2000 rpm, suitable for disc temperature to 100C
15-cm disc
40,000
30-cm disc
60,000
Free-standing system, speeds from 200 to
4000 rpm, suitable for disc temperatures to 100C
15-cm disc
75,000
30-cm disc
90,000
70-cm disc
120,000
Options
For either system, typical options are:

a. Heat/cool system, to provide cooling at the walls to
20C and heating/cooling at the disc for 5C to 120C
b. Injector system, 2000-mL capacity, with twin walls to allow
heating cooling; feed rates from 0.07 to 7 mL/s;
fast down, with index and control system
c. Stirrers for the injectors
d. Cooled deector ring system
e. Receivers, for operation up to 10 bar
1L
2L
4L
f. Additional instrumentation
Measurement of heat transfer uid ow rate
Measurement of temperature difference across disc
Added temperature measurements (per channel)
Added pressure measurement (per channel)
3.
Price
Price
17,500
5,000
1,000
1,400
980
1,400
1,960
1,400
400
100
400
CONCLUSION
It will be apparent from the examples cited that centrifugal elds in general, and
rotating surfaces in particular, can exert a profound inuence upon process
engineering. Our experience at Newcastle University has repeatedly demonstrated
that the greatest gains are achieved when the SDR is presented with the most
severe process conditions. While our original target was simply to reduce equipment size and installed cost, it rapidly became apparent that reduced size alone
would be insufciently persuasive for the acceptance and adoption of SDR technology. However, it has now been demonstrated that in addition to yielding
a better product (i.e., tighter size/molecular weight distributions, improved purity,

etc.), the SDR can transform the whole business process.
As with any radical step, the main obstacle to its implementation is the normal human resistance to change. In order to overcome this it is vital that chemists
who are developing new processes be as fully conversant with SDRs as with their
beakers and asks. There is therefore a latent market for miniature versions of this
equipment throughout the worlds industrial and teaching laboratories. Once the
cultural block is overcome and company decisionmakers fully appreciate the
breadth of impact in prospect, then the process industry will be fully prepared to
meet the challenges of the new century.
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Woods WP. The hydrodynamics of thin liquid lms owing over a rotating disc.
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Thomas S, Faghri A, Hankey W. Experimental analysis and ow visualization of a
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Wasden FK, Dukler AE. A numerical study of mass transfer in free-falling wavy
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Oron A, Davies SH, Bankoff SG. Long-scale evolution of thin liquid lms. Rev
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Brauner N, Maron DM, Dukler AE. Modeling of wavy ow in inclined thin lms in
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Brauner N, Maron DM. Characteristics of inclined thin lms, waviness and the associated mass transfer. Int J Heat Mass Trans 1982; 25(1):99110.
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Higbie R. The rate of absorption of pure gas into a still liquid during short periods of
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Ramshaw C. The opportunities for exploiting centrifugal elds. Heat Recovery
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Ramshaw C, Winnington TL. An intensied absorption heat pump. Proc Inst Refrig
1988; 85:2639.
Gilchrist K, Lorton R, Green RJ. Process intensication applied to aqueous Li
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on Heat Transfer, Nottingham, U.K., Sept. 1012, 2001.
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Aoune A, Ramshaw C. Process intensication: heat and mass transfer characteristics

of liquid lms on rotating discs. Int J Heat Mass Trans 1999; 42:25432556.
Jachuck RJJ, Ramshaw C. Process intensication: heat transfer characteristics of
tailored rotating surfaces. Heat Recovery Systems CHP 1994; 14(5):475491.
Boodhoo KVK, Jachuck RJJ, Ramshaw C. Process intensication: spinning disc polymerizer for the manufacture of polystyrene. In: Ramshaw C, ed. 1st International
Conference on Process Intensication in the Chemical Industry, Antwerp, Dec. 1995.
Boodhoo KVK, Jachuck RJJ, Ramshaw C. Spinning disc reactor for the intensication of styrene polymerisation. In: Semel J, ed. 2nd International Conference on
Process Intensication in Practice, Antwerp, Oct. 1997.
Oxley P et al. Evaluation of spinning disc reactor technology for the manufacture of
pharmaceuticals. IEC Res 2000; 39(7):21752182.
Vicevic M, Jachuck RJ, Scott K. Process intensication for green chemistry:
rearrangement of -pinene oxide using a catalyzed spinning disc reactor. 4th International Conference on Process Intensication for the Chemical Industry, Brugge,
Belgium, Sept. 10, 2001.
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Hetherington P, Scalley MJ, Jachuck RJ. Process intensication: continuous production of barium sulphate using a spinning cone precipitator. 4th International Conference on Process Intensication for the Chemical Industry, Brugge, Belgium, Sept. 10,
2001.
4
Compact Multifunctional Heat Exchangers:
A Pathway to Process Intensication
B. Thonon and P. Tochon
1.
INTRODUCTION
In the rst part of this paper, the different technologies of compact heat exchangers
are presented and their range of application is given. The second part presents the
state of the art for heat transfer and uid ow characteristics for single-phase,
evaporation, condensation, and heat and mass transfer. The last part presents
applications of compact multifunctional heat exchangers.
As proposed by Shah and Mueller (1), heat exchangers may be characterized by the compactness factor, in m2/m3, and it is generally admitted that values
greater than 700 m2/m3 characterize compact heat exchangers. Often, compact
heat exchangers also refer to nontubular heat exchangers, even if shell-and-tube
heat exchangers can have high compactness factors. For the heat exchanger considered, the hydraulic diameter ranges from less than 1 mm to 10 mm. There are
mainly two types of compact heat exchangers: the plate type (primary surface
heat exchanger) and the platen type (secondary surface heat exchanger). These
two types of heat exchangers are described and new technologies are presented.
In the process industry, there are only four basic operations: reaction, separation, mixing, and heat transfer. The traditional unit operation is to perform each
task in one or more pieces of equipment sequentially, for example, heat transfer in
heat exchangers and reaction in reactors. Combining two or more tasks in one piece
of equipment is implemented only for control or enhancement purposes; one example is cooling in a jacketed stirred-tank reactor. But this is not an intensied process,
because it requires a batch operation, which has poor efciency, and the reaction
cannot be controlled effectively. Examples of multifunctional heat exchangers are:
Multistream heat exchanger (heat transfer between more than two uids)
Reactor heat exchanger (reaction and heat transfer)
Reux condenser (heat transfer and separation)
This chapter presents the state of the art in compact heat exchanger technology and provides heat transfer and mass transfer characteristics of these devices
and their use in the process industry.
Heat transfer is commonly required in the process industry for heating, cooling, vaporizing, or condensing. In most cases, only two streams (one hot and one
cold) are in thermal contact within the heat exchanger. The most commonly used
heat exchanger is the shell-and-tube heat exchanger, which has poor heat transfer
performance and requires a signicant volume and ground area. Compact heat
exchangers and enhancement technologies allow reducing the heat exchanger
volume, to increase its effectiveness and to reduce capital and operating costs.
Compact heat exchanger technologies are sufciently advanced, but their
use and acceptance in the process industry are not yet widespread. Reasons are
the lack of awareness of their benets and the absence of reliable design methods
and investigations under actual operating conditions. Compact heat exchangers
include plate heat exchangers as well as platen heat exchangers, which are
characterized by hydraulic diameters between 1 and 10 mm. But recent developments in manufacturing techniques, such as printed circuit heat exchangers and
diffusion-bonded and superplastic-formed heat exchangers, allow reaching hydraulic
diameters below 1 mm. These heat exchangers offer compactness greater than
1000 m2/m3 and are suitable for industrial processes.
Rapid advances in range of design and operational reliability have made
compact heat exchangers attractive for many applications in various industries.
Their high performance has already made their use widespread in the automotive,
aerospace, air conditioning, refrigeration, and electrical equipment industries for
single-phase and phase-change duties. In the automotive industry, plate-type heat
exchangers are used as heaters, evaporators, and condensers (2), and since the
1970s, the volume/heat capacity ratio has been divided by a factor of 2 (Figures 1
and 2). This improvement has been achieved because of a radical change in heat
exchanger technology and by the adoption of mass production systems integrating innovative technologies.
Compact heat exchangers produced individually are generally more expensive
than a conventional shell-and-tube unit, and their payback time will be longer.
But taking space, weight, and convenience into account compact heat exchangers
can be used cost effectively in a wider range of applications than the niches currently being used in the process industry (3).
FIGURE 1 Progress in evaporator technology. (From Ref. 2.)
2.
2.1.
COMPACT HEAT EXCHANGER TECHNOLOGY

Classication of Compact Heat Exchangers
Heat exchangers can be classied in many different ways, such as according to

transfer processes, number of uids, surface compactness, ow arrangements,
heat transfer mechanisms, type of uids (gasgas, gasliquid, liquidliquid, gas
two-phase, liquidtwo-phase, etc.), and industry. Heat exchangers can also be
classied according to the construction type and process function (Figure 3). Refer
FIGURE 2 Progress in condenser technology. (From Ref. 2.)
FIGURE 3 Classication of heat exchangers.
to Shah and Mueller (1) for further details. In the follo1wing sections, only nontubular heat exchangers will be described.
2.2.
Plate Heat Exchangers
Plate heat exchangers (PHEs) were formerly used for milk pasteurization and
gradually became the standard choice for heat treatment in the liquid-food industry. Actually, pasteurization must be considered a biological reaction, because the
native composition of the liquid is denatured during the heat transfer process. In
practice this denaturation leads to fouling. The facility of dismantling plate heat
exchangers is one of the main reasons for their extensive use in the food industry.
Furthermore, because the heat transfer coefcients are high, the uid path length
will be shorter and relatively well dened. Due to the lack of large dead areas in the
channels, the corresponding residence time distribution is short and homogeneous.
Eventually, with the development of larger plates, their use began to grow
quickly in the chemical, petrochemical, district heating, and power industries, but
essentially for single-phase duties. The concept of phase change in PHEs originated
in the 1970s for ocean thermal-energy conversion (OTEC) applications; the working uids were Freon R22 or ammonia (4). These rst studies on evaporation and
condensation have been used for the development of PHEs in the refrigeration
industry (510). Now PHEs have come to be used more often in the process
industry (1112), but their use is still not widespread.
In terms of technology, PHEs are made from corrugated plates (Figure 4)
that are pressed together. The plate size ranges from 0.02 m2 to over 3 m2 with conventional pressing technology (Figure 5), but can reach up to 15 m2 for explosionformed plates (Figure 6). The hydraulic diameter lies between 2 and 10 mm for
most common plates, but free passages and wide gap plates exist for viscous uid
applications. Typically, the number of plates is between 10 and 100, which gives
550 channels per uid. Furthermore, the use of high-quality metal and manufacturing techniques makes lead plate heat exchangers less prone to corrosion
failure than shell-and-tube units (13).
To ensure tightness, three technologies are available: gaskets, semiwelded
or totally welded, and brazing. The gasketed PHE is the most common type, with
the gasket material selected as a function of the application (temperature, uid
nature, etc.). Temperatures up to 200C and pressure up to 25 bars can be
achieved by such heat exchangers. For applications where gaskets are undesirable
(high pressure and temperature or very corrosive uids), semiwelded or totally
welded heat exchangers are available (Figure 7). The last variant is the brazedplate heat exchanger. The plate pattern is similar to conventional gasketed units,
but tightness is obtained by brazing the pack of plates. For common applications
copper brazing is used, but for ammonia units nickel brazing is possible. This
technology leads to inexpensive units, but the plate size is generally limited to
less than 0.1 m2. The drawback is that the heat exchanger cannot be opened, and
fouling will limit the range of application.
FIGURE 4 Plate heat exchanger. (Courtesy of Alfa-Laval Vicarb.)
FIGURE 5 Corrugated plates. (Courtesy of Alfa-Laval Vicarb.)
2.3.
Spiral Heat Exchangers
The spiral heat exchanger consists of two metal sheets that are welded together and
then rolled to obtain spiral passages. The passages can be either smooth or corrugated; in some cases, studs or spacers are introduced between the metal sheets.
These devices have two functions: (1) to adjust the spacing and (2) to induce turbulence and increase heat transfer. The general ow conguration can be crossow
(single or multipass) or counterow, depending on the conguration of the inlet and
outlet distribution boxes. The heat transfer surface ranges from 0.05 m2 for refrigeration applications (Figure 8) to 500 m2 for industrial processes (Figure 9). Spiral
heat exchangers are often used for phase-change applications, because the geometry of the hot and cold stream channels can be adapted to the process specications.
Recent developments in manufacturing technologies (laser welding) have
allowed the manufacture of cost-effective recuperators based on the spiral concept (Figure 10) or the folded-plate recuperator (1415).
2.4.
Plate-and-Shell Heat Exchangers
The basic principle of these heat exchangers is to insert a bundle of plates in a

shell (Figure 11). On the plate side, the uid ows inside corrugated or embossed
channels (more often in two passes). On the shell side, the ow is similar to shelland-tube heat exchangers, and bafes can be inserted. This technology can be
used for revamping an application, because the shell can be kept identical to that
for a bundle of tubes. These heat exchangers are often used in the process industry as boilers (boiling on the shell side) because high pressures can be reached very
easily on the shell side. Furthermore, a large gap on the shell side allows the use
of dirty services, because cleaning is possible via removal of the bundle of plates.
2.5.
PlateFin Heat Exchangers
Aluminium platen heat exchangers (PFHEs) were initially developed in

the 1940s to provide the aerospace industry compact, light, and highly efcient
heat exchangers for gas/gas applications. Because the mechanical characteristics
of aluminum are increased at low temperatures, this technology has been used
since 1950 for the liquefaction of natural gases. Nowadays, aluminum plate
n heat exchangers are extensively used in applications such as air separation,
hydrocarbon separation, and industrial and natural gas liquefaction (16). The
platen heat exchanger offers process integration possibilities (12 simultaneous
FIGURE 6 Explosion-formed plate. (Courtesy of Packinox.)
FIGURE 7 Various welded plate heat exchangers.
FIGURE 8 Spiral heat exchanger for the refrigeration industry. (Courtesy of

Spirec.)
different streams and more in one single heat exchanger) and high efciency under
close temperature approach (12C) in a large variety of geometric congurations.
The brazed platen exchanger consists of stacked corrugated sheets (ns)
separated by at plates, forming passages that are closed by bars, with openings
for the uid inlet and outlet (Figures 12 and 13).
FIGURE 9 Spiral heat exchanger for the process industry. (Courtesy of Kapp.)
FIGURE 10 Laser welding of a spiral recuperator. (Courtesy of ACTE.)
In its simplest form, a heat exchanger may consist of two passages, with the
cooling uid in one passage and the warming uid in the other. The ow direction of each of the uids relative to one another may be countercurrent, cocurrent,
or crossow.
The ns and the parting sheets are assembled by fusion of a brazing alloy
to the surface of the parting sheets. The brazing operation happens in a vacuum
furnace in which the brazing alloy is heated to its point of fusion. All parts in
FIGURE 11 Shell plate heat exchangers. (Courtesy of ACM and Barriquand.)
FIGURE 12 Components of a brazed aluminum platen heat exchanger.

(From Ref. 12.)
contact are bonded by capillary action (Figure 14). Once the brazing alloy has
solidied, the assembly becomes one single block. All passages for ow distribution and heat transfer of the streams are contained in the internal geometry of
the block. Inlet and outlet headers with nozzles for the streams are tted, by welding, around the openings of the brazed passages. These nozzles are used for connecting the heat exchanger to existing plant pipework.
Numerous n corrugations have been developed, each with its own special
characteristics (Figure 15). Straight ns and straight perforated ns act like parallel tubes with a rectangular cross section. Convective heat exchange occurs due
to the friction of the uid in contact with the surface of the n. The channels of
serrated ns are discontinuous, and the walls of the ns are offset. For air ows,
FIGURE 13 Platen heat exchangers. (Courtesy of Nordon Cryognie.)
louver ns are extensively used; for process applications (single- and two-phase),
continuous or offset strip ns are used.
For higher-temperature applications or when aluminum is not acceptable,
stainless steel (temperatures up to 700C) or copper materials can be used. For
very high temperatures (gas turbine heat recovery; T 1200C), a ceramic
platen heat exchanger has also been developed (17) (Figure 16).
For high-pressure applications in the hydrocarbon and chemical processing
industries, a titanium compact heat exchanger has been developed by RollsLaval. This heat exchanger consists of diffusion-bonded channels that are created
by superplastic forming of titanium plates (18). This heat exchanger can handle
high pressure and corrosive uids and is suitable for marine applications.
2.6.
Flat Tube-and-Fin Heat Exchangers
The concept of at tube and ns in heat exchangers has been developed in the
automobile industry for engine cooling and air conditioning (1921). In such
applications one of the two uids is air and the other is either water or a refrigerant. The nonequilibrium of the heat capacities of the two uids leads to the adoption of different enhancement technologies for both uids. Generally on the air
side the surface is nned (plain or louver ns), and on the other side the uid
ows in small-diameter channels (Figures 17 and 18). The technology is based on
FIGURE 14 Stainless steel brazed platen heat exchanger. (Courtesy of

Nordon.)
assembling aluminum elements, by either mechanical expansion or brazing. For

conventional applications, the pressure can be up to 20 bars. Recently, heat
exchangers with operating pressures up 140 bar have been manufactured (22) for
car air conditioning systems, using carbon dioxide as refrigerant.
2.7.
Microchannel Heat Exchangers
Microchannel heat exchangers are compact heat exchangers where the channel
size is around or lower than 1 mm. Such heat exchangers have been developed for
severe environments, such as offshore platforms (23). New applications are also
arising for high-temperature nuclear reactors (24). To manufacture such small
channels, several technologies are available (25): chemical etching, micromachining, electrodischarge machining, etc.
The most common one is the printed circuit heat exchanger developed by
the Heatric Company. The channels are manufactured by chemically etching into
FIGURE 15 Different n geometries.
FIGURE 16 Ceramic recuperator. (Courtesy of Cramiques et Composites.)
a at plate. The plates are stacked together and diffusion bonded. These heat
exchangers can support pressures up to 5001000 bar and temperatures up to
900C (not simultaneously with high pressure). The typical size of the channels
is 1.0 2.0 mm, and the plate size can be up to 1.2 0.6 m (Figure 19). The
processing technique is as exible as for platen heat exchangers, and crossow
FIGURE 17 Condenser. (Courtesy of Livernois.)
FIGURE 18 Extruded aluminum minitube.
and counterow congurations are employed. The main limitation of the

microchannel heat exchanger is the pressure drop, which is roughly inversely proportional to the channel diameter. For high-pressure applications, the pressure
drop is not a constraint; but for other elds of application it will be the main barrier to the use of such heat exchangers.
More recently, Chart-Marston has developed the Marbon heat exchanger (26).
This heat exchanger is made of stainless steel plates stacked and bonded together
(Figure 20). Several congurations are possible: (1) shell and tube, and (2) platen.
The use of such a heat exchanger as a chemical reactor is under consideration,
and the thermal and hydraulic characterization has been undertaken as Europeanfunded project (27).
Very compact heat exchangers are also used for cooling electronic devices
or microreactors (Figure 21). In these heat exchangers the channel size ranges from
50 m to 1 mm. Single phase and boiling are encountered in such applications
(28). Applications in the chemical processing industries are also foreseen (29).
These units can be very small in size and the heat duty per unit volume is very
high, up to15 kW/cm3.
2.8.
Matrix Heat Exchangers
Perforated, or matrix, heat exchangers are highly compact and consist of a stack
of perforated plates made of high-thermal-conductivity material, such as copper
or aluminum, alternating with spacers of low thermal conductivity, such as plastic or stainless steel. The pack of alternate low- and high-thermal-conductivity
FIGURE 19 Printed circuit heat exchanger. (Courtesy of Heatric.)
plates are bonded together to form leakproof passageways between the streams
(Figure 22). The main bonding technique adopted is diffusion bonding; more
information can be found in Ref. 30.
Such heat exchangers have been developed for cryogenic and lowtemperature applications (31) and for fuels cells (32). They are suitable for a large
range of operating conditions, but there is very little information on their thermal
and hydraulic behavior. Furthermore, as the heat is transferred by conduction in
the plate, the temperature distribution is not homogeneous.
2.9.
Selection of Heat Exchanger Technology
The selection of the technology of compact heat exchangers depends on the operating conditions, such as pressure, ow rates, and temperature, as well as on other
parameters, such as fouling, corrosion, compactness, weight, maintenance, and
reliability. Table 1 summarizes the major limits for the different types of compact
heat exchangers.
FIGURE 20 Marbond heat exchanger. (Courtesy of Marston.)
3.
3.1.
SINGLE-PHASE FLOW
Flow Pattern
For corrugated heat exchangers, the ow is almost three-dimensional, and the

velocity eld is difcult to measure. Flow visualization (3334), realized in a
high-scale channel, clearly shows a recirculation area downstream of the corrugation edges (Figure 23). These areas are large at low Reynolds number (left of
picture). But the transition to turbulent ow (Figure 24), which occurs at
Re 200, reduces the size of these areas. Local information (3538) on the heat
FIGURE 21 Microchannel heat exchangers.
FIGURE 22 Matrix heat exchanger.
transfer and velocity elds indicates that the heat transfer coefcients are linked
to the ow pattern and to the mixing intensity in the channel; variations of 50%
were measured. Furthermore, the size of the recirculation areas could be limited
by a proper design or by choosing appropriate operating conditions. The work of
Amblard (39) and Hugonnot (34) has shown that choosing the appropriate corrugation angle, and with the Reynolds number above a critical value, a quasiplug
ow can be obtained. This indicates that corrugated heat exchangers could be suitable for chemical reactions. The angle of corrugation has some inuence on the
global ow pattern. If we consider the entire channel as a two-dimensional medium,
the ow behavior can be studied. At this scale the ow can be considered homogeneous if there is the same ow rate through the channel width. Thonon et al. (37)
have shown that for low aspect ratio and low corrugation angle ( 30), there is
ow inhomogeneity, up to 15% of the ow rate distribution. But at high corrugation angle or for higher aspect ratio (Ar 2), the ow is almost homogeneous.
In platen heat exchangers, the ow structure depends on the n geometry.
Continuous ns can be assimilated to rectangular channels and the ow is almost
identical to pipe ows. For offset strip ns or louvered ns, there is a high degree
of mixing (40), and the ow becomes turbulent even at low Reynolds number
(Figure 25).
3.2.
Heat Transfer and Pressure Drop
For corrugated heat exchangers, extensive information is available in the literature

(3742); these studies have shown that the major geometric parameter is the
corrugation angle. The enhancement of heat transfer, compared to a smooth channel, is up to six times greater. But at the same time, the pressure drop can be
increased by a factor of 100. Other geometric parameters are also inuential, and
manufacturers are continuously improving the plates design.
For platen heat exchangers in single-phase ow, the heat transfer coefcients are related to the developed heat transfer surface, and the area ratio must
be taken into account. As related to the projected surface, the overall heat transfer
coefcient is very high. Heat transfer and pressure drop can be estimated from
correlations (4344), but these correlations give only an estimate of the performance, because local modication of the n geometry will affect heat transfer and
pressure drop.
For microchannel heat exchangers there is a large discrepancy between
various experimental reports (45). Recent studies (46) have shown that down to
TABLE 1 Operating Conditions of Compact Heat Exchangers
Technology
Aluminum platen
heat exchanger
Stainless steel platen
heat exchanger
Ceramic platen heat
exchanger
Diffusion-bonded
heat exchanger
Spiral heat exchangers
Matrix heat exchangers
Flat tube-and-n
heat exchanger
Brazed-plate heat
exchanger
Welded-plate heat
exchanger
Plate-and-shell heat
exchanger
Gasketed-plate heat
exchanger
Graphite-plate heat
exchanger
Plastic-plate heat
exchanger
Maximal
pressure
(bars)
Maximal
temperature
(C)
80120
70200
10
No
80
650
2
No
1300
No
5001000
8001000
2
No
30
1000
200
400
800
200
2
2
2
Yes
No
No
30
200
No
3040
300400
2
Yes/no
3040
300400
Yes/no
2025
160200
2
Yes
180
Yes
200250
Number of
streams Fouling
2
Yes/no
FIGURE 23 Flow structure in a corrugated channel: laminar ow (Re 150).
0.5 mm, there is no signicant deviation, compared to large tube correlations, but
the size of the channels has to be accurately measured. More work is still needed
to fully understand heat transfer and uid ow in submicronic channels.
3.3.
Fouling
The design of heat exchangers under foulant conditions results in oversizing, thus
substantially raising the cost of plants. Fouling is also responsible for process
inefciencies, due to increased thermal resistance. In water-cooling applications,
particulate and precipitation fouling are frequently responsible for the decrease in
heat transfer performance. Hence, the thermal and hydraulic performances need
to be well understood if the heat exchange capability of practical equipment
needs to be accurately predicted.
FIGURE 24 Flow structure in a corrugated channel: turbulent ow (Re 5000).
FIGURE 25 Flow structure in platen heat exchangers.
Plate heat exchangers are frequently used in industrial processes because

they are more compact and have higher thermal performance than conventional
shell-and-tube heat exchangers, and it is generally admitted that plate heat exchangers are less prone to fouling than conventional shell-and-tube heat exchangers
due to the higher level of the shear stress. Measured fouling resistances (4750)
clearly indicate that fouling resistance values are about 10 times lower in corrugated channels than on a plain surface and that the geometry (Figures 26 and 27)
and the uid velocity (Figure 28) are the major inuential parameters. For instance,
it has been shown that the fouling resistance is almost inversely proportional to
square of the uid velocity. This implies that the uid velocity has to be controlled properly while operating plate heat exchangers.
FIGURE 26 View of the deposit (30 corrugation angle at a velocity of 0.5 m/s).
FIGURE 27 View of the deposit (60 corrugation angle at a velocity of 0.5 m/s).
While sizing plate heat exchangers, the great sensitivity of fouling to the
uid velocity and channel geometry precludes the use of a single value for the
fouling resistance. If the TEMA fouling resistance values are applied to plate heat
exchangers, excess heat transfer surface will be required, which can lead to poor
efciency. It is often recommended that the fouling margin not exceed 25% of the
FIGURE 28 Void fraction in a corrugated heat exchanger.
extra heat transfer surface. Furthermore, the inverse velocity dependence of the
fouling resistance needs to be taken into account at the design stage. If the extra
surface required for fouling is provided by adding plates, a maximum heat duty
is reached; but adding more plates will nally reduce the heat duty. In design procedures, this needs to be taken into account. In the case of severe particulate fouling conditions, 60 corrugation angle plates should be selected rather than lower
corrugation angles, and a minimum uid velocity of 0.3 m/s is suggested.
4.
4.1.
PHASE-CHANGE HEAT TRANSFER

Two-Phase Flow Characteristics
During vaporization or condensation, thermal and hydraulic performances depend

essentially on the two-phase ow structure. Furthermore, as very often in industrial processes, the heat exchanger operates in thermosyphon or under natural circulation; knowledge of the pressure drop and liquid holdup is of major importance.
But there is very little information on two-phase ow characteristics in compact
geometries.
Carey (51) has studied pressure drop and void fraction in different types of
compact heat exchangers and has outlined the differences with plain tube geometries. Kreissig and Muller-Steinhagen (52) and Margat et al. (53) have shown
that the principles of the methods developed for plain tubes can be used but need to
be adapted. The main results of these studies are that the liquid holdup is signicantly affected by the mass ow rate (Figure 28); the liquid holdup is underestimated by conventional correlation; the two-phase ow multiplier can be estimated
from a Chisholm-type correlation.
Winkelmann et al. (54) have studied airwater ows in a corrugated heat
exchanger. Flow visualization and two-phase pressure drop measurements have
been performed. The ow visualizations have shown that the ow pattern is complex
and that a wavy or a lm ow occurs in most cases (Figure 29). The two-phase
pressure drop depends on the total ow rate and vapor quality, and Chisholm-type
correlation is proposed. More work is required to characterize the ow structure
in compact heat exchangers and to develop predictive methods for the frictional
pressure drop and the mean void fraction.
4.2.
Vaporization
Vaporization is the most common unit operation to be found in the process industry; the use of compact heat exchangers as evaporators began 40 years ago for the
concentration of sugar or salt solutions. Nowadays, compact heat exchangers are
used in several industrial processes, and this is particularly true for platen heat
exchangers, which are closely integrated in distillation and separation processes
of natural and industrial gases. In most cases, evaporation takes place in an upward
FIGURE 29 Two-phase ow visualization in plate heat exchangers.
ow and the uid enters subcooled. The heat exchanger operates either in natural
or forced circulation. In the refrigeration industry, the heat exchangers are often
located directly after the expansion valve, so a two-phase mixture is fed at the
bottom of the heat exchanger. The main problem with such a conguration is to
obtain a homogeneous phase distribution among the channels. Some manufacturers insert a distribution device in the inlet port, and it has been shown that a signicant improvement in thermal performance can be achieved. For large compact
heat exchangers operating under two-phase ow at the inlet, each phase of the
mixtures is fed independently in the channel in order to ensure an effective phase
distribution.
The design of compact heat exchangers for vaporization duties requires
knowledge of the heat transfer coefcients, and it is generally admitted that the
basic mechanisms occurring during ow boiling are similar to those encountered
in plain tubes (5557), but no general predictive method is available. For plate
heat exchangers, most of the data published have been obtained with pure refrigerants, and the operating conditions are rather different than those encountered in
the process industry. The general trend of these studies is that the heat transfer
coefcients are signicantly higher than those obtained in conventional plain
tubes, but the pressure drop is also increased. Concerning boiling of mixtures, compact heat exchangers provide high single-phase heat transfer coefcients; hence
the vapor phase will be well mixed, and no major degradation of the heat transfer coefcient should be observed.
Concerning platen heat exchangers, the design of such units is much more
complicated because up to 12 different uids can ow in the heat exchangers.
For distillation and separation processes, the uids encountered are mixtures, and
specic pinch methods have been developed (5859); a temperature approach of
less than one degree can be obtained. To optimize the number of layers per uid
and the type of ns, the heat transfer coefcients need to be accurately predicted
in the different boiling zones (subcooled, nucleate, convective, dryout, etc.).
Therefore, tests were performed with cryogenic uids, hydrocarbons (6061), and
refrigerants (62) in order to measure the heat transfer coefcients under actual ow
and geometric conditions. Tests with cryogenic uids are required because the
behavior of such uids is signicantly different than that of organic uids.
Microchannel heat exchangers are used for boiling applications, but there is
a lack of data for process uids. Studies using water or refrigerant at low pressures
have outlined differences in the ow pattern and in the heat transfer coefcients
(6364). This comes from the fact that the bubble diameter is limited by the channel size. For low and intermediate vapor qualities, the heat transfer coefcients are
increased as compared to plain tubes of larger diameters. But for higher vapor qualities, partial dryout may occur and will reduce heat transfer. Because microchannel
heat exchangers might operate under large temperature differences, estimation of
the critical heat ux is important; but most of the correlations were obtained for at
plates and single tubes, so their extension to microchannels is doubtful (65).
To select and apply a boiling method to compact heat exchangers, several
facts must be taken into account. The method must be based on the fundamental
mechanisms occurring, because purely empirical and curve-t methods cannot be
generalized. The basic assumptions for developing such a method is that both
nucleate boiling and convective boiling occur and that the dominant mechanism
depends on geometric and operating conditions (Figures 30 and 31). The effect of
FIGURE 30 Vaporization in a platen heat exchanger.
FIGURE 31 Vaporization in plate heat exchanger.
geometry must be taken into account in the convective area, and that of the operating conditions in the nucleate regime. It is assumed that nucleate boiling correlations, established for plain tubes, are sufciently accurate and general to be
applied for compact heat exchangers. In the convective regime, the heat transfer
coefcient is reported to the single-phase liquid heat transfer coefcient, and an
enhancement factor is introduced to take into account the liquidgas interactions.
The main questions are to evaluate the single-phase heat transfer coefcient of the
given geometry, especially at low Reynolds numbers, and to characterize the
enhancement factor. The fundamental problem is to learn whether enhancement
factors developed for plain tubes can be applied successfully to compact geometries. Work is being carried out in several R&D organizations, and knowledge on
boiling in compact geometries should be improved in the near future.
4.3.
Condensation
Condensation occurs in many industrial processes, but rarely with pure uids.
The uids encountered are mixtures, and noncondensable gases are often present;
this makes the condensation process very complex.
In compact geometries the heat transfer coefcient depends on the two-phase
flow pattern (5167). For low condensation rates, the heat transfer is gravity
controlled, and the heat transfer coefcient depends on the liquid lm thickness.
For higher condensation rates, the heat transfer coefcient depends on the vapor
shear effect, and for small passages the liquidvapor interaction leads to high heat
transfer coefcients.
In the case of mixtures or in the presence of a noncondensable gas, the condensing vapor must diffuse through the gas to the phase interface. For this to happen a partial pressure gradient toward the phase interface is necessary. The partial
pressure of the vapor falls from a constant value at a rather large distance from the
phase interface to a lower value at the interface. Correspondingly, the accompanying saturation temperature also falls toward the interface. Therefore, during condensation, the condensing vapor arrives by diffusion at the condensate surface, and
it is the thermal resistance in the vapor that limits the process. Hence in order to
improve the heat transfer, one must reduce the thermal resistance on the vapor
side. Several factors can enhance the condensation process by reducing the vaporside resistance. During condensation of mixtures or of vapors that contain noncondensables, the heat transfer on the vapor side can be improved by raising the
vapor velocity. It has been shown that the heat transfer coefcient can be improved
by approximately 30% by increasing the vapor velocity. The use of a nely undulated surface can also achieve signicant augmentations in heat transfer during
condensation. It has been shown that corrugation can promote turbulent equilibrium between the phases and thus contribute to the increase in heat transfer.
Compact heat exchangers are characterized by small hydraulic diameters
(110 mm), and there is no reliable design method to estimate heat transfer coefcients during condensation in such small passages. In the available literature,
condensation of mixtures and of vapor in the presence of noncondensables has
been studied, but essentially for conventional geometries (plain tubes), and only
few results have been published with uids representative of actual process conditions (hydrocarbons). A 2002 study (68) has shown that in laminar regime there
was a signicant mixture effect (decrease in the heat transfer coefcient), but in
turbulent regime the mixtures behave as pure uids (Figure 32). This outlines the
high degree of mixing encountered in such heat exchangers, which is not surprising, since the geometric pattern of the plates is similar to modern column packing.
5.
5.1.
HEAT TRANSFER AND MASS TRANSFER

Macromixing
Macro- and micromixing are two major issues for compact multifunctional heat
exchangers. Macromixing is closely linked to the ow pattern and has often been
studied using ow visualization techniques. An effective macromixing will give
high transfer rates and homogeneous ow distribution in the channel. The typical
scale of macrostructures ranges from half of the channel height to one-tenth of the
channel height. Micromixing is associated with much smaller scales and will
affect the reaction rate.
In this section, we will focus on two technologies able to produce both heat
transfer and mixing: the corrugated heat exchanger and the platen heat exchanger.
FIGURE 32 Mixture effect during condensation.
These heat exchangers have a exible design and high heat transfer performance
and might be suitable for combined heat transfer and mass transfer services. The
thermal-hydraulic performances of the two technologies were presented in previous sections. Flow visualization has often been used for analyzing ow structures,
but it only gives access to qualitative information or time-average measurements.
Using advanced numerical methods allows simulating single-phase ow in complex geometries, such as those encountered in compact heat exchangers. The
determination of the mixing ability for water at a Reynolds number equal to 2000
is managed under the aspects of the computational uid dynamics (CFD) method.
An extensive review of turbulence models useful for compact heat exchanger
simulation is available in the literature (70). The most appropriate model for each
selected geometry will be discussed next.
For corrugated heat exchangers, the ow is almost three-dimensional.
Analyzing the stream function inside the 60 heat exchanger (Figure 33), we can
see that ow is mainly in the direction of the ow inlet, which is a characteristic
of subchannel ow. However, a small part of the uid is deviated by the channels:
furrow ow. So for this angle, quasiplug ow can be obtained, which is in
FIGURE 33 Stream function inside the 60-angle plate heat exchanger.
accord with the work of Amblard (39) and Hugonnot (34). The ow can be considered homogeneous since there is the same ow rate through the channel width.
This indicates that high teta corrugated plate heat exchangers could be suitable
for chemical reactions where macromixing is needed. Analyzing the stream function inside the 30-angle heat exchanger (Figure 34), we can see that the ow feature is equally in the direction of the ow inlet (subchannel ow) and inside the
furrow (furrow ow). This result is in good agreement with Gaiser (35).
For a two-dimensional wavy channel, a numerical analysis performed at
GRETh (69) has shown that the mixing efciency of corrugated channels is excellent because one corrugation is nearly sufcient to have perfect mixing (Figure 35).
For nned passages, all the described phenomena (Figure 36) are in good
accord with the regime predicted by the literature (70). Indeed, the ow hits the
front edge of the rectangular obstacle and separates immediately. The shear layer
reattaches to the wall and splits in two parts: one part ows upstream, creating a
recirculating and high-shear area; the other is convected downward by the mean
ow. With time, the shear layer becomes unstable near the reattachment point,
and it oscillates; it generates a vortex production inside the bubble and a
growth of the recirculating area. Due to impinging shear layer instabilities, the
FIGURE 34 Stream function inside the 30-angle plate heat exchanger.
FIGURE 35 Numerical analysis of the mixing efciency in a corrugated channel.
FIGURE 36 Closeup of the ow pattern inside the offset strip n geometry.
long bubble is broken, and an eddy is liberated and convected toward the trailing
edge. At the same time, the bubble length decreases. This vortex shedding occurs
on both faces of the obstacle, and a Von Karman street is formed in the wake of
the n.
In platen heat exchangers, the ow structure depends on the n geometry.
For offset strip ns, there is a high degree of mixing (25), and the ow becomes
turbulent even at low Reynolds numbers (Figure 37). Indeed, after six rows of ns
(e.g., about 20 mm), the ow is homogeneous, so the macromixing in the platen
heat exchanger is very efcient.
5.2.
Micromixing
Micromixing technologies have only recently been applied to the design of

miniaturized devices for chemical applications, so called microreactors. The main
components of such microreactors are mixers and heat exchangers.
FIGURE 37 Evolution of a passive scalar inside the offset strip n geometry.
Two ranges of applications can be distinguished:

The laminar regime for highly viscous uids (such as glue), slow reactions,
and long residence time
The turbulent regime for classical gas- or liquid-phase reactions, fast reactions, and low residence time
The present work will only focus on the turbulent regime, which is characterized by eddies with a wide range of length and time scales. The largest eddies
are typically comparable in size to the characteristic length of the mean ow. The
smallest scales are responsible for the dissipation of turbulent kinetic energy,
which is related to the turbulent uctuation of the velocity. The higher the uctuation, the smaller the scales in the ow and the better the micromixing efciency.
So for highly turbulent ows (high velocity or large hydraulic diameter), the
micromixing will be very efcient, without any inventive turbulent generators.
However, for compact heat exchangers where the hydraulic diameter is not large
(a few millimeters) and the velocity not very high (maximum 1 m/s), enhancement techniques are needed in order to lower the turbulent-transition limit.
The mixing efciency is determined by both the value of the pressure drops
and the turbulent energy dissipation, (m2/s3):

where is given by

pu
L
and L is the total length of the passage, is the voidage of the passage, p is the
pressure drop through the passage, and is the density of the uid. The higher the
mixing efciency, the better is the micromixing.
For corrugated heat exchangers, using the numerical simulation for both
60 and 30, we can evaluate directly from the computation and from classical correlation (57) (Table 2). The lower the angle, the lower the mixing efciency. Indeed, while lowering the angle, the ow pattern moves from subchannel
ow (helicoidal motion) to furrow ow (duct ow), which reduces the mixing.
The mixing efciency is very low (below 10%), so corrugated heat exchangers,
which are able to produce high heat ux, e.g., high macromixing, are not able to
produce micromixing.
For platen heat exchangers, using the numerical simulation for the OSF
geometry, we can evaluate directly from the computation and from classical
correlation (8) (Table 2). The OSF geometry is able to produce both macro- and
microturbulent scales. For the Reynolds number considered, the fully turbulent
TABLE 2 Micromixing Performance for Plate Heat

Exchangers (PHE) and Offset Strip Fin (OSF) Heat Exchangers
PHE
30 angle
Turbulent intensity (%)
(m2/s3)
(W/kg)
(%)
6.2
0.43
13.1
3.2
60 angle
OSF
11.0
2.01
51.0
5.7
10
17.1
24.1
71
regime is not achieved (one must increase the velocity or the plate width by a factor of 2), but this geometry is efcient for heat transfer and mixing. It could be a
good concept in the area of temperature-controlled reactions.
5.3.
Two-Phase Flow Heat Transfer and Mass Transfer
Numerous industrial operations involve a heat transfer between a liquid phase and
a gaseous phase, with an important mass transfer effect, either as desorptionevaporation or as absorption-condensation. Here are some examples: reconcentration, by evaporation, of solvents, toxic industrial efuents; production, by
absorption, of industrial aqueous acid solutions; reversible or irreversible chemical
reactions (oxidation, hydrogenation, sulfonation); purication of permanent gases
(air, smoke) by scrubbing of soluble vapors; desorbers and absorbers for heat pumps,
where these two operations occur simultaneously.
In these multifunctional processes, heat transfer and mass transfer are two
combined and simultaneous functions, and the objective is to substantially improve
these functions in order to save energy, to increase the process efciency, and to
reduce the size and cost of industrial plants. Corrugated pads are often used in the
dehumidication process or in chemical heat pumps, but a higher efciency could
be reached by using diabatic units, where the wall could exchange heat with the
liquid lm.
6.
6.1.
APPLICATIONS
Feed/Efuent Heat Exchangers
Feed/efuent heat exchangers are used in many industrial processes to warm up

the uid before the reactor and to cool it down after treatment at high temperature. The conventional design of such heat exchangers is based on shell-and-tube
units. But to increase the thermal effectiveness of the heat exchangers, the
required heat length becomes very important, and high pressure drop will occur.
The alternative to conventional shell-and-tube units is to use plate-type heat

exchangers (71). The advantages of PHEs are a high thermal effectiveness for a
low pressure drop, compactness, and a low propensity to fouling (72). In the rening industry, large PHEs are used in hydroteater (HDT and HDS); the aim of
these treatments is to reduce the naphtha contaminants (sulfur, hydrogen, arsenic,
lead, etc.).
With the use of such units, two main problems arise: two-phase ow distribution and fouling. At the inlet of the efuent, the ow is a two-phase mixture
(gas oil hydrogen) with vapor qualities up to 20%. To ensure a homogeneous
flow distribution, the two phases are fed independently at the inlet of each channel
(up to 200 channels in parallel). These devices allow reaching high thermal effectiveness and a low-temperature approach. Concerning fouling, because these heat
exchangers are totally welded and cannot easily be cleaned, tests have been performed under laboratory conditions and on site to measure the fouling resistance.
Full-scale tests, realized at the Belgium Rening Corp in Antwerp (Figure 38), have
shown that after two years the thermal performance remained constant. A more
precise study was also performed using the Alcor fouling apparatus. A PHE and
shell-and-tube unit were connected in parallel; under similar operating conditions, the PHE exhibited no fouling while the shell-and-tube heat exchanger
reached fouling resistance values up to 3 104 m2 K/W.
Work is still required to optimize the design of such PHEs because the heat
transfer mechanisms are complex. On the feed side, a complex mixture is vaporized; on the efuent side, the mixture is condensed with the presence of noncondensable gases.
6.2.
Process Evaporators
Concentration of liquid by evaporation is widely used in industry, and a large

variety of techniques have been adopted. Two cases are considered: (1) the efuent is desolved in water (salt solution, for example); (2) the efuent and the water
act as a mixture (wateracid solutions, for example). In the rst case, the concentration process is very efcient and high concentration can be obtained. In
specic cases, crystallization of the efuent can be achieved. Most of the technological developments have been obtained on the projects dealing with desalination of seawater or the sugar industry. For mixtures, the liquid efuent to be
concentrated is partially evaporated in a heat exchanger; at the outlet, the vapor
phase is richer with more volatile compounds and the liquid phase is richer with
less volatile compounds. The evaporator acts as a rst stage of distillation. The
effectiveness of the evaporation process depends essentially on the mixture-phase
equilibrium. In most of the cases, the heating uid is steam. As a consequence,
the channel geometry must me adapted on each side of the heat exchanger to
achieve optimal performance. Furthermore, as in most cases, the evaporating uid
FIGURE 38 Process ow sheet. (Courtesy of Packinox.)
has high fouling capacities, so the evaporating side must be cleanable and the
dead zone should be avoided.
Different types of evaporators are used in concentration processes: (1) ash
evaporation through a discharge valve, (2) horizontal tubular or plate reboilers
(submerged or falling lm), (3) vertical tubular or plate evaporators (climbing or
falling lm), (4) specic evaporators (direct contact, scraped surface, etc.). Compact
heat exchangers are mostly used as vertical evaporators with either falling lm
(Morgenroth et al. (73)) or climbing lm (Brotherton (12), Patel and Thomson (11)).
A special high-capacity compact falling-lm evaporator has been developed for
sugar plants. The use of falling-lm evaporators allows one to reach higher heat
transfer coefcients than with climbing-lm evaporators, especially for low temperature differences. Compared to conventional systems, the overall heat transfer
performance can be up to two to ve times higher, as a function of the uid
viscosity. Plate heat exchangers are also used as evaporator in sugar plants, with
a similar level of enhancement. All the tests realized (lab scale, pilot and industrial units) have shown that plate heat exchangers, even with small hydraulic
diameters, are not more sensitive to fouling than plain tubes. Other applications
in concentration processes of such compact heat exchangers should be developed,
especially in the area of mixture concentration.
6.3.
Integrated Heat Exchangers in Separation Processes
Distillation and separation processes for purifying products requires up to 40% of

the overall energy demand in chemical processes (Trambouze (74)), and great
efforts have been made by engineers to reduce this energy consumption. The integration of the reboiler and the condenser in distillation columns has already been
studied, but the entire potential of integrated heat exchangers has not been achieved
(Lyon et al. (75)). As an example, plate heat exchangers have been installed in an
isopropanol dehydration plant as reboilers and condensers, and they have been
found to be very effective from the viewpoint of heat transfer.
Condensers and evaporators used in distillation processes are generally
based on the horizontal shell-and-tube design, and this conventional design leads
to large units, which have generally low energy efciency. The integration is not
optimal, and the heat exchanger is still a part of the unit. Introducing compact heat
exchangers in place of shell-and-tube units will permit greater compactness and
lower energy consumption. Because the heat exchanger operates purely in countercurrent, heat is available at a higher temperature than with horizontal shells. For
long-term developments, diabatic distillation and separation units must be studied.
Reux condensers are often used in the top of a distillation column, as a
rst stage to separating the lighter and heavier components. Because the liquid
ow and gas ow are countercurrent, a critical gas ow rate exists above which
ooding occurs. Although considerable work in the literature has been devoted to
free-falling lms (mostly in pipes), the issue of ooding in countercurrent gas/
liquid ow has not been settled yet. Furthermore, the literature concerning ooding in narrow passages is extremely poor. Thus, for the case of compact condensers, there is no reliable tool for engineering-type predictions of ooding.
From the viewpoint of heat transfer, reux ows are more complex to study than
downward ows. Heat and mass transfer occur simultaneously between the
phases, and heat transfer is present between the liquid phase and the walls.
Literature provides neither experimental data nor a reliable prediction method for
these special system conditions. Studies about condensation inside channels have
been carried out only for concurrent downward ow of pure vapors in tubes with
large diameters. At present the design parameters for reux condensation can
only be estimated by the classical annular-ow model presented in heat transfer
handbooks. However, this model is not applicable under the given conditions, and
it is known from practical applications that the real condensation rate in compact
heat exchangers deviates drastically from predictions according to the classical
model. Modeling reux condensation (dephlegmation) in a compact platen heat
exchanger has been carried out (Urban et al. (76)), and the critical aspect raised
is the distribution of the liquid lm on the ns and the importance of the owdistribution device. An integrated heat exchanger distillation column has been
developed by Nakaiwa et al. (77), and a plate technology has been adopted. The
analysis outlines the energy savings that can be obtained as well as the higher
compactness.
Aluminum platen heat exchangers are often used as condensers in distillation and separation processes, but they require nonfouling and noncorrosive
uids. In the chemical industry, stainless steel or welded-plate heat exchangers
have been used as top condensers of distillation columns, because they can be
either directly installed inside the column or closely integrated outside (Figure 39),
FIGURE 39 Overhead reux condensers.
thereby avoiding extra piping and a pump for the condensate. In these compact
heat exchangers, condensation can take place in downward or reux ows. For
reux condensation, ooding may occur at high gas-ow rates, and the design of
nontubular heat exchangers is essentially based on correlations and methods
developed for plain tubes or larger hydraulic diameters. Studies on reux ows in
noncircular and small-hydraulic-diameter channels are required for a better design
of such apparatus.
Looking more closely at the basic structure of compact heat exchangers, it
can be noticed that the geometry is quite similar to the packing for distillation
columns. Because the wetting area is signicantly higher than for plain tubes and
higher mixing occurs in liquid lms, an additional rectication effect may occur
during reux condensation. This phenomenon needs to be evaluated because it
may reduce the height of the distillation column.
6.4.
Reactor Heat Exchangers
The development of integrated chemical reactor heat exchangers requires sizing

tools for aiding the design and operation of the process. The thermal performance
of these heat exchangers is of prime importance for a global analysis of energy
efciency. Furthermore, a local analysis of ow and heat transfer conditions is also
required for a better characterization in terms of chemical reactors (mixing intensity and residence time distribution).
At bHr Group (Phillips et al. (78)), tests performed on fast exothermic reactions have shown that energy savings up to 40% could be achieved and that the
amount of by-product was signicantly reduced. Extension of this work to commercial compact heat exchangers is currently being considered; the rst results
indicate that chemical heat exchangers (CHEs) could be suitable as continuous
chemical reactors.
Catalytic plate reactors already exist, but their range of application is
extremely limited (Jachuck and Ramshaw (79)). The basic idea is to bring into
contact the heat source (catalytic reaction) and the heat sink (cooling medium).
The catalyst is coated as a thin layer on one side of the plate, and on the other side
ows the coolant uid. For dehydrogenation applications, a plate-type catalytic
reactor has been developed (Arakawa et al. (80)); the benets are its higher exibility, via the control of the process temperature, and its higher productivity, via
the reduction in by-product formation. An alternative solution is to pack small
balls of catalyst between two plates. Plate catalytic reactors can operate under
high heat uxes and probably allow innovative reaction schemes (reaction with
pure oxygen or under pressure).
At ECN, an example of coupling reactions has been studied for reforming
of methanol. Combustion and reforming of methanol are done in two catalytic
compartments of the reactors. The catalyst has been coated on the internal
surfaces of a stainless steel platen heat exchanger. A monolith structure is used
for each reacting channel, and a model has been developed to calculate the heat
transferred between the channels. This heat exchanger reactor has been developed
for integration in a fuel cell plant.
The design of a heat exchanger reactor has to match several objectives:
The residence time must be sufcient to ensure a complete reaction within
the heat exchanger.
The uid temperature must be controlled, which implies high heat transfer
coefcients.
If the feed and the reactant are not premixed and well dispersed, a sufcient
turbulent intensity must be generated by the channel geometry.
The pressure drop must be acceptable.
The chemical process gives the enthalpy of reaction, the ow rate, the reaction
time, and the required reaction temperature. The rst step in the sizing procedure
is to calculate the required number of channels for the heat exchanger. Then the
pass arrangement is selected in order to achieve the highest possible Reynolds
number within an acceptable pressure drop. For example, if the total number of
channels is xed by the residence time: channels in series will induce high velocities and high pressure drop; channels in parallel will induce low velocities and
low pressure drop. The second step is to estimate the heat transfer coefcient and
to check that the heat ux can effectively be controlled by the secondary uid (the
lower heat transfer coefcient should be on the reaction side).
The use of compact heat exchangers, where the channel characteristic
dimension is between 1 and 10 mm, allow high heat transfer and mass transfer
coefcients, even for low Reynolds numbers. The limitation will come from the
mixing intensity, which may not be sufcient to ensure droplet breakdown and to
avoid droplet coalescence, which will directly affect the reaction. Preliminary
studies have shown that corrugated heat exchangers and OSF platen heat
exchangers are in turbulent ow even at low Reynolds numbers (Re 300) and
that they should be suitable for chemical reactions. Investigation of the uid ow
is of prime interest for such applications, and advanced numerical methods provide local and instantaneous values that can be used to characterize the chemical
reaction. These advanced CFD methods may also be used to develop specic
compact heat exchangers for chemical reactions as well as mixing devices.
Microchannels are also envisioned as a structure for heat exchanger reactors. If the channel dimensions range between 100 and 500 m, the area per unit
volume is very high and allows catalytic reactions within the heat exchanger. An
example of such a heat exchanger reactor is given by Rebrov et al. (81). Several
studies are ongoing for applications in ne chemicals, reaction screening, and
micro hydrogen reformers (29).
7.
CONCLUSIONS
In this chapter, the different types of compact heat exchangers have been reviewed
and their applications described. Single-phase ow applications are now common
in the process industry; due to their high thermal effectiveness, compact heat
exchangers are real alternatives to conventional shell-and-tube units.
For multiphase applications, the use of compact heat exchangers is still not
widespread, but in some industries these heat exchangers are widely used. In particularly, in the refrigeration industry, plate heat exchangers are often used as boilers and condensers. A great opportunity to transfer knowledge and technology can
be applied to compact heat exchangers. On the one hand, within the new environmental requirements, mixtures will replace the conventional refrigerants (pure uids), and the refrigeration industry is not used to dealing with mixtures. Transfer of
knowledge from the process industry, which is used to dealing with mixtures, could
help the refrigeration industry. On the other hand, because the refrigeration industry already uses compact heat exchangers, the transfer of technology to the process
industry will be fruitful. New applications for compact heat exchanger should also
arise in environmental systems (Shah et al. [82]). Heat exchangers can also be considered an active component in the process and not only a utility. For instance, heat
exchanger reactors (Phillips et al. [27]) or diabatic distillation columns (Nakaiwa
et al. [77]) may be designed using compact heat exchanger technology.
Process intensication (PI) is described as a key for future development in
process plants (Green [83]), and because the cost of energy is now decreasing in
Europe, the search for compactness in equipment is the goal to be achieved. Therefore, adopting compact heat exchangers is probably the most effective way to
intensify a process. To support and develop intensive technologies, there is a need
for basic studies on heat transfer and mass transfer in compact geometries (R&D
projects) and also targeted actions on specic applications (demonstration projects).
As outlined at the Compact Heat Exchangers for the Process Industry conference
(Shah [8486]), the development of new products must be realized in collaboration with the process industry, and the reliability of compact heat equipment is the
rst goal to achieve. Furthermore, manufacturers must propose manufacturing
standards and design methodologies. Finally, the high potential of compact heat
exchangers clearly matches the objectives of process intensication, and a much
wider use should emerge within 510 years.
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5
Process Intensication Through
Microreaction Technology
Wolfgang Ehrfeld
Ehrfeld Mikrotechnik AG, Wendelsheim, Germany
1. MICROTECHNOLOGY AS A KEY FOR THE ADVANCED

DESIGN OF CHEMICAL PLANTS
Since the middle of the 20th century, general technological progress has been
dominated essentially by a unique strategy of success, which constantly aims at
comprehensive miniaturization and integration of functional elements in technical
systems. The most outstanding development took place in microelectronics, where
integrated circuits with hundreds of millions or even billions of transistors have
become products of our daily lives. More recently, micromechanical, microoptical,
microuidic, and many other microdevices have become the basis for a multibillion
dollar business, the market for microtechnology (13). The products of microtechnology have achieved a key position in information, communication, entertainment, automotive, and medical technologies.
In the chemical and pharmaceutical industries, biochemists were the rst or,
at least, the fastest to make an interdisciplinary move into the promising eld of
microtechnology. Terms like lab on a chip, microarrays, microuidics, and micro
total analysis systems have become familiar to all working in the life sciences and
at the front line of genomics, proteomics, glycomics, metabolomics, and all the other
omics in this area. They regard biomolecules to some extent like a source of data
and, consequently, have no problems applying information-based technologies to
innovations in their own eld. In the same way, large information technology (IT)
companies have started to enter the area of life sciences, utilizing their traditional
strengths in combination with the concepts of microreaction technology.
Researchers in chemical engineering are also intensively analyzing the possibilities potentially offered by the general strategy of miniaturization and integration to realize a radical change in design philosophy for modern chemical
plants. This research and development work started at ICI in the late 1970s, and
the term process intensication was used to characterize the novel concept. The
main intention was to achieve much lower investment, operating, and maintenance
costs for chemical plants, without decreasing their production capacity, by means
of a dramatic reduction in plant size; they aimed at a reduction factor of 100 or
even 1000 (4,5).
This intention may look more like a dream than a serious concept. However,
the technological progress even in standard plant items has proven, beyond doubt,
that this concept has a realistic basis. One may just consider, on the one hand, a
standard stirred-tank reactor with a cooling jacket having a volume of about 10 m3
and, on the other hand, a potentially equivalent reactor for the same production
capacity consisting of a static mixer and a compact heat exchanger having a
volume of about 0.1 m3 (6). This simple comparison demonstrates the superiority of continuous operation over batch processing with regard to specic plant
volume and its importance in process intensication. Many other potential examples exist, such as spinning disk reactors, vortex scrubbers, reactor-mixing systems, and, of course, multifunctional reactors, which integrate reactions and unit
operations.
There is no doubt that the ultimate development of process intensication
leads to the novel eld of microreaction technology (Figure 1) (79). Because of
the small characteristic dimensions of microreaction devices, mass and heat transfer processes can be strongly enhanced, and, consequently, initial and boundary conditions as well as residence times can be precisely adjusted for optimizing yield and
selectivity. Microreaction devices are evidently superior, due to their short response
time, which simplies the control of operation. In connection with the extremely
small material holdup, nearly inherently safe plant concepts can be realized. Moreover, microreaction technology offers access to advanced approaches in plant design,
like the concept of numbering-up instead of scale-up and, in particular, the possibility to utilize novel process routes not accessible with macroscopic devices.
As a matter of fact, microfabrication methods have to be introduced into
chemical engineering in order to prot from the potential advantages of microreaction technology. Although this is a difcult hurdle, a few chemical companies
have successfully started to utilize microreaction technology for commercial syntheses of ne and special chemicals. Nevertheless, much effort must still be spent
to transfer further promising research results into commercial application and to
FIGURE 1 Evolutionary development through process intensication.
get away from traditional strategies in chemical engineering. In the following,

a comprehensive analysis covering these aspects will be given.
2. EFFECT OF MINIATURIZATION ON UNIT OPERATIONS
AND REACTIONS
2.1. Enhancement of Heat Transfer
and Mass Transfer Processes
Diffusion, thermal conductivity, and viscosity are physically similar phenomena
that involve the transport of a physical quantity through a gas or liquid. The driving forces for the corresponding transport uxes of mass, energy, and momentum
are the gradients in concentration, temperature, and velocity, respectively, where
in all three cases the uxes are in the same direction as the gradients. For given
differences in these properties, a decrease in the characteristic dimensions results
in an increase in these gradients and, correspondingly, in higher mass and heat
transfer rates as well as in higher viscous losses. Accordingly, mixing and heat
exchange systems with extremely high transfer rates per unit volume can be realized by miniaturization; on the other hand, however, the effect of viscous losses
has to be taken into account.
Besides the effect of decreasing linear dimensions on the corresponding
gradients, the effective surface area for exchange processes has to be considered.
With decreasing characteristic dimensions, the surface-area-to-volume ratio of
the system increases. This results in a corresponding enlargement of the specic

interface area, i.e., of the area per unit mass or unit volume, for transfer processes,
so, in connection with the enhancement of the gradients, i.e., the driving forces
for heat and mass transfer, extremely efcient mixers and heat exchangers can be
realized by miniaturization. Furthermore, the amount of material in a system is
reduced with the reciprocal third power of the characteristic dimensions, and,
consequently, the response time of the microdevice is extremely reduced so that
in most cases large differences concerning temperatures and concentrations are
diminished immediately.
It was demonstrated in many cases that highly exothermal reactions can be
performed under isothermal conditions using the channels of micro heat exchangers as reaction volumes (Figure 2) (10). Pioneering work on this subject started
in the late 1980s, when micro heat exchangers with extremely high transfer rates
per unit volume were produced by means of advanced mechanical micromachining methods (Figure 3) (11). Meanwhile, specic heat transfer rates of more than
20 kW per cm3 have been achieved, and a broad spectrum of materials has been
successfully applied.
A wide variety of micromixers are also available that allow mixing times in
the submillisecond range (8,12). They utilize mainly the concept of multilamination,
where two streams of uids are split into a large number of small substreams and fed
alternately into an interdigital ow system, where they merge into a joint stream
(Figure 4). Other concepts are based on the principle of splitting, side-to-side
arrangement, and further splitting to generate an increasing number of substreams
with different compositions, as known from large-scale static mixers. Vortex-type
micromixers have also abeen applied.
A wide range of applications for micromixers exists in the elds of gasliquid
suspensions and liquidliquid emulsions, with extremely small bubble and droplet
sizes, respectively. A high uniformity concerning size distribution is achievable;
in particular, the specic power consumption for generating suspensions and
emulsions is much lower than in the stirring devices or high-pressure jets usually
applied in the macroscopic range (8,13). Accordingly, micromixers are promising tools to improve the performance of phase transfer and other exchange
processes.
2.2. Inherent Process Restrictions in Miniaturized Devices
and Their Potential Solutions
As a matter of fact, miniaturization inevitably results in a number of process
restrictions, and completely new problems arise, too. There are, above all, the
problems of blockage of microstructures by solid particles and fouling effects.
Moreover, corrosion might be much more dangerous for microscopic than for
macroscopic devices.
FIGURE 2 Microreactor for parallel screening of catalysts for partial oxidation of methane.
(Source: D. Hnicke, TU Chemnitz.)
FIGURE 3 Micro heat exchanger produced by means of mechanical

micromachining. (a) Platelet with grooves of 30-m depth and 70-m width.
(b) Assembly of crossow heat exchanger. (c) Final devices. (Source:
Forschungszentrum Karlsruhe.)
Nevertheless, if the solid particles are small enough, they will have no negative effect on the operation of a microreactor. On the contrary, microreactors can
even produce pigments of higher quality, i.e., smaller size and better uniformity,
than macroscopic devices. This positive result was obtained experimentally at
Clariant Company; consequently, a microreactor pilot plant for pigment production
is under construction (14). By means of highly efcient micromixers, Siemens Axiva
Company succeeded in improving the synthesis of acrylate resins. They could avoid
a detrimental portion of high-molecular-weight resin and, consequently, fouling
of the main continuously operating reactor. Evidently, there are at least concrete
chances to get around some of the problems resulting from small characteristic
dimensions.
There is, of course, no possibility of avoiding all problems inherently connected with small dimensions. For instance, gravitational forces cannot be efciently
utilized to transport uids at small characteristic dimensions, since the effects of
surface forces might far exceed those of mass or bulk forces. This problem is
immediately evident when regarding the reux in a miniaturized distillation column or the settler in a micromixer/microsettler system. To some extent, rotating
devices can be applied and centrifugal forces can be utilized for material transport.
This approach has been demonstrated successfully in microuidic systems, but it
is not a general solution. Consequently, other methods for phase separation are
required for miniaturized process devices, such as microltration to break emulsions
and the utilization of hydrophobic and hydrophilic surfaces or capillary effects.
Finally, surface effects will become more and more dominant in chemical reactions when the characteristic dimensions are reduced, which may produce advantages or disadvantages, depending on the respective type of reaction.
2.3. Consequences for the Selection of Reaction Routes
and Plant Design
The extreme enhancement in mass and heat transfer rates through miniaturization
of process devices results in fundamentally novel design possibilities with respect
to selecting alternative reaction routes and plant design. In contrast to macro
devices like large stirring tanks, the starting conditions for a chemical reaction can
be set precisely with respect to time and concentration because of the much faster
mixing of educts in a micromixer. The reaction starts at precisely dened time and
position with a spatially uniform composition. Thus, unfavorable reaction conditions
FIGURE 4 Micromixers. (a) Interdigital structure of a multilamination micromixer. (b) Principle of split-and-recombine static micromixers. (Source: IMM.)
due to incomplete mixing are minimized that eventually result in undesired side
and secondary reactions and, consequently, losses in yield and selectivity.
The high heat transfer rates achievable in micro heat exchangers and reactors
avoid unfavorable reaction conditions resulting from hot spots or thermal runaway
effects. An optimum temperature or temperature prole for the reaction can be
chosen with respect to spatial distribution and time. Thus, a fast-owing uid element can be cooled down or heated up very rapidly, in fractions of a millisecond.
Because of the small thermal mass of microdevices, a periodic change of temperature of the reactor can be realized, with a typical time constant of some seconds.
All these examples offer possibilities to improve yield and selectivity.
Since micro reactorsexcept for high-throughput screening in combinatorial
materials researchare usually operated under continuous conditions, it seems
simple to adjust the optimum residence time by means of a suitable delay loop or
channel that is also favorable with respect to yield and selectivity (Figure 5). However, the ow conditions in microdevices are generally characterized by a low
Reynolds number; consequently, a parabolic HagenPoiseuille prole will exist
in long channels and ducts. This ow prole results in an unfavorable broadening
of the distribution of residence time. Special channel congurations allow one to
reduce this effect.
2.4.
Process Control and Safety
The inherent advantage of precise adjustment of the starting and boundary conditions for chemical reactions and unit operations in microdevices provides a
novel basis for process control. Taking into account, in addition, the small holdup,
FIGURE 5 Process intensication by setting the optimum residence time.
FIGURE 6 Explosion-proof continuous synthesis in the explosive range. The

reaction system consists completely of ame-retarding microchannels.
it is evident that an extremely short response time is a further inherent advantage

of microreaction devices with respect to process control.
As a result, there is a unique chance to utilize alternative reaction routes
for chemical synthesis that so far have not been applied commercially, for reasons
of safety or difculties in process control or because it is fundamentally impossible to realize such reaction routes using macroscopic devices. This is the case, in
particular, for controlled reactions in the explosive regime (Figure 6) (15). This is
accessible by means of microreaction devices, since, due to their small characteristic dimensions, they act like ame retention bafes. Moreover, the small dimensions allow reactions to be performed at extremely high pressure, which is of
importance for chemical processes using supercritical solvents.
2.5. Sustainable Development by Numbering-Up
and Distributed Production
The safety problems connected with the storage of large quantities of educts and
products remain, of course, unchanged when a conventional plant is replaced by a
microreaction plant with the same production capacity. Nevertheless, this problem
may be reduced by replacing a large plant by several small plants for distributed
production. In contrast to conventional plants with macroscopic process devices,
where scale-up usually results in a considerable reduction of specic investment
costs, microreaction plants may instead prot from the mass production of microdevices in reducing specic investment costs. Scale-up for achieving the desired
production capacity can be done only at one site, while a plant comprising a large
number of identical chemical microdevices according to the numbering-up concept

can be split up for production at several sites. As a result, microreaction technology
may contribute to the strategy of sustainable development by saving resources due
to a higher yield and, in particular, by exible production on site and on demand.
There are a number of further advantages to the numbering-up concept.
Research results can be transferred into production faster, plants can be constructed
in a shorter time, and the production capacity can be adjusted more exibly to
variations in demand. Since mass production of microdevices may result in relatively a low cost per piece, novel cost-saving maintenance and repair concepts
based on disposable elements might be introduced.
3. FROM BASIC PROPERTIES TO TECHNICAL
DESIGN RULES
In contrast to microelectronics, where extremely powerful software tools and
detailed design rules exist for the development of ultralarge-scale integrated circuits, there are no corresponding comprehensive means in microreaction technology available to date. Such design tools should comprise mathematical modeling
of ow and chemical reactions in miniaturized systems as well as specications
for suitable materials and simulation of manufacturing processes applicable to the
respective microreaction devices.
Since it will take several years to realize such an integral software toolbox,
individual approaches with separate steps have to be applied to meet gradually the
requirements of microreactor design. Standard software for computational uid
dynamics is directly applicable in this context, and there are also powerful software
tools for the simulation of special steps in microfabrication processes. However,
there has been rather little experience with materials for microreactors, optimization of microreactor design, and, in particular, the treatment of interdependent
effects. Consequently, a profound knowledge of the basic properties and phenomena of microreaction technology just described is absolutely essential for the successful design of microreaction devices.
For instance, proper design rules must take into account that mixing and
heat exchange systems with extremely high transfer rates per unit volume can be
realized via miniaturization but that an increase in viscous losses may counterbalance the positive effects. Accordingly, suitable gures of merit must be dened
for micromixers and micro heat exchangers that consider the ratio of mass or heat
uxes to pressure losses. However, the value of such a gure of merit should be
always considered in context with further boundary conditions of the process and
the interdependence of several process properties. Decreasing the characteristic
dimensions of a system results, as already explained, in a reduction in the material
holdup and a simultaneous enlargement of the surface-area-to-volume ratio of the
system. These aspects also determine the speed of mixing and heat transfer and,
consequently, the degree of miniaturization required in a specic case. Such aspects

have to be considered for a favorable design of a microreaction system; in some
cases, extremely small dimensions are not necessary to avoid unfavorable reaction conditions resulting from hot spots or thermal runaway effects.
If large amounts of materials have to be transported, a favorable design should
instead consider large pumps rather than arrangements with many micropumps,
which, in most cases, are commercially unattractive for cost reasons and technically less suitable because of their comparatively low efciency.
4. MICROFABRICATION OF REACTION
AND UNIT OPERATION DEVICES
4.1.
General Requirements
Since the production of chemicals in a continuous process is inevitably connected

to a transport of material, three-dimensional microfabrication processes are required
in order to realize sufciently large cross sections for channels and ducts as well
as reaction volumes. Meanwhile, a wide variety of such processes as well as
design and test methods exist that all essentially originated from either semiconductor technology or precision engineering. Thin-lm methods, applied to a large
extent in semiconductor technology, are less suitable for the generation of threedimensional microreaction devices but are widely used for surface processing and
protection as well as for manufacturing sensor elements.
Because of the extremely wide variety of reactions, educts, products, and
process conditions, a sufciently broad spectrum of materials is required to realize
suitable microdevices for chemical processes. Metals and metal alloys, plastics,
glass, ceramic materials, semiconductor materials like silicon, and various auxiliary materials for sealing, surface treatment, etc. have been successfully applied for
realizing microreaction devices.
Besides such basic aspects concerning the shape of and materials for microreaction devices, costs play a major role in the selection of a microfabrication
process. In this respect, the number of pieces and the precision that is really
required, as well as aspects like availability and manufacturing experience, must be
taken into account. In contrast to the situation some years ago, the prerequisites for
cost-effective mass fabrication as well as small-scale production or rapid prototyping have essentially changed. Modern commercial equipment for the production of
microdevices is available that allows unreliable and uneconomic laboratory-scale
manufacturing devices to be replaced.
Mathematical modeling of the device function may also help to cut costs,
since it allows more realistic specications to be worked out with regard to functional requirements. In addition, mathematical modeling of the process sequence
for microfabrication and assembly will be useful for cost saving. Such hard and
soft aspects will be considered in more detail in the following analysis of microfabrication methods for reaction devices.
4.2.
LIGA Technology
The LIGA technology allows the production of ultraprecise micro structures with
an extreme aspect ratio from a wide variety of materials (16,17). It is based on a
combination of deep lithography, electroforming, and molding processes. In the
rst step of the manufacturing sequence, a pattern from a mask or by means of a
serial beam-writing process is transferred into a thick resist layer on an electrically conductive substrate. Ultraprecise microstructures with an extreme aspect
ratio can be generated by deep X-ray lithography. Using special epoxy resists
like SU 8, which utilizes intrinsic optical waveguide properties of irradiated
crosslinked regions, favorable results are also achievable by means of UV lithography.
In the second step, the three-dimensional relief-like structure of the resist
polymer generated by deep lithography is transferred into a complementary metallic structure by means of electroforming, starting from the electrically conductive
substrate. Usually a nickel sulfamate electrolyte is applied, but there are also proven
electrolytes available for deposition of other metals and metal alloys.
The metal structure generated by means of electrodeposition may be the nal
product in some special cases. In general, however, it is used in a third step as a
master tool for a replication process, such as injection molding, casting, or embossing, for mass fabrication of microstructures. A wide variety of mold materials can be
applied for micromolding, e.g., organic polymers, preceramic polymers, and ceramic
and metallic powders with organic binders for subsequent sintering, so that most
material requirements for chemical microdevices can be favorably met.
It should be emphasized that the development of the LIGA technology originated from a special requirement in nuclear process engineering. Curved micronozzles with characteristic dimensions in the micrometer range were needed as
mass products for aerodynamic separation of the uranium isotopes in the framework of a large technological development work at the Karlsruhe Nuclear
Research Center (Figure 7). Today there are a number of LIGA products that evidently have promising markets in the elds of micro-optics and integrated optics,
molecular biotechnology, and microactuators. More recently, LIGA components
and systems have been successfully applied to chemical engineering and
microreaction technology, respectively. A number of chemical companies and, of
course, research institutes utilize devices such as micromixers, micro heat
exchangers, and micro bubble columns as well as modular systems with integrated
functional elements for reaction, heat transfer, mixing, separation, and uid distribution for process development. LIGA devices are also seriously being considered by the chemical industry for the production of ne chemicals.
FIGURE 7 Double-deecting micronozzle for aerodynamic separation of uranium isotopes manufactured by LIGA technology from nickel. The smallest
characteristic dimensions achieved in such devices are below 10 m. (Source:
Institute of Nuclear Process Engineering at the former Karlsruhe Nuclear
Research Center, now Forschungszentrum Karlsruhe, Siemens.)
4.3.
Wet and Dry Etching Processes
Wet etching processes are widely used to produce microstructures by means of

transferring resist patterns into various materials. However, for most materials only
isotropic etching processes exist, so, because of lateral underetching of the resist
pattern, only shallow microchannels or other shallow structures can be generated at
the surface of a bulk material. Three-dimensional structures can be manufactured
when the pattern is etched completely through thin foils, which then have to be
stacked in order to realize deep microchannels with a high aspect ratio (Figure 8).
Isotropic etching has been applied several times for manufacturing microreaction devices. The technological expenditure is relatively low, but there are
some restrictions concerning accuracy, surface roughness, and geometrical
design. The product spectrum comprises various types of heat exchangers, micromixers, separators, reaction units, and even integrated devices with several functional elements.
Wet chemical anisotropic etching of monocrystalline silicon has been widely
applied in microtechnology (18,20). This method is based on the dependence of
etching velocity on crystal orientation, so only a few basic geometries can be
FIGURE 8 Microetched foil of stainless steel for manufacturing micro heat

exchangers by stacking and diffusion welding. (Source: Ehrfeld Mikrotechnik,
tztechnik Herz.)
realized. Besides silicon, there has been very little manufacturing experience with
other monocrystalline, inevitably very expensive, materials. Consequently, wet
chemical anisotropic etching is in general not very attractive for manufacturing
chemical microdevices because of strong restrictions with respect to shape and
material. Nevertheless, the technological expenditure is low, and material problems can also be solved via the deposition of protection layers. A number of
microuidic devices have been manufactured by means of this method, such as
micropumps, microvalves, and ow-distribution systems.
Besides anisotropic etching of monocrystalline materials, another wet
chemical etching process exists that uses a special type of photosensitive glass (19).
A wafer consisting of such glass is irradiated through a mask with UV light and
subsequently heated to a temperature between 800 and 900 K. This results in a
crystallization of the irradiated regions that can be dissolved much faster in hydrofluoric acid than the nonirradiated parts. This method has been successfully applied
to produce microreaction devices such as mixers, heat exchangers, and micro titer
plates from glass.
Precise microstructures with nearly any cross-sectional shape can be generated by means of anisotropic plasma-etching methods, where again silicon is the
most important and proven material (18,20). Usually, a mask pattern is transferred
into a thin layer consisting of a material resistant to plasma etching on a silicon
wafer. Subsequently, silicon is etched by means of a uorine-containing lowpressure plasma that generates gaseous silicon compounds.
In order to generate microstructures with an extremely high aspect ratio, the
directed etching process is connected with a subsequent deposition process from
the plasma where the walls oriented in parallel to the etching direction are covered
with a plasma polymer resistant to the reactive plasma (21). By means of multiple
repetition of directed etching and side wall passivation, channels and other structures
with nearly vertical walls can be realized; accordingly, extremely high aspect ratios
are achievable for nearly any cross-sectional shape (Figure 9).
FIGURE 9 Channel structure of a phase separator generated by ASE deep

etching of silicon. (Source: IMM.)
This so-called advanced silicon etching (ASE) process achieves etching

velocities on the order of 0.2 mm per hour. The ASE dry etching method has, of
course, limitations concerning, e.g., material selection and surface smoothness or
the brittleness of silicon, which makes it nearly impossible to use it directly as a
mold insert in micromolding processes. Nevertheless, it is possible to transfer
ASE silicon structures into complementary metal structures by electroforming.
For a number of applications, ASE is evidently a favorable alternative to LIGA in
manufacturing devices for microreaction technology.
4.4.
Mechanical Micromachining
In the past few years, impressive progress has been made in so-called mechanical
micromachining, utilizing technologies based on so-called ultraprecision machining.
Complex three-dimensional microstructures have been generated with shape accuracies in the submicrometer range by means of milling, turning, and grinding
(11,22). Three- and ve-axis ultraprecision micromilling machines are available
as commercial products. Using diamond tools, an extremely low surface roughness of a few nanometers is achievable for nonferrous materials. Progress has also
been made in machining stainless steel by using ultrane-grain hard metal tools
and novel technologies like vibration cutting. In addition, mechanical micromachining has been successfully applied with brittle materials. Micromixers,
micro heat exchangers, and reaction systems have been successfully produced by
means of this technology (Figure 3).
It is evident that there are hardly any limitations concerning the generation
of microstructures for chemical microdevices with complex geometries,
extremely high aspect ratio, and high precision from a wide variety of materials
by means of mechanical micromachining. Rather, restrictions may exist when
manufacturing closely packed channels or other structures, because of the nite
size of the tools. Also, manufacturing costs may become a problem in mass
fabrication; but in such a case, mechanical micromachining may be helpful for
manufacturing mold inserts for mass fabrication by means of micromolding.
Moreover, there are other mechanical methods for high-volume production, like
punching and embossing, that have been successfully applied in fabricating, e.g.,
micro heat exchangers.
4.5.
Microelectrodischarge Machining
An interesting alternative to standard mechanical micromilling, turning, drilling,

and grinding methods is microelectrodischarge machining (EDM), which is virtually unlimited with respect to the geometrical shape of the work piece (23). Material
is removed in a discharge between the electrically conductive work piece and an
electrode by small sparks in a dielectric uid such as oil or deionized water. An
important advantage in micromachining is that the forces acting on the work piece
in EDM are extremely low. The disadvantages of micro EDM are a relatively large
surface roughness, limitations in miniaturization because of the nite size of the
electrodes and the spark gap in the electrical discharge, and very long machining
times, so this method is essentially used to manufacture mold inserts or prototypes.
The methods of mechanical micromachining and micro EDM have been
extensively applied to the fabrication of components such as micro heat exchangers,
mixers, and reaction channels as well as chemical microsystems with integrated
heat exchange, reaction, mixing, and distribution elements (Figure 10).
4.6.
Micromachining by Means of Laser Radiation
Microfabrication by means of laser radiation covers a wide range of different

methods (24,25). On the one hand, these are processes where material is removed
in an intense electromagnetic eld by melting, evaporation, decomposition, photoablation, or a combination of these phenomena. On the other hand, generating
processes exist where structures are built up from liquid resins, laminated layers,
or powders using, e.g., photochemically induced crosslinking of organic compounds
FIGURE 10 Micromixing element generated by microelectrodischarge machining. (Source: Ehrfeld Mikrotechnik, Zumtobel.)
FIGURE 11 Part of a static micromixer manufactured by laser ablation from

aluminum oxide. (Source: Ehrfeld Mikrotechnik, Heidelberg Instruments
Microtechnologies.)
in stereolithography or powder solidication by laser sintering. In addition, welding

by means of laser radiation is of major importance for the connection and assembly of microdevices.
There are no restrictions worth mentioning concerning materials in micromachining by laser radiation, which is a real advantage for chemical microdevices
(Figure 11). However, limitations exist to achieving critical dimensions below
10 m and low surface roughness. Removal of material is also often connected with
the generation of debris, which reduces accuracy. Since laser-based microfabrication
processes, except lithography, are essentially serial rather than parallel machining
methods, their productivity is comparatively low. Nevertheless, they offer a huge
potential in rapid prototyping.
Laser-based micromachining processes have been applied to date only on a
relatively small scale for manufacturing chemical microdevices (27). This will
probably change relatively soon, since rapid prototyping will become more and
more important for developing novel microreaction devices.
5.
IMPLEMENTATION OF MICROREACTION TECHNOLOGY
Microreaction technology has created a novel basis for:

Accelerating screening in combinatorial material development
Realizing extremely powerful tools for the evaluation of new reaction pathways
Implementing comprehensively the concept of process intensication for
the production of ne and special chemicals (Figure 12)
Following the development route of miniaturization in the life sciences, the

implementation of microreaction technology in combinatorial material development has been very successful. Companies like Symyx, located in Silicon Valley,
whose business is based on the highly effective synthesizing and screening of a
huge number of chemical compounds, have demonstrated that faster development
and cost savings are achievable by means of microreaction devices. Not only can
the amount of reactants, auxiliary substances, waste, energy, and space be minimized, but all the other advantages of microreaction devices mentioned earlier can
also be favorably utilized (see, e.g., Ref. 27). The research work of such companies
is focused on more efcient catalysts, new polymers, high-performance phosphors
for illumination, and, of course, drug development and many other substances.
Promising work in this direction is also being done at universities and government research centers (7,8,26,28).
Researchers at BASF have shown that microreactors can be utilized that
give access to operating conditions that cannot be realized by means of macroscopic
equipment. They succeeded in improving yield and selectivity in a highly exothermal two-phase reaction in connection with the synthesis of a vitamin precursor.
At Degussa company, a microreactor test facility for proprietary reactions is
under construction. The major focus in this context is the implementation of
microreaction devices as powerful tools for process development and, in particular, for the evaluation of new reaction pathways.
Companies like Clariant and Merck use microreactors for production, and
they are obviously convinced that the ultimate development of process intensication leads to microreaction technology. In contrast to other companies, Clariant
FIGURE 12 Microreaction technology aims at production of (a) information,

(b) tools for process development, and (c) chemicals.
FIGURE 13 Modular microreaction system consisting of functional elements

for reactions and unit operations arranged on a base plate. The cube-shaped
modules of stainless steel with built-in microstructures have a side length of
25 mm and can be operated at pressures up to 100 bar. (Source: Ehrfeld
Mikrotechnik.)
has reported about its work and its promising progress (14). Researchers at Clariant
assume that about 15% of future production facilities will be based on microreaction technology.
However, microfabrication methods that are usually unfamiliar to chemical
engineers have to be introduced to prot comprehensively from microreaction
technology. This transition from standard manufacturing methods of plant components to the development and production of microdevices is also inevitably
connected with the application of special materials that are not yet proven in chemical engineering. In addition, novel design rules that have not existed until now
should be implemented for the long term to speed up the development of novel
devices.
Essential progress is to be expected from the introduction of so-called
modular microreaction systems. The system developed by Ehrfeld Mikrotechnik
comprises single functional elements for reactions, unit operations, transport,
measurement, and control. The modules can be arranged and connected in a wide
variety of congurations and serve as a toolbox for realizing development platforms
similar to microplants (Figure 13). By means of such platforms, the optimum operation conditions of chemical processes as well as favorable plant congurations
can be determined and novel reaction routes tested. There is also a wide range of
applications in combinatorial chemistry. Since the microplants are usually set up
for continuous operation, they have a comparatively high productivity and can be
utilized directly for small-scale production of special chemicals.
6.
CONCLUSIONS
Future progress in chemical engineering will be strongly determined by process

intensication through microreaction technology. It offers fundamentally novel
opportunities to save direct costs in the areas of development, investment, operation, and maintenance as well as to reduce indirect follow-up expenditures in
connection with storage, transport, and changes in demand or market trends.
A roadmap of microreaction technology for novel process routes and efcient
production is shown in Figure 14. Nearly all major chemical, chemical engineering, and pharmaceutical companies are interested in or even active in analyzing
the potential of microreaction technology. Moreover, there are a number of powerful three-dimensional microfabrication technologies that should meet nearly all
requirements concerning geometries as well as materials of microreaction devices
in prototyping and mass fabrication.
However, the implementation of a novel technology needs time. It is necessary to prove carefully the potential advantages, to develop a sufciently broad
scientic basis, to implement reliable and cost-effective fabrication of chemical
microdevices on an industrial basis, to gain experience in the design, construction,
FIGURE 14 Roadmap of microreaction technology for novel process routes

and efcient production.
and operation of microreaction plants, and nally to demonstrate real commercial

success. Meanwhile, a lot of effort has gone in this direction, but there is still a
multitude of tasks to solve until decisionmakers will be convinced enough of the
commercial prospects of microreaction technology to accept the inevitable nancial risks of technological progress.
REFERENCES
A comprehensive overview of the international development work on microreaction technology can be found in the Proceedings of the International Conferences on Microreaction
Technology, which are listed in the following.
Ehrfeld W, ed. Proceedings of the 1st International Conference on Microreaction Technology. Berlin: Springer, 1998.
Ehrfeld W, Rinard I, Wegeng R, eds. Process Miniaturization: 2nd International
Conference on Microreaction Technology, IMRET 2; Topical Conference Preprints.
AIChe, New Orleans, 1998.
Ehrfeld W, ed. Proceedings of the 3rd International Conference on Microreaction Technology. Berlin: Springer, 2000.
Rinard I, ed. 4th International Conference on Microreaction Technology. Topical Conference Proceedings. AIChE Spring National Meeting, Atlanta, GA, March 59, 2000.
Matlosz M, Ehrfeld W, Baselt JP, eds. Proceedings of the 5th International Conference on
Microreaction Technology. Berlin: Springer, 2001.
Rinard I, ed. 6th International Conference on Microreaction Technology, Conference
Proceedings. AIChe Spring Meeting, New Orleans, March 1014, 2002.
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Bundesministerium fr Bildung und Forschung. Frderkonzept Mikrosystemtechnik
2000, Bonn, Germany, Jan 2000.
Stankiewicz AI, Moulijn JA. Process intensication: transforming chemical engineering. Chem Eng Prog 2000; (Jan):2233.
Green A, Johnson B, John A. Process intensication magnies prots. Chem Eng
1999; (Dec):6673.
Wood M, Green A. A methodological approach to process intensication. IchemE
Symposium Series No. 144, 1998:405416.
Jensen KF, Hsing I-M, Srinivasan R, Schmidt MA, Harold MP, Lerou JJ, Ryley JF.
Reaction engineering for microreactor systems. Proceedings of the 1st International
Conference on Microreaction Technology. Berlin: Springer, 1998:29.
Ehrfeld W, Hessel V, Haverkamp V. Microreactors. In: Ullmanns Encyclopedia of
Industrial Chemistry. 6th ed. Weinheim: Wiley-VCH, 1999.
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Mayer J, Fichtner M, Wolf D, Schubert K. A microstructured reactor for the catalytic

partial oxidation of methane to syngas. Proceedings of the 3rd International Conference on Microreaction Technology. Berlin: Springer, 2000:187196.
Schubert K, Bier W, Linder G, Seidel D. Herstellung und Test von kompakten
Mikrowrmebertragern. Chem Ing Tech 1969; 61:172173.
Lwe H, Ehrfeld W, Hessel V, Richter T, Schiewe J. Micromixing technology. Proceedings of the 4th International Conference on Microreaction Technology. AIChE
Spring National Meeting, Atlanta, GA, March 2000.
Bayer T, Heinichen H, Natelberg T. Emulsication of silicon oil in watercomparison
between a micromixer and a conventional stirred tank. Proceedings of the 4th International Conference on Microreaction Technology. Atlanta, GA, AIChE Spring
National Meeting, March 2000:167173.
Wochner M. Mikroreaktorenkleine Ergnzung fr grosse Kessel, Clartext No. 3/
2002.
Hagendorf U, Jnicke M, Schth F, Schubert K, Fichtner M. A Pt/Al2O3 coated
microstructured reactor/heat exchanger for the controlled H2 /O2 reaction in the
explosion regime. Proceedings of the 2nd International Conference on Microreaction
Technology, AIChE Spring Meeting, New Orleans, LA, March 1998, 8187.
Ehrfeld W, Mnchmeyer D. Three-dimensional microfabrication using synchrotron
radiation. Nucl Inst Meth Phys Res 1991; A303:523531.
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Ehrfeld W, Baselt JP, eds. Proceedings of the 5th International Conference on
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Carl Hanser Verlag, 2001:279322.
Freitag A, Dietrich TR, Scholz R. Glass as a material for microreaction technology.
Proceedings of the 4th International Conference on Microreaction Technology. AIChE
Spring National Meeting, Atlanta, GA, March 2000:4854.
Rangelow IW, Kassing R. Silicon microreactors made by reactive ion etching. Proceedings of the 1st International Conference on Microreaction Technology. Berlin:
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Weck M. Ultraprecision machining of microcomponents. In: Weck M, ed. Proceedings of the International Seminar on Precision Engineering and Microtechnology,
Aachen: European Society for Precision Engineering and Nanotechnology, July 2000.
Michel F, Ehrfeld W, Koch O, Gruber H-P. EDM for microfabricationtechnology
and applications. In: Weck M, ed. Proceedings of the International Seminar on
Precision Engineering and Microtechnology, Aachen, July 2000.
Bremus E, Gillner A, Hellrung D, Hcker H, Legewie F, Poprawe R, Wehner M,
Wild M. Laser processing for manufacturing microuidic devices. In: Proceedings of
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mesopore systems for the successful performance of heterogeneously catalysed reactions. In: Ehrfeld W, ed. Proceedings of the 1st International Conference on Microreaction Technology., Berlin: Springer, 1998:2026.
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6
Structured Catalysts and Reactors:
A Contribution to Process Intensication
Jacob A. Moulijn, Freek Kapteijn,
and Andrzej Stankiewicz
Delft University of Technology, Delft, The Netherlands
1.
INTRODUCTION
In this book the chemical plant is focused upon. Therefore, the present chapter
emphasizes chemical reactors for the chemical process industry. But it should be
made clear that structured packings and catalysts also have a large potential in
consumer products. Chemical reactors form the heart of a (petro-)chemicals production plant. Given the large variety of plants it is no surprise that a wide variety
of chemical reactors are used. Catalytic reactors can be roughly divided
into random and structured reactors. It is useful to start with a summary of the
major basic concerns (apart from high activity, selectivity, etc.) for catalytic
reactors:
Catalyst quality on a microscopic length scale (quality, number of active
sites)
Catalyst quality on a mesoscopic length scale (diffusion length, loading,
proles)
Ease of catalyst separation and handling
Heat supply and removal
Hydrodynamics (regimes, controllability, predictability)
Transport resistance (rate and selectivity)

Safety and environmental aspects (runaways, hazardous materials, selectivity)
Costs
On each of these, random and structured reactors behave quite differently. In
terms of costs and catalyst loading, random packed-bed reactors usually are most
favorable. So why would one use structured reactors? As will become clear, in
many of the concerns listed, structured reactors are to be preferred. Precision in
catalytic processes is the basis for process improvement. It does not make sense
to develop the best possible catalyst and to use it in an unsatisfactory reactor. Both
the catalyst and the reactor should be close to perfect. Random packed beds do
not fulll this requirement. They are not homogeneous, because maldistributions
always occur; at the reactor wall these are unavoidable, originating form the
looser packing there. These maldistributions lead to nonuniform ow and concentration proles, and even hot spots can arise (1). A similar analysis holds for
slurry reactors. For instance, in a mechanically stirred tank reactor the mixing
intensity is highly non-uniform and conditions exist where only a relatively small
annulus around the tip of the stirrer is an effective reaction space.
Catalytic conversion and separation are conventionally carried out in separate pieces of equipment. A combination of functions in single units is an elegant
form of process intensication. When one of the functions is a chemical reaction,
it is referred to as a multifunctional reactor. A good example is catalytic distillation technology from the CDTech Company. They have introduced elegant technology for desulfurization of oil (2). Structured reactors will play a key role in the
design of novel processes based on multifunctional reactors (3). A monolith is a
good example. Monolithic catalysts are shown in Figure 1.
FIGURE 1 Monolithic structures of various shapes. Square-channel cordierite

structures (1, 3, 5, 6), internally nned channels (2), washcoated steel monolith (4).
FIGURE 2 Low-pressure-drop reactors used for tail-gas treating.
Depending on ones point of view, a monolith can be considered a reactor

or a catalyst; the borders between catalyst and reactor vanish (4,5). Other structured reactors also deserve attention, but for the message it sufces to limit the
discussion to monolithic reactors.
2.
OVERVIEW OF STRUCTURED REACTORS
Structured reactors and catalysts are encountered in a large variety (3,6).

Structured catalytic reactors can be divided into two categories. The rst involves
a structured catalyst, whereas the second one involves normal catalyst particles
arranged in a nonrandom way. In the rst category, the catalyst and the reactor are
essentially identical entities.
Because of their low pressure drop, structured reactors in practice dominate
the eld for treating tail gases. Figure 2 presents the major types of reactor. The
monolithic reactor represents the class of real structured catalytic reactors,
whereas the parallel-passage reactor and the lateral-ow reactor are based on a
structured arrangement of packings with normal catalyst particles.
Structuring is possible at all length scales. In structured reactors the level is
considered above that of a single particle. Structuring can be done based on dedicated structured catalyst shapes in such a way that the catalyst is an integrated part
TABLE 1 Subdivision and Typical Examples of Structured Reactors

Structuring on the level of the catalyst
and the reactor
Monoliths
Extruded parallel-channel systems
(honeycombs), usually ceramic
Emission reduction for cars
Ozone decomposition in airplanes
Selective catalytic reduction of NOx
Arrays of corrugated plates
Arrays of bers
Gauzes
Ag
Methanol formaldehyde
Pt/Rh
NO production from ammonia
HCN production from methane
Foams
Catalytic membranes
Structuring exclusively on
the level of the reactor
Three-levels-of-porosity (TLP)
reactors
Bead-string reactors
Membrane-enclosed catalytic
reactors
of the reactor shape. An alternative is to arrange catalyst particles in such a way

that a structured reactor is the result. Table 1 gives the subdivision together with
typical examples. By inspection of Figure 2, most of them can be recognized.
2.1.
Monolithic Catalysts and Reactors
Monoliths usually are made from ceramics, but metals are also used. They can be
produced by extrusion of support material (often cordierite is used, but various
types of clays or typical catalyst carrier materials, such as alumina and titania, are
also used), a paste containing catalyst particles (e.g., zeolites, V-based catalysts)
or a precursor for the nal product (e.g., polymers for carbon monoliths).
Alternatively, catalysts, supports, or their precursors can be coated onto a monolithic support structure (washcoating). Zeolites have been coated by growing
them directly on the support during the synthesis (7). The coating literature and
patents represent a large eld, and, in principle, a variety of preparation procedures are available. All major catalyst support materials, ceramic and polymeric,
have been extruded as monolith (4,8). Metallic support structures are used for
automotive applications (9). The choice for a certain catalyst type will strongly
depend on the balance between maximizing the catalyst inventory and catalyst
effectiveness. For slow reactions, a high catalyst loading is desired and the pure
catalyst-type monolith is desired; for fast reactions or if diffusion is slow, a thin

coating with a maximum geometric area is preferred.
Monoliths are the dominant catalyst structures for three-way catalysts in
cars (1013), selective catalytic reduction catalysts in power stations (1417) and
for ozone destruction in airplanes. What causes this popularity? The catalyst consists of one piece, so no attrition due to moving particles in a vibrating case
occurs. The large open frontal area and straight channels result in an extremely
low pressure drop, essential for end-of-pipe solutions like exhaust pipes and stack
gases. The straight channels prevent the accumulation of dust. In all these applications the reaction system is relatively simple; a single uid phase (gas) has to
be treated at reasonable conditions. More demanding applications of monoliths
are now being investigated, fast reactions at high temperatures such as steam
reforming, partial oxidation of hydrocarbons to syngas, and oxidative dehydrogenation (1820). These examples are limited to single-phase applications. As
will be discussed later, monoliths for multiphase applications have already proven
their value.
Monoliths are industrially produced in large quantities by extrusion. This
leads to the attractive situation that, although they are sophisticated structures,
they are commercially available at reasonable cost. Of course, monolithic catalysts have disadvantages. They share with packed-bed catalysts the requirement
of sufcient stability or in any case good regenerability. With respect to mass
transfer and heat transfer characteristics, the major limitations are the laminar
ow through the channels, no interconnectivity between the channels, and a poor
radial heat conductivity. The latter two properties are much better for the foamtype monoliths, but with a trade-off in a higher pressure drop and/or lower catalyst loading (sites/m3). In principle, a laminar ow velocity prole is associated
with low mass transfer rates and a wide residence time distribution. Fortunately,
for gases, due to the small channel size and high diffusivity, this radial transport
in the channels is sufciently fast. Typical time scales for diffusion are given in
Table 2. In liquid phases the diffusivity is three orders of magnitude smaller,
which is one of the reasons that monoliths do not enjoy a high popularity in
liquid-phase operations. It will be shown that this is based on a misconception.
TABLE 2 Diffusion Time Scales in Catalytic Reactors (lD2/2D)
Gas
Liquid
Liquid in cat pore
Liquid in zeolite pore
D (m2/s)
lD for 1 mm
lD for 0.1 mm
lD for 1 m
105
109
1010
1011
50 ms
500 s
5000 s
50,000 s
0.5 ms
5s
50 s
500 s
50 ns
500 ns
5 ms
50 ms
The honeycomb-type monoliths are characterized by a very high geometric

surface area. Dependent on the cell density, this can exceed 3000 m2/m3reactor!
Figure 3 shows the values for three different cell densities, i.e., for 200, 400, and
600 cpsi (cells per square inch). These examples are quite realistic. At present the
normal monolith for cars is a 400-cpsi monolith. The values for the geometrical
surface amount to 3440 m2/m3reactor. In packed beds this value is much lower in
order to avoid unrealistic pressure drops. It is to be expected that future monoliths
will exhibit even larger geometric surface areas. That alone makes them highly
useful for process intensication programs.
Metal monoliths can be shaped rather freely. A good example is given in
Figure 4 (9), where it can be seen that in these parallel-channel systems the structure of the channels is such that the turbulence increases. The reasoning behind
that is the wish to counteract the low mass transfer rates associated with laminar
ow in the thin channels of the monolith.
2.2. Gauzes
The appearance of gauzes is illustrated by Figures 5 and 6 (9). The use of noble
metal gauzes goes back to the beginning of the 20th century for the oxidation of
ammonia into NO. This work followed up work of Ostwald, who applied platinized asbestos and later a roll of corrugated strip of Pt. Probably, this was the rst
application of a structured reactor.
FIGURE 3 Geometric surface areas for three different cell densities.
FIGURE 4 Shaped channels in metal monoliths in order to increase mass

transfer in gas-phase applications.
2.3. Structured Packings

It is often suggested to coat structured packings of the type given in Figure 7
with catalysts, in the same way as monoliths. However, in normal applications
this does not lead to a satisfactory reactor. The geometric surface area is orders of
magnitude smaller than packed beds and monoliths. Of course, this problem can
be solved by packing the channels with catalyst particles. Also, they can be
applied as mixing device to be used for a good inlet distribution in the case of
FIGURE 5 Pt/Rh gauze for the production of NO from ammonia.
multiphase reactors. Later it will be seen that combinations of static mixers and
monolithic catalysts have a high potential in process intensication.
2.4.
Foams
Foams are to some extent the negative images of packed beds. They can be used
when turbulent mixing is important. Figure 8 gives an example of a foam that is
used as a carrier for a molten salt catalyst in diesel soot trapping and combustion.
The openness and the mixing characteristics of foams have stimulated research in
the potential application in soot trapping. An advantage is the robustness of the
FIGURE 6 Details of a Pt/Rh gauze before (A) and after (B) use in the oxidation of ammonia into NO.
FIGURE 7 Structured packing (Sulzer Katapak-K).
system: Plugging does not occur. A disadvantage is the relatively low trapping
efciency. In combustion foams result in stable combustion behavior.
2.5.
Arranged CatalystsThree-Levels-of-Porosity (TLP) Reactors
Three-levels-of-porosity (TLP) reactors (2123) are alternatives for monolith

reactors in certain applications. Conventional catalyst particles can be arranged in
any geometric conguration. In such arrays, three levels of porosity can be distinguished: the pore space within the particles, the intraparticle space, and the
space between the arrays. An example of such a TLP reactor is the parallelpassage reactor (PPR); see Figure 9 (24). The catalyst particles are conned
between wire gauze screens that divide the reactor into a large number of catalyst
layers with empty passages in between.
The gas ows along the catalysts layers instead of through the bed as in a
traditional xed-bed reactor. Because the gas ows through straight channels
(ca. 10 mm wide), the pressure drop over the PPR is much lower than over a
xed-bed reactor. Reactants are transferred from the gas to the catalyst inside the
gauzes, mainly by diffusion. The PPR is very suitable for treating dust-containing
gases, e.g., ue gases from power plants, because dust will not be collected on the
catalyst particles as a result of the straightness of the gas passages.
Bead-string reactors represent the limit of parallel-passage reactors: They
contain single-catalyst-particle subunits. Figure 10 gives a schematic representation (25).
Bead-string reactors have the advantages of lateral-ow reactors but not the
disadvantage of the low mass transfer rates in the units of the lateral-ow reactors.
FIGURE 8 Foam as a catalyst support (alumina impregnated with Cs2SO4.V2O5).
FIGURE 9 Example of the TLP reactor: parallel-passage reactor (PPR). (Adapted

from Ref. 24.)
The disadvantage, of course, is the high cost, due to the difcult, labor-intensive
production. In a recent patent of ABB, an arrangement is claimed that combines
the advantages of the bead-string reactor with an easily produced arranged catalyst
conguration: Monolith channels are packed with catalyst particles, resulting in
strings of particles. This was described as a structured packed bed (26).
The reactor internals, consisting of structured packings packed with catalyst
particles, are also examples of arranged catalysts, e.g., the Sulzers Katapak-S type.
Multifunctional reactors often are also structured reactors. A good example
is the membrane reactor (27,28). Two types can be distinguished, those based on
a catalytic membrane and those in which the membrane only provides a selective
separation function without being catalytically active itself. The former is an
example of a structured catalyst, while the latter belongs to the category of
arranged catalysts. The reactor containing a nonactive membrane is referred to as
a membrane-enclosed catalytic reactor (MECR). In the following, an example of
a MECR is described.
2.6.
Membrane-Enclosed Catalytic Reactor (MECR)
Catalytic membrane reactors are not yet commercial. In fact, this is not surprising. When catalysis is coupled with separation in one vessel, compared to separate pieces of equipment, degrees of freedom are lost. The MECR is in that respect
more promising for the short term. Examples are the dehydrogenation of alkanes
in order to shift the equilibrium and the methane steam reforming for hydrogen
production (29,30). An enzyme-based example is the hydrolysis of fats described
in the following.
2.6.1. Production of Fatty Acids by Fat Hydrolysis in a Membrane

Reactor
A recent development at laboratory scale is the application of an enzyme (lipase)
to catalyze the hydrolysis: Water and fat are mixed at low temperature (300 K) in
a continuous stirred-tank reactor (CSTR). The water phase contains the enzyme.
A much purer glycerol solution is obtained than in the conventional process. The
disadvantage is that the equilibrium is not favorable.
An elegant solution has been proposed based on a membrane reactor consisting of a module with hollow cellulose bers [see Fig. 11 (31)]. The enzyme is
placed at the inner side of the bers, to which the fat is fed. Water passes at the
FIGURE 10 Schematic (a) and reactor conguration (b) of the bead-string

reactor.
FIGURE 11 Membrane reactor for the production of fatty acids. (Adapted

from Ref. 31.)
outside and diffuses through the membrane to react at the fat/lipase interface. The
fatty acid formed stays in the oil phase, whereas the glycerol formed is transported through the membrane into the water phase. Laboratory studies show
nearly complete conversions.
3.
GAS-PHASE REACTIONS
It is fair to state that by and large the most important application of structured
reactors is in environmental catalysis. The major applications are in automotive
emission reduction. For diesel exhaust gases a complication is that it is overall
oxidizing and contains soot. The three-way catalyst does not work under the conditions of the diesel exhaust gas. The cleaning of exhaust gas from stationary
sources is also done in structured catalytic reactors. Important areas are reduction
of NOx from power plants and the oxidation of volatile organic compounds
(VOCs). Structured reactors also suggest themselves in synthesis gas production,
for instance, in catalytic partial oxidation (CPO) of methane.
3.1.
Environmental Catalysis
Converters for cars are usually ceramic monoliths and occasionally metal based.
Without much exaggeration, they can be claimed to be one of the major successes
of recent decades in the area of chemical engineering and catalysis. In the beginning, the catalytic converter was placed underbody, where sufcient space was
available and where the temperature was expected to be mild. There was no need
for process intensication! Later, performance became critical, mainly because of

the observation that under steady-state conditions the converter works well but
cold start emission is relatively large. Options that are offered include a catalyst
close to the engine, electrically heated catalysts, and combinations of catalyst and
adsorbent.
Initially, packed beds were also used. They, however, were no success, and
at present monoliths are applied exclusively. This should not be misunderstood.
Monolith means literally a single stone. However, metal-based analogues are
also included in the denition of monolith. In fact, for catalytic converters in cars,
in addition to ceramics, metal-based monoliths have been and still are used. A
major advantage of metal was the thin wall thickness that could be achieved.
Later, industry succeeded in manufacturing ceramic structures of comparable
wall thickness. In view of their higher resistance against corrosion, ceramic
monoliths are now more generally applied than metal ones.
Structured catalysts are also essential in diesel exhaust gas purication.
State-of-the-art solutions are marketed by PSA and by Johnson Matthey. The truck
market is dominated by diesel engines. In that application, space requirement is
a major issue, and intensication is badly needed. Space velocities exceeding
100,000 h1 are demanded. Reactive structured lters are the way to go.
In the wake of the spectacular application of monoliths in the treatment of
automobile exhaust gas, the potential of monoliths in other applications was studied. Gas-phase reactions were the major area. Catalytic oxidation has received a
lot of attention. Low-NOx burners based on monoliths were designed, catalytic
oxidation of VOCs also benets from structured catalysts, basically because of
the low pressure drop and the resistance against dust.
Originally, packed-bed reactors were applied in selective catalytic reduction (SCR). They could be used only in low-dust applications (15). They were
successfully replaced by several types of structured catalysts, viz., honeycombs,
plate-type catalysts, and parallel-ow systems. Also, this technology is without
doubt successful. Volatile organic compounds are destroyed by combustion in
structured catalysts usually containing Pt or Pd. Compared to automotive applications, the size of the reactors is large. Figure 12 explains the engineering for the
destruction of VOCs of the large gas ows in industry (9).
3.2.
Production of Syngas
In the production of syngas, the following reactions are usually undesired. The
desired reaction is the production of CO/H2 mixtures according to
2CH4 O2 2CO 4H2
whereas sequential oxidation giving CO2 and H2O is not desired. This calls for
short residence times (ms), short diffusion length (as small as possible a diameter
FIGURE 12 Industrial unit for SRC containing metal monolith units.
of the catalyst particle), and the absence of nonuniformity with respect to temperature and concentrations. Moreover, the pressure drop in this type of application should be minimal. It is obvious that a structured reactor should be used. This
leaves three candidates:
Monolith
Gauze
Foam
Foams have the highest turbulence and the highest pressure drop. Probably because of the rst phenomenon they are the most suited, although gauzes
also might be good. Monoliths have the advantage of being well dened, but
the absence of radial heat transport will lead to scale-up problems: When a catalyst in a channel would die, the temperature will drop, and so will the viscosity, leading to a leak in the reactor. It is clear that radial heat transfer is a key
issue (as it is in packed beds). Advanced designs have been described in the literature. By adapting the geometry, turbulence can be enhanced. Figure 4 illustrates
this.
Gauzes are the state of the art for many millisecond-reactions performed in
industry. The best-known examples are the oxidation of ammonia to NO for the
production of nitric acid and the Andrussov process, in which HCN is produced
from methane and ammonia (32):
NH3 CH4 1.5O2 HCN 3H2O
The temperature in this process is quite high, 11001200C. It is not surprising
that under these severe conditions extended reorganization of the alloys takes
place. This is shown in Figure 6 for the oxidation of ammonia into NO.
Many more options are imaginable. A good example is the crosscurrent
monolith (Figure 13). In theory such a system allows ideal heat exchange
between adjacent channels. Such an elaborate structure might look improbable.
However, Corning recently led a patent claiming the direct extrusion of crosscurrent structures. So these advanced reactor types might be applied in practice
in the future. Naphtha cracking, as a large-scale endothermic reaction, might be
a good case for such a reactor.
3.3.
Scale-Up
Scale-up of structured reactors is usually easier than for packed-bed reactors. The
major point is that the hydrodynamics are independent of the scale of the reactor
(assuming a good inlet device). When the radial temperature prole is also independent of the scale, scale-up is straightforward. This is the case for millisecond
reactors. In these reactors, rates are very high; as a consequence, in exothermic
reactions they operate adiabatically. So they scale easily.
FIGURE 13 Crosscurrent monolithic structure.
4.
MULTIPHASE REACTIONS
Various types of reactors are being used commercially for multiphase applications, the major ones being the slurry reactor, the bubble-column reactor, and the
trickle-bed reactor (5). Figure 14 gives a schematic of these three types of reactor. Each reactor has its own advantages and disadvantages. Slurry catalysts are
small (typically 50 m), while trickle-bed particles are larger (millimeter scale),
in view of the allowable pressure drop over the bed. The particle size is a crucial
parameter. In general it can be stated that larger particles are less efcient and,
even more important, are less selective in those reactions where the desired product is subject to the following undesired reaction (A B C, with B as the
desired product). In that often-encountered case, the slurry reactor is more selective than the trickle bed reactor. In terms of process intensication, a mechanically
stirred-tank reactor often is not a good choice. In practice it is no exception that
gasliquid mass transfer is rate determining. This implies that only the part of the
space close to the tip of the stirrer(s) is well used. A large part of the reactor does
not contribute much to the productivity and, depending on the kinetics, will lead
to low selectivity. Moreover, the major disadvantages of the slurry reactor are the
separation of product and catalyst and catalyst attrition. The trickle-bed reactor is
much more convenient, but large particle sizes are unavoidable. An important
limitation of trickle-bed reactors is that, in practice, they are nearly always operated cocurrently, to avoid liquid entrainment by the gas (ooding). Some
important commercial applications, however, would benet from a countercurrent operation, especially for equilibrium-limited reactions and in the case of
strong product inhibition (33). Examples are hydrotreating processes like
hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrocracking.
Only for large particles or low ow rates could this operational mode be achieved
in a packed bed [Synsat process (34)]. Deep desulding is a good example of a
reaction where the concentration prole in countercurrent operation is more optimal from a reaction kinetics point of view (2,35). Also, more active catalysts
(e.g., noble metals) can be used in the last part of the reactor (catalyst proling)
that are more susceptible to H2S poisoning and, as a consequence, are not suitable for cocurrent operation. Overall, countercurrent operation leads to deeper
desulfurization with smaller catalyst units or to larger throughputs (21). In all
FIGURE 14 Schematic representations of three basic gasliquidsolid reactor

systems.
three reactor types, in principle a runaway is possible because when hot spots
would be formed, large amounts of reactants can reach the hot spot, leading to a
classical runaway. It will be shown that structured reactors based on monoliths are
imaginable that do not possess the unfavorable properties mentioned. In current
practice, one application is known. AKZO-NOBEL (previously EKA-NOBEL)
operates ve plants based on the anthraquinone process, in which the reduction
step is carried out in monolith reactors (36,37). Many multiphase reactions have
been carried out at laboratory scale, and in industry interest is also increasing, as
is apparent from patents (26,3846). Recently, monolith structures have been
tried in photocatalysis. This might well be an important application in the future.
4.1.
4.1.1.
Hydrodynamics and Mass Transfer in Monoliths

Cocurrent Operation
For cocurrent gasliquid ow, several ow regimes can occur. The preferred one
is usually the so-called Taylor, or slug, ow (47 49). This type consists of gas
bubbles and liquid slugs owing consecutively through the small monolith channels. The gas bubble lls up the whole space of the channel, and only a thin liquid lm separates the gas from the catalyst (Figure 15). For two reasons, the rate
of mass transfer is large. First, the liquid layer between bubble and catalyst coating is thin, increasing mass transfer. Second, the liquid slugs show an internal
recirculation during their travel through a channel. Because of this, radial transfer of mass is increased. Moreover, the gas bubbles push the liquid slugs forward
as a piston, and a type of plug ow is created. Compare this with single-phase liquid ow through the channels. Because of the low channel diameter, the ow will
be laminar and, as a consequence, the radial transport will be extremely slow,
leading to very poor reactor performance: Rates are slow and the reactor exhibits
strong nonplug-ow behavior. For multiphase operation under slug-ow conditions, the mass transfer increase is an order of magnitude larger than for singlephase liquid ow, whereas the increase in frictionthat is, pressure dropis
much less [Figure 16 (50)]. A fortunate nding is that Taylor ow conditions are
easily realised under practical conditions.
Ideally, in contrast to packed beds, scale-up of monolithic reactors is very
simple. When we know the behavior of one channel, we should be able to predict
the whole reactor. Is this really true? Compared to a packed bed, a monolithic reactor differs in radial transport. When the initial distribution of liquid in the radial
direction is nonideal, going down through the reactor, this unfavorable distribution
does not change. In a packed-bed reactor this happens to a certain degree. Therefore
in scale-up, the reactor inlet system has to be designed well so that the distribution
of the liquid in the top of the reactor is ideal. We found that if a bubble emulsion on
top of the monolith is present, a satisfactory distribution seems to be guaranteed, as
found for trickle-bed reactor operation. We carried out a large experimental program and dened the conditions where this happens to be the case. It appeared that
FIGURE 15 Taylor ow through a single tube. Left: picture of airwater ow;

middle: schematic representation of the gas and liquid slugs; right: CFD
velocity pattern in a liquid slug showing the liquid recirculation.
the ow rate has to be above a specied minimal value. Stacking of monolith pieces
on top of each other or with some spacing in between, to allow some radial mixing,
does not seem to have a negative impact on the ow characteristics.
So the ow rates have to be sufciently high (linear velocities > 0.1 m/s) in
order to guarantee a good distribution of liquid over the cross section of the reactor. One might wonder if upow of gas and liquid is not to be preferred, because
lower ow rates might be applied. This appeared not to be the case. Again, high
ow rates are needed to establish a good gasliquid ow distribution. It might be
worthwhile to investigate whether systems can be developed or conditions established that allow low ow rates. Combinations of monolithic catalyst packages
with the Sulzer type of contactors are being conceptually investigated in our
group. They might increase the window of operability toward lower ow rates.
FIGURE 16 Relative increase of friction and mass transfer due to gasliquid

Taylor ow, compared to developed laminar ow in small tubes. represents the dimensionless length of a liquid slug, Re the Reynolds number
based on the liquid.
Moreover, they might lead to exibility, allowing more compact reactor systems.
The rst results are promising.
4.1.2.
Mass Transfer
Mass transfer was studied experimentally in various ways. Nonreactive studies

involved the uptake or release of oxygen by the liquid for the measurement
of gasliquid transfer (5153), while in reactive studies the overall gassolid or
liquidsolid transfer could be determined. As an example of the performance, a
monolith in the hydrogenation of -methylstyrene was compared with a tricklebed reactor under identical reaction conditions in cocurrent mode. Per unit reactor volume, the washcoated 400-cpsi monolith yielded a hydrogenation rate more
than four times higher. For a reaction that is mass transfer controlled, this stresses
the better mass transfer in the monolith. Overall, the Ni was used 40 times more
efciently in the monolith than in the trickle-bed reactor, even in spite of the use
of an eggshell catalyst in both cases. In spite of the high rates observed, it was felt
that not all the Ni in the washcoat layer was optimally used (5,54). In subsequent
work a more eggshell type of coating was realized and the rates observed were an
order of magnitude higher. Mass transfer is usually expressed as the factor kla, the
mass transfer coefcient times the exposed surface area per unit volume a. Values
of kla depend strongly on the gas and liquid properties, but for many systems values of 0.5 s1 are found, and values even much larger than 1 s1 possibly apply.
TABLE 3 Comparison of Gas-to-Liquid

Mass Transfer in Three Common
Three-Phase Reactor Types
Reactor type
kla (s1)
Trickle bed
Slurry
Monolith
0.050.2
0.10.3
1
This is one order of magnitude higher than in conventional reactor types (1),
which underlines the process intensication potential of monolithic reactors.
In Table 3 the three common reactor types are compared. Obviously, the
monolithic reactor in the Taylor-ow regime leads to a high degree of process
intensication. When these numbers are recalculated into production rates, values
of 40 mol/m3reactor-s were found. Figure 17 illustrates the high value in relation to
the Weisz window of reality. This demonstrates the attractiveness of using
monoliths in fast catalyzed gasliquidsolid reactions.
4.1.3. Countercurrent Operation in Monoliths
and Arranged Packings
Under practical conditions, countercurrent operation in a packed bed reactor is
not feasible, because ooding occurs (55,56). The reason is that in the small interstitial space, extended momentum transfer takes place between the liquid owing
down and the gas owing upward. At velocities used in industry this would imply
FIGURE 17 High productivity of multiphase monolith reactors.
that the particle size has to be increased by an order of magnitude. This leads to
unacceptable internal diffusion limitations. Clearly, momentum transfer has to be
decreased while maintaining high rates. This can be done by structuring the catalyst or by clever arranging of the catalyst particles in the reactor.
Various arranged catalyst structures are used or can be envisaged. Figure 18
gives an overview of the most important ones. The principle of these structures is
that relatively large channels are present, leaving space for countercurrent ow
without extended momentum transfer. In catalytic distillation a lot of experience
has already been gained in packings based on particles arranged in bales (2).
From an extensive study, it appeared that in structured reactors as well, countercurrent operation is possible at industrially relevant conditions. The breakthrough
was the design of optimal monolithic structures and dedicated inlet and outlet
systems. For example, good results were obtained by cutting the monolith under
an angle of 70 as the optimal value (57) or by a special outlet construction, guiding the liquid away from the exit (Figure 19). Finned tubes exhibit outlet ooding mainly only, whereas the unnned tube also exhibits inlet ooding. The
unnned tube has a larger hydraulic diameter due to the absence of the ns and
hence a wider ooding-free region. Injecting the gas via a capillary and guiding
away the liquid through quartz wool plugs even enlarges this region for the nned
channel. This graph illustrates that current operating region for trickle bed reactors (HDS) is well covered by the nned monoliths (58).
FIGURE 18 Various arranged particle packings.
FIGURE 19 Flow map for countercurrent gasliquid ow (n-decane/air) through

finned channels with different outlet geometries. Indicated are the ooding
limits for single tubes. Finned tubes exhibit mainly only outlet ooding,
whereas the unnned tube also exhibits inlet ooding. The unnned tube has
a larger hydraulic diameter due to the absence of the ns and hence a wider
ooding-free region. Injecting the gas via a capillary and guiding away the
liquid through quartz wool plugs even enlarges this region for the nned
channel. This graph illustrates that current operating region for trickle-bed
reactors (HDS) is well covered by the nned monoliths (From Ref. 58.)
4.1.4.
Monolith Reactors
The catalyst to be used in a reactor operation can be coated as a thin layer on the
channel walls, and, hence, the reactor can be described as a frozen slurry reactor. The diffusion length is small and well controllable.
The catalyst loading often is relatively small, but using thicker coatings or
using a monolith extruded from the catalyst support, e.g., an all-alumina monolith, can increase it. The high cell density of the monoliths creates a high geometric surface area. Using a packed bed, unrealistically small particles would be
needed to achieve this. Catalyst separation and handling are as convenient as in a
common packed bed.
Scale-up is in principle straightforward. Larger channel geometries (e.g., in
the internally nned monolith channels) allow countercurrent operation of gas
and liquid. Monolith reactors are intrinsically safer. The monolith channels have
no radial communication in terms of mass transport, and the development of runaway by local hot spots in a trickle-bed reactor cannot occur. Moreover, when the
feed of liquid or gas is stopped, the channels are quickly emptied.
From the foregoing it should be evident that monolithic reactors (and other
structured reactors) in many respects are superior to classical reactors. Indeed, for
several reactions, monolithic catalysts have been reported, although, except for
one case, only at the bench or pilot scale. The interesting points are to demonstrate that the theoretically outlined advantages are indeed present. Compared
to classical reactors they in fact boil down to a larger reactor productivity, a
better selectivity control, and a higher efciency. The rst point also implies a
better catalyst utilization. Obvious is the fact the catalyst is xed in a reactor and
pressure drops are low.
Highly exothermal reactions can be applied by external heat exchange
(1,39). If a CSTR-type reactor is not desired, the horizontal reactor with interstage cooling is an attractive alternative.
The hydrogenation step in the anthraquinone process of AKZO-Nobel is an
industrial realization of a monolithic reactor and includes a lot of pioneering work
from the Anderson group (5963). More examples of the use of monoliths can be
found in Refs. 5 and 64.
In our own group, in cooperation with a chemical industry, we have studied
the selective hydrogenation of pyrolysis gasoline, a by-product of the naphtha
cracking that can be upgraded to gasoline by selectively removing gum-forming
dienes and styrene-like molecules, leaving intact the internal alkenes. This study
(65) demonstrated the plug-ow behavior needed for such a selective conversion
and the efcient use of the active phase, which was at least a factor of 3 4 better
than in a trickle-bed operation. The hydrogenation of -methylstyrene, mentioned earlier, is an even more appealing example of better active-phase utilization and conrms the good mass transfer properties.
An attractive property of monolithic reactors is their exibility of application in multiphase reactions. These can be classied according to operation in
(semi)batch or continuous mode and as plug-ow or stirred-tank reactor or,
according to the contacting mode, as co-, counter-, and crosscurrent. In view of
the relatively high ow rates and fast responses in the monolith, transient operations also are among the possibilities.
The cocurrent monolith reactor, with its plug-ow characteristics, can in
principle be used in downow, upow, and horizontal-ow modes, provided a
good gasliquid distribution is secured (66). The last mode might solve a major
problem in practical applications of monoliths: Because, for hydrodynamic reasons, high ow rates are needed, the reactor length tends to be very large. The
process intensication potential of horizontal conguration, the so-called in-line
monolithic reactor (ILMR), has recently been demonstrated by Stankiewicz (67)
for one of the large-scale hydrogenation processes of DSM. It has been shown
that the conventional reactor system, consisting of a stirred-tank reactor and a
packed-bed reactor, could be replaced by an ILMR ca. 30100 times smaller
(depending on the type and thickness of the washcoat) (Figure 20). Research with
respect to this type of reactor is in progress. An important outcome of the research
might be that coupling of monolithic elements, mixing units and heat exchangers,
FIGURE 20 Process intensication in the in-line monolithic reactor, ILMR.
leads to exible cascade reactor setups, enabling multistep synthesis in one pass.
Further extension of the in-line monolithic reactor concept on other unit operations could possibly lead in the future to much more compact, safer, and environmentally friendly chemical plants, in which pipelines would not only serve for
sending gases and liquids, but be made functional and used for reactions or separations (68).
The best studied mode is cocurrent downow. It can be envisaged in two
ways, with either a controlled ow of gas or a free recirculation due to entrainment by the liquid at the entrance of the monolith (Figure 21). This reactor is an
alternative to the bubble-column reactor often used in biotechnological applications. Since high reactor types are being used and large gas-ow rates are
required, the energy input to introduce and compress the gas for injection at the
bottom is relatively high. In the downow monolith reactor, this gas injection is
automatically achieved. The cocurrent reactor type can easily be used as a stirred
reactor type by a large recirculation ow without extremely high energy input due
to the low pressure drop. An external heat exchanger can be scaled independent
of the reactor to deliver the required heat duty (1,5).
Of course, monoliths have disadvantages. They are at this moment more
expensive than particle catalysts. In xed-bed operation, they will have to exhibit
FIGURE 21 Conguration of a cocurrent downow monolith reactor with free

gas recirculation. Only liquid is recirculated, and an external heat exchanger
can be scaled independent of the reactor to deliver the required heat duty.
FIGURE 22 Cocurrent/countercurrent Syn Technology process scheme.
a sufciently long lifetime. In quickly (irreversibly) deactivating reactions, they

will not be used. Of extreme importance is that the inlet distribution should be
secured. In cocurrent ow, both gas and liquid have to be in contact evenly with
the catalyst at the monolith walls.
Countercurrent operation is appealing in many respects and is already executed in practice. An example is the desulfurization process of Syn Tech, where
co- and countercurrent operation are combined (see Figure 22).
Apart from the GLS-type, LLS- and GLLS-type catalytic reactions are also
possible using monoliths. The attractive property is to bring reactants efciently
in contact with the solid catalyst. But there is more. They can be applied in stripping,
extraction, evaporation, drying, and distillation, in coas well as in countercurrent
modes. Monoliths are then used as low-pressure-drop and low-energy-consuming
contacting devices. The combination with catalysis is then obvious to arrive at a
multifunctional reactor system in which reaction and controlled reactant addition
or product removal is achieved. These applications are not restricted to gaseous
or liquid phases, but also work in solid phases. The straight channels are ideal for
xed- or moving-bed applications (Figure 23), the former to combine an optimized catalyst inventory and liquid holdup while still having a relatively low ow
resistance of a single pellet-string reactor. Moreover, existing catalysts can be
applied. The use of nned channels gives even more freedom. This could be
FIGURE 23 Monolith structure packed with catalyst particles (catalyst bale)

for structured xed-bed or moving-bed applications.
considered a structured trickle-bed reactor, where longer residence times can be

achieved than in a straight-channel monolith. Blocks of monoliths lled with particles may nd application in catalytic distillation or three-levels-of-porosity
reactors (26), replacing the catalyst bales (5).
Channels lled with a single particle string have much better solid ow characteristics than a packed bed, so application of monoliths as the moving-bed reactor internal is seducing. This opens a wide range of applications, covering
moving-bed adsorption processes, moving-bed applications for deactivating catalysts (reforming, hydrodemetallization, dehydrogenation), solid trickle-ow reactors, and regenerative processes where a moving catalyst is alternatingly subjected
to different atmospheres and transport reaction intermediates and/or heat (FCC,
butane to maleic anhydride oxidation). The channel structure also works as a ow
straightener, providing better plug-ow characteristics in large-diameter entrainedow reactors, which suffer from back-mixing of catalyst at the reactor wall.
Evaluating the properties of catalytic reactors, there are three important
aspects that strongly determine the overall performance: the amount of catalyst and
intrinsic kinetics, the transport phenomena (diffusion inside and outside the catalyst),
and the hydrodynamics in the reactor. In classical reactors these are strongly interrelated and cannot be dened and designed independently. As an example, for fast
reactions small catalyst particles are desired from the point of view of catalyst effectiveness, but a packed bed with small particles will result in an unacceptable pressure
drop. Therefore an optimum has to be sought for the particle size. The elegance of
structured reactors is that these three aspects can be designed and optimized fairly
independently, resulting in an optimized reactor performance. Figure 24 shows the
situation for a monolith channel in a gasliquid reaction. The zeolite catalyst should
be very small to take advantage of its high activity. It is embedded in a washcoat
layer on the wall of the monolith channel of a thickness that yields the required catalyst effectiveness and selectivity. The channel diameter determines the type of ow,
in this case Taylor ow, which optimizes the mass transfer from the gas and liquid
phases to the solid catalyst. The straight monolith channels already ensure a low
pressure drop across the structure. This is a structured system covering about 10
orders of magnitude, from nanometers to several meters.
If the aim of the catalytic process is to optimize yield and selectivity, one
can distinguish two extremes: fast reactions and slow reactions (Figure 25). In
slow reactions, the intrinsic reaction kinetics control the process, so the catalyst
inventory should be as high as possible. Increasing the wall thickness of a monolith can have the desired effect. In fact the degree of variation in this way is virtually from 1090 volume %, whereas a packed bed will always yield an
inventory of around 60% or lower if hollow catalyst particles are used.
In fast reactions, mass transfer or intraparticle diffusion becomes controlling. Thinner catalyst coatings, Taylor ow, etc. can be applied to optimize these
FIGURE 24 Schematic representation of the operation of a monolith channel,

washcoated with a zeolite catalyst, under Taylor-ow conditions.
FIGURE 25 Aspects controlling the performance of a three-phase catalytic

reactor, indicating the exibility of the use of monolithic catalysts.
requirements. If mass transfer is controlling, the productivity is proportional to

the geometric surface area of the monolithic structure. Increasing cell densities
are recommended, without yielding unacceptable pressure drops. These examples
exemplify the potential power of the application of monolithic structures in catalytic reactors.
5.
CONCLUSIONS
Monolithic and other structured catalysts exhibit favorable properties with respect
to practical convenience, high rates, high selectivity, and low energy consumption. From an engineering point of view, the easy scale-up and the potential of
high safety are also appealing. This is not limited to single-phase processes, but
they are also well placed for multiphase processing.
Monoliths exhibit a large exibility in operation. They are well suited for
optimal semibatch, batch, continuous, and transient processing. Catalytic conversion can be combined with in situ separation, catalytic reactions can be combined,
heat integration is possible, and all lead to process intensication. In the short term,
catalytic monoliths will be applied to replace trickle-bed reactor and slurry-phase
operations in view of the better overall conversion and selectivity performance.

Monoliths allow efcient use of small catalyst particles, e.g., zeolites, and have a
substantial exibility with respect to catalyst inventory in a reactor. Multifunctional reactor operations like reactive stripping and distillation are challenging
applications that are not too far away. Several options exist for applications in the
oil renery and the chemical process industry.
The essence of the use of a structured reactor is that it allows the decoupling of intrinsic reaction kinetics, transport phenomena, and hydrodynamics. In
this way those phenomena that control the overall behavior of a catalytic reactor
can be optimized independently, giving rise to excellent reactor performance.
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7
Inline and High-Intensity Mixers
Andrew Green
BHR Group Limited, Craneld, England
1.
INTRODUCTION
High-intensity inline devices are often used to mix uids in the process industries.
Such devices include simple pipes, bafed pipes, tees, motionless mixers, dynamic
mixers, centrifugal pumps, ejectors, and rotor/stator mixers. In addition to their
traditional application in physical processes such as mixing and dispersion, such
devices can provide very effective environments for mass transfer and chemical
reaction to take place. Furthermore, combining effective inline mixing with heat
transfer is the basis of combined heat exchanger reactors (HEX reactors).
The chapter provides insight on the importance of mixing and how it relates
to process intensication using inline mixers. Design information for inline
devices such as motionless mixers, T mixers, ejectors, and HEX reactors is provided.
This should assist the reader to: (a) understand the advantages and disadvantages
of these devices as process tools for single-phase, gasliquid, and liquidliquid
applications, (b) evaluate manufacturers bids, and (c) identify opportunities for
intensifying processes, as either a retrot for existing plant or as a new process.
1.1.
Why Is Mixing Important?
Consider a simple chemical reaction, where two reactants A and B come together
and produce a product R:
AB R
The reaction will have an intrinsic kinetic rate, usually dependent on the local
concentrations of A and B. Often it will produce heat (exothermic reaction) or
require heat input (endothermic reaction). If this is not removed (or supplied) fast
enough, the temperature will rise (or fall), possibly by tens or even hundreds of
degrees. Clearly this could have disastrous consequences, particularly because
the rate of reaction will increase with temperature, potentially leading to a runaway reaction. For the reaction to take place, A and B need to be brought together;
the reactor must be mixed. This is usually not a problem in a chemists beaker,
where mixing can be very rapid. However, if it scaled up to a batch stirred vessel,
mixing inevitably becomes slower and may take several minutes in a typical
production-scale vessel. If this mixing time is slower than the reaction time, the
reaction will be articially slowed down. It becomes mixing, rather than kinetic,
limited. In other words, process inefciency is built in. For highly exothermic
reactions, matters become even worse. As a vessel is scaled up, the ratio of heat
transfer area to volume reduces, so its ability to remove heat reduces. To cope, a
process design chemist will alter conditions to slow the reaction down. This might
involve running at lower concentrations (i.e., more solvent) or operating semibatchfeeding B in slowly over many minutes or hours so that the system can
cope with the heat release. If a chemical reaction that would naturally take
place in a few seconds is slowed down to take 12 hours or more, it is clearly
inefcient.
Reactions are rarely as simple as this. There will often be other reactions
competing with the desired reaction; for example,
AB R
RB S
In other words, the desired product R reacts with reactant B to form by-product S.
If the second reaction is much slower than the rst, there should not be too much
S formed. However if mixing is slow, the rst reaction can be articially slowed
down, which will then tend to favor production of Sand yield will reduce. The
ow pattern in the reactor will also inuence the production of S. For backmixed ow, as occurs in a stirred vessel, the product stream from the reaction
zone will be continually recirculated back into contact with the reactant stream,
exposing R to fresh B. In a plug ow reactor, reactants are brought together in
the reaction zone and then removed, reducing the likelihood of the formation of
S. To summarize, production of R will be optimized by ensuring that mixing is
faster than the desired reaction step and that the reactor operates in plug ow.
The reactor is the nucleus of the process. Getting the uid dynamics right
in the reactor means improved safety, productivity, and selectivity, which in turn
inuences upstream (reduced raw material costs) and downstream (reduced separation and waste treatment costs); see Figure 1.
FIGURE 1 Importance of mixing on reactor design.
1.2.
Process intensication (PI) has various denitions, but from the point of view of
this chapter it is considered to be a design philosophy in which the uid dynamics of the plant are designed to meet the chemical and physical requirements of
process so that it can proceed at its optimal rate. As such, it integrates chemistry
and chemical engineering approaches. This can be illustrated by the generalized
S curve shown in Figure 2. If plant performance is poor (e.g., the mixing rate
is much lower than the natural speed of the desired reaction), then so is process
performance (e.g., selectivity). As plant performance improves (e.g., the mixing
rate is increased), so does process performance, up to the point where it becomes
chemistry limited. An optimum PI design will be one where the chemistry is
FIGURE 2 S curve of plant and process performance.
designed to give (in the absence of plant restrictions) the desired process performance; the plant is then designed to operate at the point at the top of the S curve
as it attens out. Moving further to the right means overdesign and increased
capital and/or running costs.
In summary, PI aims to match:
Mixing rate to reaction rate
Heat transfer performance to heat generation
Residence time to reaction time
Flow pattern to reaction scheme
1.3.
Motionless (Static) Mixers
A wide range of motionless (static) mixers is available on the market (Figure 3).
They are pipe inserts that generate radial mixing (i.e., across the pipe) and (for multiphase systems) interfacial surface area (e.g., to produce ne bubbles or droplets).
The energy for mixing is extracted from the mean ow; as such, an extra pumping
FIGURE 3 Motionless mixers: Chemineer HEV; Sulzer/Koch SMV and SMX;

Chemineer Kenics.
duty is incurred. Originally designed for laminar-ow applications, they nd wide

use in all ow regimes. The number of elements required for any application is
dependent on the difculty of the mixing duty, more elements being necessary for
difcult tasks.
Motionless mixers (and inline mixers in general) present an alternative to
the more traditional agitated vessel. These devices are particularly useful for the
continuous processing of chemicals but are also incorporated as part of a batch
system in pump-around loops.
1.3.1.
Attributes and Benets
Mixing in a motionless mixer is rapid and is achieved by the action of splitting

and twisting of the ow by the mixer elements. Energy dissipation rates are high,
with typical values between 10 and 1000 W/ kg, compared to an upper limit of
around 5 W/kg in conventional equipment, such as stirred tanks. These large dissipation rates give rise to much higher mixing rates for intensied mixers when
compared to stirred tanks.
When two phases are mixed together (gasliquid, immiscible liquidliquid),
a ne dispersion of bubbles or drops and a high specic interfacial area are produced because of the intensive turbulence and shear. For this reason, resistance to
interphase mass transfer is considerably smaller than in conventional equipment.
In addition, a wide range of gasliquid ow ratios can be handled, whereas in stirred
tanks the gas-ow rate is often limited by the onset of ooding. Mass transfer
coefcients (kLa) can be 10100 times higher than in a stirred tank.
The ow pattern in a motionless mixer is approximately plug ow; i.e., different elements of uid spend similar time periods in the mixer. Residence time
is usually short. The combination of rapid mixing and uniform, short, residence
times is specically favorable for carrying out reactions with fast kinetics.
Motionless mixers are compact, thus requiring a small site and a lower capital expenditure (CAPEX). Inherent safety is improved due to a smaller reacting
inventory. In addition, since there are no moving parts, sealing problems are
reduced and maintenance is minimized.
1.3.2.
Limitations
High-intensity mixers are not suited to slow reactions (i.e., reaction times greater
than a few minutes) where long residence times are required. However, it should
always be questioned whether the reaction is intrinsically slow or whether it has
been articially slowed to operate safely in a stirred tank. Because these reactors
are almost by denition designed to meet the needs of a specic reaction, there
can be a lack of exibility if a multiproduct plant is required. This has, however,
been addressed by BHR Groups FlexReactor (Figure 4), which combines motionless mixers in a highly recongurable package.
FIGURE 4 FlexReactor (from BHR Group).
2.
2.1.
MIXING CONCEPTS
Reynolds Number
The Reynolds number is the ratio of inertial to viscous forces in a ow. For a pipe:
Re p
u p d p
(1)
The value of Re indicates the ow regime for a specic system. A particular

regime is a property of the ow eld, not the uid, which is why the Reynolds
number is useful. Re is an important parameter for mixing considerations because
the ow regime determines the mixing mechanisms of the ow eld. At high Re,
inertial forces dominate. Energy input is required to sustain turbulent eddies, which
are active at different length scales; a degree of self-mixing exists. At low Re,
viscous forces dominate. External energy input is required to stretch, chop, and
fold uid and accelerate molecular diffusion. Ultimately, all energy input is dissipated to heat.
2.2.
Hydraulic Diameter
The empty-pipe Reynolds number is based on the inner pipe diameter and superficial uid velocity [Eq. (1)]. If the pipe contains a motionless mixer, Eq. (1) needs
to be modied to take into account the metal in the mixer, which reduces the
effective diameter but increases the uid velocity (because it blocks part of the
cross section). The theoretically sound characteristic dimension for a motionless
mixer is the hydraulic diameter, given by
dH 4
Area open to flow

Wetted perimeter
(2)
The mixer velocity is the supercial velocity divided by the mixer voidage (),
giving
Re H
u p d H
(3)
For a motionless mixer, ReH Rep, and values of dH /dp vary signicantly from
mixer to mixer, as shown in Table 1.
2.3.
Pressure Drop
In motionless mixers the energy input for mixing is provided by the pressure loss
from the mean ow. All manufacturers can provide pressure drop data. These are
usually given as a friction factor or as a multiplier for the empty-pipe pressure
drop. Values range from 30 to 1000 times the empty-pipe friction factor.
2.3.1.
Friction Factors
Care must be taken when comparing the pressure drop in motionless mixers,
because three denitions exist. In this chapter, Moodys friction factor is adopted,
TABLE 1 Ratios of Hydraulic Diameter to Pipe
Diameter for Motionless Mixers
Manufacturer
Mixer type
dH /dp (%)
Sulzer/Koch
SMV
SMX
SMXL
Kenics KMS
HEV
725
33
48
48
86
Chemineer
T1
which is the ratio of the pressure loss in one diameters length of pipe to the mean
velocity pressure:
fM
2p( d p / Lm )
(4)
u 2p
For fully turbulent ow (generally ReH 10,000), fM is roughly constant. For

laminar ow (ReH 1000), the product fM Re is a constant. Between these values (transitional ow), fM is a function of Re.
Approximate fully turbulent friction factors for motionless mixers are given
in Table 2. (Note: These gures are approximate and for comparison purposes
only; they should not be used for design. The true friction factors vary slightly
with Re and scale.)
The other friction factors in common use are the Newton number and
Fannings friction factor. The relationship between the three is:
fM

2 Ne

Moodys
Newton number
4 fF
Fannings
(5)
2.3.2. Pressure Drop and Energy Dissipation:

Turbulent Flow
For motionless mixers, energy is extracted from mean ow. Data can be correlated using an analogy with a rough pipe:
Re p
u p d p
(6)
This can then be used to determine the total energy dissipation rate in the mixer
(in W/kg):

Qp
f u3
M
Vm
2d
(7)
TABLE 2 Approximate Friction Factors for Motionless Mixers

Manufacturer
Mixer type
fM
(approx.)
Sulzer/Koch
SMV
SMXL
Kenics (KMS)
HEV
Empty pipe
6
2.5
2
0.4
0.0010.03
Chemineer
Equation (7) illustrates how critical the pipe diameter is to the energy dissipation rate: At xed throughput,

I
d7
(8)
The energy dissipation rate is a critical parameter in motionless mixers, because

it affects the rate of mixing. However, not all of the energy dissipated is useful for
mixing; in particular, laminar dissipation due to shear at the pipe wall or the mixer
does not contribute to mixing. Total energy dissipation can be split into dissipative losses (ED) and turbulent energy dissipation ( ):
ED
2.4.
(9)
Turbulent-Mixing Length Scales
Turbulent mixing is a complex phenomenon that takes place at a number of scales.

Three scales of mixing can be dened (macromixing, mesomixing, and micromixing). Macromixing, or blending, is the spreading of an additive by convective ow
patterns and turbulent dispersion. It occurs at scales of typically 102 103 m.
Following this dispersion, the largest turbulent eddies are broken down into the
smallest turbulent eddies; this is the process of mesomixing, which occurs at
scales of typically 103 104 m. Below the size of the smallest eddy, viscous
forces dominate; this is the scale of micromixing. Various processes occur at this
scale, starting with folding and wrapping (engulfment, at scales of 104 105 m),
followed by stretching of small eddies with diffusion (106 107 m).
3.
MIXING AND REACTION
For a reactive process, the reactants must be brought into contact by mixing
before a reaction can occur. In a motionless mixer in turbulent ow, the pressure
drop denes the turbulent energy dissipation rate, which then determines the
macro-, meso-, and micromixing rates.
3.1.
Slow Reactions
For a slow reaction, the mixing rates are all much faster than the inherent kinetics;
in this case the mixing and reaction processes are decoupled. For a motionlessmixer system, there must be sufcient residence time downstream of the mixer for
the reaction to go to completion. For long reaction times, a stirred tank can be used
to give the required residence time. The process then becomes:
Component mixing
t 1/2m
reaction
t 1/2r
products
The term slow needs to be used with care in PI applications. With mixing
times typically well below 1 second, reactions of only a few seconds duration can
be considered slow for a motionless mixer.
3.2.
Fast Reactions
For a fast reaction, the time scales for mixing and reaction are of the same order
(i.e., t 1/2m t 1/2r ), so mixing and reaction are no longer consecutive processes but
simultaneous:
Component mixing and reaction
t 1/2m , t 1/2r
products
For fast reactions, the mixing rate can limit the product rate of formation
and, as described in the next section, product quality/yield.
3.3.
Multiple Fast Reactions
Chemical processes often involve multiple, competing reactions. A common situation is that of a competitive-consecutive reaction, such as that described in
Section 1.1, where reactant A and the desired product R are competing for reactant B. The selectively for waste product S can be dened as
XS
2cS
c R 2c S
(10)
With very fast mixing (t1/ 2 m << t1/ 2), the distribution of products is determined by the relative kinetics of the two reactions: If the desired reaction is much
faster than the undesired reaction, Xs will tend toward zero. However, slow mixing compared to the fastest reaction (i.e., t1/ 2 m >> t1/ 2 ) slows down the desired
reaction, leading to high waste selectivities, Xs 1. It should be noted that in this
analysis, t1/ 2 m is the maximum of the three mixing time scales (
macro,
meso,
micro).
Dependent on the mixing conditions, geometry, and chemistry, any one mixing
time scale can be rate determining.
4.
4.1.
MIXING PERFORMANCE OF INLINE MIXERS

Macromixing (or Blending) Performance
Measurements of macromixing by, for example, a motionless mixer are based

on the coefcient of variation (CoV), which is a statistical measure of radial
homogeneity at the macroscale. It is dened as the standard deviation of concentration measurements made at the exit of a mixer divided by the mean
concentration:
CoV
(ci c ) 2 ] / (n 1)
i 1

c
c
(11)
n is the number of measurements (e.g., conductivity probes or sampling positions)

used over the pipe cross section (usually 9). ci is the time-averaged concentration
of the ith probe. CoV characterizes the degree of blending achieved between an
additive and the bulk stream. The lower the CoV, the better the streams are mixed.
A CoV of 5%, or 0.05, is often used as the benchmark. The physical meaning of this value is that there will be a 95% probability that all samples taken will
be 2CoV (i.e., 10%) of the mean mixed concentration. Correlations for CoV
are usually expressed in terms of the ratio between the coefcient of variation
downstream to the coefcient of variation at the inlet to the mixer [i.e.,
CoV/(CoV)0].
4.2.
Blending Correlations
4.2.1.
Empty Pipe: Turbulent Flow
Blending performance for an empty pipe is critically dependent on where and

how the uid is injected [Eqs. (12) and (13) and Ref. 1].
Centerline injection: CoV/(CoV)0 2 exp(0.75f D1/2 L /d )
Wall injection (low velocity): CoV/(CoV)0 2 exp(0.25 f
(12)
1/ 2
D
L /d ) (13)
It can be shown that

(CoV)0 (Q/q)1/2
(14)
For example, for q/Q 104, Rep 105, fD 0.02, and CoV 0.05, L/d for centerline injection is 78, whereas for wall injection it is 234.
It should be noted that when additive ow has signicant momentum, much
more rapid blending is possible (so-called T mixer). An optimum value of momentum ratio between main ow and additive can be found (see Ref. 2 for details).
4.2.2. Turbulent and Transitional Flow Mixing
in Motionless Mixers
Motionless-mixer manufacturers usually have experimentally based correlations
to predict macromixing performance in turbulent ow. These often use slightly
different bases, so care has to be taken when comparing performance.
For the Koch/Sulzer SMV in turbulent ow (Rep 2000), signicant mixing continues to be achieved for several diameters downstream of the mixer.
Usually mixing is measured/dened two diameters downstream of the mixer, and

performance is given by (3)
CoV/(CoV)0 2 exp(1.5 L /d p )
(15)
where
(mixing length)
L Lm 2dp
Lm nLe
(mixer length)
Equation 15 applies for viscosity ratios B/A 100 and shows that the mixing
length to achieve a given CoV is 13 times shorter than for an empty pipe. To take
advantage of the mixing downstream of the mixer, SMV elements are often
spaced out in pairs in turbulent ow. The length of one element depends on the
mixer diameter: For mixer diameters 100 mm, the length of an element (Le) is
equal to one pipe diameter, but for mixer diameters 100 mm, Le 0.5dp.
For the Chemineer Kenics and HEV mixers, a correlation has been developed that covers both mixers (4). For fully developed turbulent flow
(ReH 8700):
log10 [CoV/(CoV) 0 ] 1.65Re 0.043
(0.0879n 0.7363)
H
(16)
For 1000 ReH 8700:

log10 [CoV/(CoV) 0 ] 0.27Re 0.24
H ( 0.0879n 0.7363)
(17)
Equations (16) and (17) are for measurements three pipe diameters downstream
of the mixer and are valid for viscosity ratios B/A 100.
The macromixing length (say, to give CoV 0.05) is insensitive to Re
under fully turbulent conditions. So for a higher velocity, though the mixer length
remains constant, the time for mixing will be shorter. Put another way, macromixing time is inversely proportional to pipe velocity.
For transitional ow, precise correlations are not available; but for both
SMV and Chemineer Kenics mixers, extra elements are required to achieve a certain degree of mixing. The SMV does not achieve signicant mixing downstream
of the mixer as in turbulent ow, so elements are not spaced out. The HEV is not
recommended for transitional ow.
4.2.3. Mixer Rankings for Turbulent-Flow
Blending Applications
The ranking of mixers for a blending application will depend on what the user is
trying to achieve. If blending efciency is most critical (i.e., achieving the
required mixing for minimum pressure drop/energy use), the most efcient mixer
is, in fact, an empty pipe. After that the ranking is:
Empty pipe HEV Kenics or SMV SMX
However, if the rate of mixing is important (i.e., the need to achieve the most mixing in the shortest length), the ranking becomes:
SMV HEV Kenics SMX Empty pipe
The performance of the HEV should be noted: It was designed to be hydrodynamically efcient and to use ow vortices, rather than metal, to achieve
mixing. Despite a low pressure drop, the HEV can achieve mixing more efciently and in a shorter length than the Kenics [as shown in Eqs. (16) and (17),
it has the same design correlation with respect to number of elements, but element spacing is shorter]. However, care needs to be taken in its installation,
because performance can be signicantly degraded if there is an uneven ow distribution at its inlet (e.g., if it directly follows a bend). The poor performance of
the SMX is to be expected because it has been designed specically for laminarow applications and is not recommended for turbulent-ow applications by its
manufacturers.
4.2.4.
Axial Dispersion
The coefcient of variation is a measure of mixing across the pipe cross section
(radial dispersion). In pipe-ow and motionless mixers, mixing along the length
of the mixer (axial dispersion) occurs. This can be described in terms of the residence time distribution (or RTD), which is a measure of age distributions for uid
elements passing through the mixer. An empty pipe has relatively high axial dispersion, primarily caused by the ow prole that is established in a pipe (i.e., the
uid in the center of the pipe ows faster than that near the walls). Motionless
mixers tend to have a much tighter RTD.
4.2.5.
Blending Correlations: Laminar Flow
Despite the wide use of the striation thickness concept in the early commercial
literature, the CoV is now the most widely used mixing index. The following correlations are valid for viscosity ratios 0.01 B/A 100, feeding into the center
of the pipe and with CoV measured 2dp downstream for Sulzer mixers, 3dp downstream for Kenics mixer.
SMX (Rep 200, Le /dp 1.0):
log10 (CoV/(CoV) 0 ) 0.19n 0.19 Lm /d p
(18)
SMXL (Rep 200, Le /dp 3.3):

log10 (CoV/(CoV) 0 ) 26n 0.078 Lm /d p
(19)
Kenics (Rem 200, Le /dp 1.5):

log10 (CoV/(CoV) 0 ) 0.098n 0.067 Lm /d p
(20)
where
n number of motionless-mixer elements
Le length of one mixer element
These data are consistent between the manufacturers and independent investigators.
4.2.6.
Mixer Rankings for Laminar-Flow Applications
As with turbulent ow, ranking depends on the requirements of the application.

Based on various literature data, where at least two datasets exist, the following
rankings can be made.
Energy efciency (most efcient rst):
SMXL Kenics SMX Hi-mixer Komax Lightnin
Ross ISG
Mixing rate (most rapid rst):
SMX Ross ISG Hi-mixer SMXL Kenics Komax
Lightnin
4.2.7.
High Viscosity Ratios
Laminar-ow blending duties involving high viscosity ratios (greater than 1000 : 1)
are classied as difcult. The SMX mixer appears to have the best track record in
achieving satisfactory results.
4.3.
Mixing with Reaction in Inline Mixers
If a mixer is to be used for reactive processes, it should be designed such that the
longest mixing time scale (whether micro-, meso-, or macromixing) is signicantly shorter than the characteristic time scale of the desired chemical reaction.
As mentioned in Section 3, any of the time scales can be rate determining.
4.3.1.
Micromixing Limited
If
micro
meso
macro , then the process is micromixing controlled. Micromixing
is a complex phenomenon (Section 2.4), but for most liquids engulfment is the
longest step. In this case, micromixing time is the inverse of engulfment rate (E)
and can be estimated by
micro
1
1

E 0.058
1/ 2
(21)
Detailed models have been developed that can predict product distribution for
competitive reactions with known kinetics under micromixing- (engulfment-) controlled conditions (5).
4.3.2.
Mesomixing Limited
In motionless mixers, mesomixing time can be estimated from

Q
meso 2.17 B
nf u
1/ 3
(22)
Numerical models for mesomixing control with reactions are being developed, although they are more complex than micromixing models and require the
input of empirically determined length scales. Mesomixing limitations give rise
to worse process performance than if micromixing alone were limiting, so if possible mesomixing time should be reduced (e.g., by increasing the number of additive feeds or reducing the additive ow rate) to the point that micromixing controls.
However, in practice this is often not possible.
4.4. Scale-Up/Scale-Down of Motionless Mixers
(Single Phase)
For systems involving fast reactions where reactor performance has been established at one scale and equal performance is required at different scales, the criteria for scale-up/scale-down are:
The mixing rate of the limiting step (characteristic time scale) should be kept
constant.
Residence time in the mixer should be constant.
The limiting mixing mechanism should not change.
The process conditions should remain the same, e.g., reactant concentrations, ow rate ratio, mixer type, relative feed position. If the friction factor,
mixer voidage, and turbulence-generating efciency do not vary signicantly
with scale, then the following scale-up rules can be applied (where k Qnew /Qold,
the mixer diameter should be rescaled from dold to dnew).
4.4.1.
Macromixing or Mesomixing Limitation
For a macro- or mesomixing limitation,

dnew k 1/ 3 dold
(23)
The resulting design will have the same number of elements at the new scale
(resident time constant), so the length of the mixer will be
d
lnew new lold
dold
4.4.2.
(24)
Micromixing Limitation
For a micromixing limitation,

dnew k 3/ 7 dold
(25)
If residence time is kept constant, fewer elements will be required at the larger
scale, and
1/ 3
d
lnew new lold
dold
5.
(26)
GASLIQUID MIXING
5.1.
Introduction
Gasliquid reactions form an integral part of the production of many bulk and
specialty chemicals, such as the dissolution of gases for oxidations, chlorinations, sulfonations, nitrations, and hydrogenations. When the gaseous reactant
must be transferred to the liquid phase, mass transfer can become the rate-limiting
step. In this case, the use of high-intensity mixers (motionless mixers or ejectors)
can increase the reaction rate. Conversely, for slow reactions a coarse dispersion
of gas, as produced by a bubble column, will sufce. Because a large variety of
equipment is available (bubble columns, sieve trays, stirred tanks, motionless
mixers, ejectors, loop reactors, etc.), a criterion for equipment selection can
be established and is dictated by the required rate of mass transfer between
the phases.
5.2.
Mixer Types
5.2.1.
Motionless Mixers
When a gas stream is introduced into a turbulent liquid ow in a motionless

mixer, the gas is broken up into bubbles. The breakup is due mainly to the turbulent
shear force of the liquid but also partly to the collision between gas and the leading edge of an element.
There are two basic operating modes:
Continuous, as a stand-alone mixer
Loop operation (either semibatch or continuous).
A stand-alone mixer requires the mass transfer/reaction to be completed

within the mixer. If the gas ow rate matches the stoichiometry of the liquid phase,
all the gas should be dissolved and reacted at the end of the mixer. This generally
involves very high volumetric ratios between gas and liquid. If there is excess gas,
there will be some gas at the mixer outlet, which needs to be separated.
5.2.2. GasLiquid Ejectors
Ejectors consist of four main sections (Figure 5):
Spinnerorients and stabilizes the ow.
Nozzleprovides a high-velocity jet of uid.
Gas chamberthe high-velocity jet creates suction in the gas chamber,
entraining gas into the ejector.
FIGURE 5 Gasliquid ejector.
Mixing tubeon leaving the gas chamber, the liquid jet attaches itself to
the mixing tube wall, resulting in a rapid dissipation of kinetic energy,
creating an intensive mixing zone known as the mixing shock region.
High turbulence in this region breaks up the gas, producing a ne dispersion of bubbles and consequently a large interfacial area for mass
transfer.
By and large, ejectors and motionless mixers have similar mass transfer
performance at a given gas-to-liquid ow ratio and energy input. However, ejectors have a number of benets and drawbacks compared to a motionless mixer. On
the positive side, the ejector suction means that a pressurized gas supply is not
required. The unrestricted mixing tube means that solid formation due to reaction
is not problematic. Against this, the operation is sensitive to changes in the
gasliquid ow ratio and diameter/length ratio. Gas-to-liquid ow ratios are also
more limited in ejectors.
5.3.
Loop Reactors
Motionless mixers and ejectors are useful for applications requiring short residence times (on the order of seconds or less). If long residence times are required,
e.g., if the reaction is relatively slow, the use of a motionless mixer alone would
lead to a very long mixer, which may not be practical. One way to overcome this
problem is to use a loop reactor, which combines a high-intensity mixer, such as
a motionless mixer or ejector, with a separation tank.
5.4.
Guide to Equipment Selection
Tables 3 and 4 summarize where different mixers/congurations are most appropriate.

TABLE 3 Application of Mixer Types and Congurations
Motionless-mixer
stand-alone
Solids present
Slow reaction
Fast reaction
Energy
efciency
important
Low gas
Pressure
Motionlessmixer loop

Ejector
stand-alone
Ejector
loop

TABLE 4 Application of Chemineer Kenics and

Koch/Sulzer SMV Mixers
Mixer type
Situation
p constraint
Space constraint
Solids present
Energy efciency important
Need for heat removal
5.5.
Kenics
SMV

Mixing Concepts
5.5.1.
Rate of Mass Transfer
The rate of mass transfer for motionless mixers and ejectors can be described by
NA KLa CLM
(27)
where NA is the amount of transferred species per unit time per unit dispersion
volume, KL is the overall mass transfer coefcient, a is the specic surface area
for mass transfer, and CLM is the log mean concentration driving force. 1/KL,
the overall mass transfer resistance, is usually dominated by the resistance in
the liquid phase, 1/kL. Consequently, the gas-phase resistance can be neglected
and KL kL. However, it is imperative that this assumption be checked, because
it does not always hold for very soluble gases or when kLa is enhanced by
reaction (6).
The large levels of turbulent energy dissipation produced in high-intensity
mixers act to reduce the bubble size, typically from 0.5 to 2.0 mm in high-intensity
mixers, compared to 1.0 to 5.0 mm in stirred tanks and bubble columns. In addition,
much higher gas-to-liquid ratios can be achieved, and turbulence enhances kL,
leading to overall mass transfer coefcients (kLa) 10100 times greater than for a
stirred tank.
5.5.2.
Reaction Regime
The relative speed of kinetics to mixing is described by the Hatta number,

t
Ha MT
tR
0.5
(28)
where tMT and tR are the time constants for mass transfer and reaction, respectively.
The lower the value of Ha, the faster the mixing relative to the intrinsic reaction
rate. Ha can be calculated from
D
2
( n A 1) nB
Ha 2A k AB CAL
CBL
n A1
kL
0.5
(29)
Reactions are often classied into four categories:

Ha 0.02
0.02 Ha 2
Ha 2
slow reaction
moderately fast reaction
very fast or instantaneous reaction
For Ha 0.02, there is a considerable scope for process intensication. If a reaction is intrinsically fast (a large reaction rate constant) the design aim is to
provide sufciently intense mixing to move it into the slow reaction regime
(Ha 0.02) such that the reaction is limited by the intrinsic reaction rate rather
than the mass transfer rate.
In order to establish the reaction regime and to design equipment, the following need to be known:
Flow pattern
Mass transfer coefcient
Bubble sizes
These can be determined from gasliquid ow rates, the energy dissipation rate
(driven by the pressure drop), and the physical properties of the uids.
5.6.
Design Guidelines and Correlations
5.6.1. Flow Patterns

Gasliquid ows are much more complicated than single-phase ows, due to the
existence of the gasliquid interface. The phases can be present in a range of possible ow regimes (ow patterns), which are dependent upon the physical properties of both phases, the ow rates, and the equipment size and orientation. The
most commonly noted ow patterns are (7):
Annular owa liquid lm on the walls and a continuous gas phase, containing a mist of liquid droplets, in the core
Intermediate slug owlarge gas voids containing liquid droplets
Bubble owcontinuous liquid ow with a dispersion of gas bubbles
Figure 6 shows the various ow patterns in horizontal ow, and similar patterns can be seen in vertical upow or downow. In general, bubble ow develops
under high liquid-ow rates and low gas-ow rates; annular ow develops under
FIGURE 6 Gasliquid ow patterns in horizontal ow.
low liquid-ow rates and high gas-ow rates; stratied ow develops in low gasand liquid-ow rates.
Bubble ow is generally more desirable for liquid-lm controlled mass
transfer processes because of the high turbulence level in the liquid phase, while an
annular ow is more desirable for gas-lm controlled processes, where the
turbulence level in the gas phase is high. However, in reactive systems, stoichiometry will often dene the gas- and liquid-ow rates, leaving no choice for the ow
pattern. Having said this, motionless mixers and ejectors can maintain the bubble
ow regime even at high gas-to-liquid ow ratios, where ooding of the impeller
would occur in a stirred tank or annular ow develop in empty pipes (Figure 7 (8)).
5.6.2.
Pressure drop
Pressure drop is a critical parameter, in that it determines pumping requirements

and enables the power input to the mixer to be calculated.
Motionless Mixers. Major mixer manufacturers agree that the Lockhart
and Martinelli parameters for two-phase ow in pipes (9) can also be applied to
motionless mixers. To estimate the pressure drop, the single-phase liquid and gas
pressure drops are rst calculated. The Lockhart and Martinelli para-meter X is
found from
X
pL
pG
(30)
FIGURE 7 Flow pattern maps for cocurrent airwater upow through motionless mixers. (From Ref. 8.)
and the two-phase pressure drop can be calculated from

p L2 pL G2 pG
(31)
where L and G are functions of X for the liquid and gas phases, respectively,
obtained from the Lockhart and Martinelli charts (Figure 8, Ref. 9) or from the
following empirical equations:
L ( 4.6 X 1.78 12.5 X 0.68 0.65) 0.5
(32)
G
(33)
X2
Ejector. Gas chamber pressure needs to be known in order to

calculate ejector power input. A semiempirical equation was developed by
Henzler (10) that related the entrainment ratio to other system variables:
QG
D
B1 0.38 m
QL
Dn
L

G
0.09
p2
1
ps
1/ 6
2( p2 ps )
L u 2j
(34)
Gas chamber pressure, ps, can be calculated from this equation through iteration.
Factor B depends on the mixing tube/nozzle diameter ratio for a given ejector
type and needs to be determined experimentally.
FIGURE 8 Lockhart and Martinelli parameters for pressure drop in multiphase ow.
The nozzle pressure, which determines the selection of the liquid pump, is
given by
D 4
1
p1 ps L u 2j 1 n
2
D1
5.6.3.
(35)
Power Input
The power input, required for calculation of the mass transfer coefcient, is calculated from Eqs. (36) and (37). For a motionless mixer, the power comes from
the gas and liquid phases; for the ejector, power comes from the liquid only.
In a motionless mixer:
p
1
P QL p QG pav ln 1 QL u L21 u L2 2
2
p2
(36)
(37)
In an ejector:
p
1
P QL p QG pav ln G QL u L21 u L2 2
2
p
2
Generally, kLa values at the same power input are similar between the two devices (11).
5.6.4.
Mass Transfer Coefcients
The amount of gas transferred is proportional to the product of the mass transfer
coefcient (kL ) and the specic area (a). Because most measurement techniques
measure this product, many correlations for kLa appear in the literature. However,
caution is advised, because they can give different predictions for the same operating conditions. Equations (38) and (39) are two examples from independent
investigators for motionless mixers, from Refs. 12 and 8, respectively:
P
k L a 1.74 104
V
P
k L a 0.64
m
0.8
(38)
0.75
(39)
The majority of reported correlations for ejectors are for loop-type congurations, e.g., (13):
P
k L a 0.044
V
0.76
with very little reported on the stand-alone conguration.
(40)
Comprehensive correlations for motionless mixers and ejectors have been

developed as part of BHR Groups HILINE Consortium, but these are available
only to members.
5.6.5.
Bubble-Size Calculations
When a gas stream is introduced into a turbulent liquid ow in a motionless

mixer, the gas is broken up into bubbles. The breakup is due mainly due to the
turbulent shear force of the liquid but, for motionless mixers, also partly to the
collision between the gas and the leading edge of an element. Gas dispersion is a
physical process and involves bubble breakup and coalescence, which can both
take place in the same mixer/reactor.
Bubble breakup and coalescence are both complex processes. In a turbulentow eld, bubbles are broken up mainly due to the turbulent shear force, and the
eventual bubble size is a balance between this force and the surface tension force.
For a given gasliquid system and ow eld, a maximum bubble size exists. Any
bubbles larger than this size will be broken up. According to theory (14), this maximum bubble size relates to gasliquid physical properties and ow characteristics:
We crit
dmax
0.6
0.6
c2 d
0.2
0.4
(41)
Wecrit is the modied critical Weber number, which is close to 1.

Coalescence occurs when two bubbles approach each other, collide, and
become one bigger bubble. Two important factors are:
Frequency of collision
Efciency of coalescence
The frequency of collision relates to the ow pattern and gas volume fraction: The
more random the ow pattern or the higher the gas volume fraction, the higher
the frequency. The efciency of coalescence relates to physical properties of the
gasliquid system. Some systems, such as airwater, have a high efciency of
coalescence and are often called coalescing systems. Other systems, such as
gasalcohol or gassalt solution, have a low efciency of coalescence and are
called noncoalescing systems.
5.6.6.
Characterization of Bubble-Size Distribution
It is useful to dene an appropriate average to characterize bubble-size distribution. For heat and mass transfer, the Sauter mean diameter (d32) is generally used:
d32
ni di3
ni di2
(42)
Hesketh et al. (2) proposed that the general equation of Hinze (14) was valid for
the turbulent dispersion of a gas using any motionless mixer or an empty pipe:
Wec
d32 Cn
0.6
0.6
2

L G
0.4
2
(43)
where Cn 0.6 and Wec 0.61.6.

The Sauter mean diameter (d32) is related to the interfacial area per unit
volume (a) and dispersed phase volume fraction by
a6

d32
(44)
where QG/(QG Q1).

If kLa and a are known, kL can be estimated and, provided the reaction
kinetics are known, Ha can be calculated from Eq. (29) and the reaction regime
deduced.
6.
6.1.
LIQUIDLIQUID DISPERSIONS
Introduction
Motionless mixers are highly effective for producing dispersions of immiscible liquids. Applications can be physical (e.g., for liquidliquid extraction)
or chemical (e.g., many nitration reactions). As with gasliquid mixing, the
most relevant parameter to measure for such applications is the Sauter mean
diameter.
6.2.
Turbulent-Flow Correlations
A range of correlations is available from the literature, usually relating the Sauter
mean diameter to the Weber number, which is the ratio of shear forces to surface
tension forces:
We c u 2p d p /
(45)
Most correlations show that d32 is proportional to the Weber number raised
to the power of 0.6, which is consistent with the theory of drop breakup by turbulent shear forces. Strictly, these correlations should be applied only where the
drop size is in the inertial subrange of turbulence, i.e.,
k d32 dp /4
(46)
where k is the Kolmogorov length scale

k (v3/ )1/4
6.2.1.
(47)
Kenics Mixer
Two very similar correlations have been developed for Kenics mixers (15,16) of
the form
d32
CWe0.6
dp
(48)
where C 0.45 for the former and 0.49 for the latter. These are valid for fully turbulent ow in a pipe (Rep 12,000), inviscid drops (d c) and were measured
with water as the continuous phase. The dispersed-phase fraction has little effect up
to a value of 0.25. Equilibrium drop size is achieved with only eight mixer elements.
For viscous drops (d up to 200 mPa) in turbulent ow, Berkman and
Calabrese (16) developed the correlation further to give
1/ 3
d32
d32
0.6
0.49 We 1 1.38Vi

dp
d p
0.6
(49)
where
d u p c
Vi
d
1/ 2
(50)
For higher viscosity ratios, more elements were needed (24 in these experiments).
6.2.2.
Sulzer (Koch) Mixers
Sulzer published correlations in the open literature for drop size. An early correlation for the SMV is (3)
d32
0.21We 0.5 Re 0H.15
dH
(51)
where We is the Weber number based on hydraulic diameter, i.e.,

We
c u 2p d H

(52)
The correlation was developed for ve 50-mm SMV elements (dH 8 mm) and
covered Reynolds numbers (ReH) in the range 20020,000 and dispersed-phase
volume fraction up to 0.25.
More recent work (17) has covered viscous drops in turbulent ow, over
a wide range of mixer types (SMV, SMX, SMXL, SMR, SMF), diameters (up to
80 mm), lengths, and dispersed-phase viscosities (up to 70 mPa):
(1 BVi)We c
d32 0.65(1 kd )
0.6

c
0.6
0.1
c 0.4

d
(53)
where Wec 1.8 and Vi is the viscosity number [Eq. (50)].

6.3. Comparison Between Motionless Mixers
and Stirred Tanks
Comparison between drop sizes for a motionless mixer and a (well-) stirred tank
under typical operating conditions yields an interesting result that similar drop
sizes can be obtained in both despite very different average energy dissipation
rates. This is down to the extremely inhomogeneous energy dissipation in a stirred
tank, where the peak rate (usually close to the impeller tip) can be similar in magnitude to that in the more homogeneous motionless mixer. However, a stirred tank
may take hours of operation to achieve an equilibrium drop size, whereas a motionless mixer will achieve it with a few elements and in less than a second. This has
implications for two-phase applications when it is important to rapidly achieve
mass transfer to complete fast chemical/physical reactions or to minimize byproduct formation from complex fast reactions.
6.4.
Scale-Up/Scale-Down
When scaling up or scaling down a liquidliquid process in turbulent ow, the

energy dissipation rate needs to be kept constant, giving
dnew (Qnew /Qold )3/ 7 dold
(54)
However, checks should be made that ow is fully turbulent at both scales and
that the drop size remains within the inertial subrange of turbulence [Eq. (46)].
As a minimum, residence time should be maintained, i.e.,
1/ 3
d
lnew new lold
dold
(55)
This suggests that fewer elements will be required at a larger scale; however, for
a conservative design on scale-up, the same number of elements should be maintained. On scaling up or scaling down, the same mixer type and feed arrangement
should be maintained.
7.
7.1.
COMBINED HEAT EXCHANGER-REACTORS (HEX REACTORS)

HEX Reactor: Concepts
The mixers discussed in Sections 46 are particularly suitable for reactions where
the required heat input (endothermic reaction) or heat production (exothermic
reaction) is modest (i.e., temperature changes on reaction would be only a few
degrees in the absence of any heat transfer). HEX reactors can be used for rapid,
highly exothermic (or endothermic) reactions; not only are the mixing rate and
residence time of a reactor matched to the kinetic rate and reaction time, but heat
transfer performance is also matched to heat production (Figure 9).
7.2.
HEX Reactor Types
HEX reactors generally fall into three basic types (18).

a. Jacketed motionless-mixer reactors (Figure 10): Motionless mixers
provide a highly effective and efcient mixing environment for rapid
reactions. Heat transfer capacity can be provided by utilizing either
single mixers in jackets or multiple mixers in a shell-and-tube geometry.
The FlexReactor (Figure 4) has been designed to package motionless
mixers in a highly recongurable unit with effective heat transfer.
b. Compact heat exchangers: There is a wide variety of commercially
available compact heat exchangers available (e.g., enhanced shell and
tube, plate and frame, platen, and diffusion-bonded). Such devices
provide extremely effective heat transfer but have not been optimized
as reactors, compromising their efciency.
FIGURE 9 HEX reactors: principle of operation.
FIGURE 10 Jacketed motionless mixer.
TABLE 5 HEX Reactor Considerations

Attribute
Bespoke HEX
Motionless mixer
FlexReactor
Typical heat
transfer
coefcient
HT density
Material of
construction
Scale-up
procedures
U 1500 W/m2-K
U 800 W/m2-K
U 600 W/m2-K
5000 m2/m3
Limited
900 m2/m3
Wide
900 m2/m3
Wide
Use more units

in parallel
Cost
Mixing
Multipoint feed
Increase tube
length/
diameter
Medium
High
Yesvariable
Availability
Residence time
High
Low
Yesbut xed
once
constructed
Low
Low
Increase tube
length/
diameter
Low
High
Yesbut
xed once
constructed
High
High
Flexibility
Low
Low
Medium
High and
variable
High
c. Bespoke HEX reactors: A good example is the MarbondTM reactor,

supplied by Chart Industries, which has been designed specically as a
heat exchanger-reactor, combining high heat transfer with effective
mixing (although its high surface area results in relatively low
micromixing efciencies). Passageways are typically of the order of a
few millimeters. Its diffusion-bonded construction is very robust, and it
can be constructed to provide an optimized feed arrangement.
The choice of reactor will be very dependent on the requirements of the
chemical reaction scheme, the relative importance of mixing and heat transfer, and
practical considerations (e.g., the effect of solids in the process; materials of construction; exibility). A comparison of the typical performance of different designs
is given in Table 5. HEX Reactors are discussed in more depth in Chapter 4.
NOMENCLATURE
Symbol
Explanation
Units
a
ci
c
CoV
Cn
C*AL
CBL
D
DAL
Dm
Dta, Dax
Dtr
d
dB
dH
dmax
dn
dp
d32
E
EB
Ep
fM
g
KL
k
kL
Interfacial area
Concentration of species i
Mean concentration
Coefcient of variation
Constant 0.6
Equilibrium concentration of A
Bulk liquid concentration of B
Stirred-tank impeller or rotor diameter
Diffusion coefcient of A in liquid
Molecular diffusivity
Axial turbulent dispersion coefcient
Radial turbulent dispersion coefcient
Droplet diameter
Feed pipe diameter
Hydraulic diameter of motionless mixer
Maximum stable drop size
nozzle diameter
Internal pipe diameter
Sauter mean diameter
Engulfment rate coefcient
Ratio of viscous to interfacial forces
Rate of direct energy dissipation
Moodys friction factor
Acceleration due to gravity
Overall mass transfer coefcient
Second-order reaction rate constant
Liquid-side mass transfer coefcient
m1
mol-m3
mol-m3
mol-m3
mol-m3
m
m2-s1
m2-s1
m2-s1
m2-s1
m
m
m
m
m
m
m
s1
W-kg1
ms2
ms1
m3-mol1-s1
ms1
Lc
Le
Lm
LR
m
N
NA
Ni
n
ne
nf
P
P1
P2
Ps
p
Q
T
t
up
v
V
X
Xi
z
Concentration integral length scale

Length of one mixer element
Length of motionless mixer
Length of reaction zone
mass
Impeller rotational speed
Mass transfer rate
Total number of moles of species i
Number of sampling positions used in
CoV measurement
Number of motionless mixer elements
Number of additive feed tubes
Power
Inlet pressure
Exit pressure
Gas chamber or suction pressure
Pressure drop over motionless mixer
Volumetric ow rate
Dimensionless time
Stirred-tank diameter
Time
Supercial pipe velocity
Velocity
Liquid volume
Lockhart and Martinelli parameter
Selectivity for product i
Ratio of mixer friction factor to pipe
friction factor
m
m
m
m
kg
rps
mol/s
mol
W
Pa
Pa
Pa
Pa
m3-s1
m
s
m-s1
m s1
m3
Greek Symbols

k

Flow rate ratio (QA,C /QB)

Shear rate
Turbulent energy dissipation rate
Efciency of turbulence generation
Voidage of a motionless mixer
Turbulence-generating length scale
Kolmogorov microscale
Dynamic viscosity
Kinematic viscosity
Fluid density
Standard deviation
Interfacial tension
Characteristic time scale
Total energy dissipation rate
Dispersed phase volume fraction
s1
W-kg1
m
m
mPa-s
m2-s1
kg-m3
N-m1
s
W-kg1
Dimensionless Groups
Da
Re
Sc
We
Wecrit
Ha
Damkohler number (k2-o cB0 /E)

Reynolds number (updp/v)
Schmidt number (v/Dm)
Motionless-mixer Weber number (cup2dp /)
Stirred-tank Weber number (c N 2D3/)
Critical Weber number (0.61.6)
Hatta number
Subscripts
1
2
av
c
d
E
G
H
j
L
MT
m
macro
meso
micro
mix
p
Q
R
R
T
1/2r
At inlet
At exit
Average
Continuous phase
Dispersed phase
Engulfment
Gas
Based on hydraulic diameter
Jet
Liquid
Mass transfer
Motionless mixer
Macromixing
Mesomixing
Micromixing
Slowest mixing step
Empty pipe
Competitive-parallel reactions
Radial
Reaction
Tangential
Reaction half-life
REFERENCES
1.
2.
3.
4.
Henzler HJ, Chem Ing Tech, 1980; 52:659661.

Hesketh RP, Russel T, Etchells AW. R&D notes. AIChE J 1987; 33(4):663667.
Streiff FA. Sulzer Tech Rev 1977; 3.
Knight CS. Experimental investigation of the effects of a recycle loop/static mixer/
agitated vessel system on fast, competitive-parallel reactions. PhD dissertation, University of Arkansas, 1994.
5. Baldyga J, Bourne JR. Principles of micromixing. J Fluid Mechanics 1986; 1:147.
6. Middleton JC. In: Harnby N, Edwards MF, Nienow AW, eds. Mixing in the Process
Industries. 2d ed. London: Butterworth Heineman, 1992:Chapter 15.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
Drahos J, Cermak. Chem Eng Processes 1989; 26:147.

Roes AWM, Zeeman AJ, Bukkems FHJ. I Chem E Symposium Series, 1984; (87):
231238.
Lockhart RW, Martinelli RC. Chem Eng Prog 1949; 45:39.
Henzler HJ. Chem Eng Tech 1980; 52:659661.
Zhu M. Proc. 1st International Conference on Process Intensication, Antwerp,
Belgium, December 68, 1995, organized by BHR Group, Craneld, UK, 5159.
Middleton JC. AIChE 71st Annual Meeting, Miami Beach, Paper 74E, 1978.
Dutta NN, Raghavan KV. Chem Eng J 1987; 36:111121.
Hinze JO. AIChE J 1955; 1:289295.
Middleman S. Ind Eng Proc Des Dev 1974; 13:78.
Berkmann PD, Calabrese RV. AIChE J 1988; 34(4).
Streiff FA, Mathys P, Fischer TU. New fundamentals for liquidliquid dispersion
using static mixers. Rcents Progrs en Gnie des Procds 1997; 11(51):307314.
Green A, Johnson B, Westall S, Bunegar M, Symonds K. Combined chemical reactor/
heat exchangers: validation and application in industrial processes. 4th International
Conference in Process Intensication, Brugge, Belgium, September 2001.
8
Reactive and Hybrid Separations:
Incentives, Applications, Barriers
Andrzej Stankiewicz
DSM Research, Geleen, The Netherlands
1.
INTRODUCTION
Integration of various steps/operations presents one of the most promising ways

for intensifying (bio)chemical processes. It can be achieved either by combining
reaction and separation in a single reactive separation step or by combining two
(or more) separation techniques in a hybrid separation unit. Such an integration
may bring a number of advantages to the process under consideration, not just a
decrease in the size of equipment.
This chapter provides a general overview of the reactive and hybrid separations and discusses their place in the intensication of (bio)chemical processes.
Written from an industrial point of view, it focuses on the application aspects of
those integrative technologies. Potential application elds are reported, along
with already existing commercial-scale operations. Special attention is given to
the barriers that hamper a broader introduction of the reactive and hybrid separations into industrial practice and the ways to overcome those barriers. The modeling and design aspects of three reactive separation methods (reactive
distillation, reactive absorption, and reactive extraction) are discussed in more
detail in Chapter 9.
2.
REACTIVE SEPARATIONSWHY INTEGRATE?
In the simplest case, integration of reaction and separation may take place on the
purely equipment level, without introducing any new functional interrelations
between the operations involvedthe reaction does not inuence the separation,
nor has the separation process any effect upon the reaction. The aimed result of
such combination can be:
Lower investment costs (compact plant layout, integral design)
Smaller inventory (safety aspects)
Improved heat management/energy utilization.
The Urea 2000plus technology, developed by Stamicarbon B.V. (1) and
described further in Chapter 12, presents a typical example of such a noninterrelating integration. The integration resulted here in a considerably smaller and
cheaper plant, with much less high-pressure equipment/piping needed and less
energy consumption. Yet the interrelations between the reaction and other operations remained basically the same as in the conventional technology.
In most cases, however, the reaction and separation are integrated in order
to benet from the interaction effect between those two, for instance,
To improve yield/selectivity (e.g., via equilibrium shift)
To facilitate separation (e.g., azeotrope problems)
For other reasons, e.g., to extend the catalyst lifetime
One speaks in those cases about reactive separations or separative reactors.
The industrially important reactive separations include:
Reactive distillation
Membrane-based reactive separations
Reactive adsorption
Reactive absorption
Reactive extraction
Reactive crystallization
2.1.
Reactive Distillation
In most industrial applications the reactive distillation is used to improve the

yield/selectivity of the required product. Figure 1 shows three examples of industrial processes, in which combination of reaction and distillation shifts the equilibrium of the reaction A B C D in the required direction (2). The length
of the reacting, distillation, and stripping zones as well as the positioning of the
reactant inlets vary in each particular case, depending on the process requirements.
On the other hand, in selective hydrogenations of dienes and aromatics (3), reactive
distillation is used to remove the single-hydrogenated product from the reaction
FIGURE 1 Examples of industrial processes employing reactive distillation:

(a) methyl tert-butyl ether (MTBE) from isobutene and methanol; (b) cumene
via alkylation of benzene with propylene; (c) ethylene glycol via hydration of
ethylene oxide.
zone, thus preventing its further hydrogenation and increasing its yield. In the
methyl acetate technology of Eastman Chemical, integration of reactive distillation
with extractive distillation in a single unit totally solved the azeotrope problem (4).
Reactive distillation can also be used as a powerful separation method in case
of mixtures containing reactive and inert components with close boiling points.
The method is schematically depicted in Figure 2. Here, a reactive entrainer is
introduced to the rst reactive distillation column, to form an intermediate product having a boiling point much more distant from the boiling point of the inert
components. In the rst column, inert components are therefore easily separated,
while the intermediate product is fed to the second reactive distillation step,
where the reversed reaction takes place and the original reactive component is
recovered and separated from the entrainer. Stein et al. (5) investigated the application of this principle to the separation of close-boiling i-butene and n-butene,
using methanol as a reactive entrainer.
Obviously, reactive distillation may lead to signicant savings on energy.
Hydrolysis of methyl acetate presents an industrial example of such energy savings.
The heat requirements of the reactive distillation-based process are ca. 50% lower
than in the conventional technology. In the alkylation of benzene to cumene reactive distillation effectively eliminated the hot spots and reduced the oligomerization of propylene (6).
Table 1 gives an overview of the possible applications of reactive distillation
reported in the literature. Very few of them have been realized so far on the commercial scale. One of the common factors that hinders a broader application of
reactive distillation is a small feasible operation window. The overlap region in the
pressuretemperature domain, in which chemical reaction and separation and apparatus design are feasible, is usually quite narrow (see Figure 2 in Chapter 9). A
possible remedy for this limitation is sought in the development of new types of
catalysts that would allow one to signicantly broaden the feasible operation window for chemical reaction.
2.2.
Membrane-Based Reactive Separations
Sirkar et al. (64) give an interesting overview of various functions that a membrane may play in a chemical reactor. Those functions are schematically shown
in Figure 3 and summarized in Table 2.
FIGURE 2 Separation of reactive and inert components with close boiling

points, facilitated by reactive distillation. (From Ref. 5.)
TABLE 1 Reported Existing and Potential Applications of Reactive

Distillation
Product/process
Butyl acrylate from butanol and acrylic acid
n-Butyl acetate from n-butanol and acetic acid
Ethyl acetate from ethanol and acetic acid
Methyl acetate from methanol and acetic acid
Hydrolysis of methyl acetate
2-Methylpropylacetate from 2-methylpropanol
and acetic acid
Amyl acetate from amyl alcohol and acetic acid
Ethyl pentenoate from ethanol and pentenoic acid
Esterication of fatty acids
Methylal from formaldehyde and methanol
TAME (tertiary amyl ether)
MTBE (methyl tert-butyl ether)
ETBE (ethyl tert-butyl ether) from ethanol and
isobutene
ETBE (ethyl tert-butyl ether) from bioethanol and
tert-butylalcohol
Diisopropyl ether from propene
TAA (tert-amyl alcohol) via hydration of isoamylene
Isopropanol via hydration of propene
Cyclohexanol via hydration of cyclohexene
Phenol from cumene
Ethylene glycol via hydration of ethylene oxide
Isobutene via dehydration of tert-butanol
Isoamylenes via dehydration of 2-methyl-1-butanol
Isophorone from acetone
MIBK (Methyl iso-butyl ketone) from acetone
Diacetone alcohol (DAA) and mesityl oxide (MO) via
aldol condensation of acetone
Acetone via dehydrogenation of propanol
Tetrahydrofuran from butanediol
Xylenes via toluene disproportionation
Hydrogenation of unsaturated hydrocarbons
Isomerization of C5-C6 parafns
Isobutene via hydroisomerization of C4 alkenes
Cumene via alkylation of benzene with propylene
Ethylbenzene via alkylation of benzene with ethylene
Cyclopentane and/or cyclopentene from
dicyclopentadiene
Purication of hydrouorocarbons
Selected refs.
7
8
9,10
11,12
13
14
15
16
17
18,19
2022
23,24
25,26
27
28
29
30
31,32
33
34,35
3638
39
40
41,42
43,44
45
46
47
48,49
50
51
52
53,54
55
56
TABLE 1 (cont.)
Product/process
Naphtha desulfurization
Dihydroxy polyether polyol via alkanolysis of
corresponding diesters
Glycine from glycinonitryle
DEC (diethylcarbonate) via carbonylation of ethanol
with dimethylcarbonate
Polyamides (e.g., Nylon 6) via hydrolytic
polymerization of amino nitriles
Nylon 66 via polycondensation
Propylene oxide from propylene chlorohydrin
and calcium hydroxide
Selected refs.
57
58
59
60
61
62
63
Among all the membrane functions listed in Table 2, catalytic membranes

probably attract the most attention. The scientic literature on catalytic membrane
reactors is exceptionally rich and includes many interesting ideas, such as heat- and
mass-integrated combination of hydrogenation and dehydrogenation processes in
a single membrane unit. Yet practically no large-scale industrial applications of
catalytic membrane reactors have been reported so far, perhaps with the exception of the Russian vitamin K technology (65). The primary reason for this is the
relatively high price of membrane units, although other factors, such as low permeability, sealing problems, as well as mechanical and thermal fragileness of the
membranes, also play an important role. Further developments in the eld of
material engineering will surely change this picture.
Possible application areas of catalytic membrane reactors include:
Dehydrogenations, e.g., ethane to ethene, ethylbenzene to styrene, methanol
to formaldehyde
Methane steam reforming
Watergas shift reaction
Selective oxidations, e.g., propane to acroleine, butane to maleic anhydride,
ethylene to ethylene oxide
Oxidative dehydrogenations of hydrocarbons
Oxidative coupling of methane
Methane oxidation to syngas
An excellent review of all potential applications of catalytic membrane reactors
studied so far can be found in the 2002 book by Sanchez Marcano and Tsotsis (66).
On the other hand, membranes are frequently employed in combination with
a bioreactor, for instance, in enzymatic pharmaceutical processes. An example
of such an application of an ultraltration membrane-reactor system for the production of s-ibuprofen is discussed further in Chapter 12.
2.3.
Reactive Adsorption
The vast majority of possible applications of reactive adsorption aim at the improvement of the product yield by shifting the equilibrium in the required direction. In
contrast to the nonreactive adsorption techniques, such as simulated moving beds
and pressure-swing adsorption, and despite its great potential [for example, a
12-fold higher conversion per pass in oxidative methane coupling (67)], the
FIGURE 3 Membrane functions in chemical reactor. (Reproduced with permission from Sirkar et al. (64), copyright (1999) American Chemical Society.)
TABLE 2 Membrane Functions in Chemical Reactor Systems

Function
Separation of products from
the reaction mixture
Separation of a reactant from

a mixed stream for introduction into the reactor
Controlled addition of one

reactant or two reactants
Nondispersive phase contacting,

with reaction at the phase
interface or in the bulk phases
Segregation of a catalyst
(and cofactor) in a reactor
Immobilization of a catalyst
in (or on) a membrane
Membrane is the catalyst
Examples
In situ product removal from enzymatic
reactor via a nanoltration or
ultraltration membrane
Removal of selected enantiomer via
a liquid membrane
Removal of water in esterication
reactions via a pervaporation
membrane
Hydrogen removal in catalytic
dehydrogenation reactions
Separation of oxygen from air for
oxidizing methane to syngas
Separation of hydrogen from
dehydrogenation reaction to oxidize
it with oxygen on permeate side
Separation of organic priority
pollutants from wastewater for
biological purication
Controlled oxygen addition in partial
oxidation reactions (to increase
selectivity)
Controlled air introduction in oxidative
dehydrogenations
Emulsion-free enzymatic splitting of
fats
Bubble-free oxygen/ozone supply in
wastewater treatment via hollowber membranes
Segregation of enzymes with respect
to molecular weight on ultraltration
membranes
Immobilization of enzymes or cells on
polymeric membranes
Immobilization of metals (Pd, Pt) on
ceramic membranes
Cation exchange membranes for
esterication reactions
Palladium membranes for
hydrogenation/dehydrogenation
reactions
TABLE 2 (cont.)
Function
Membrane is the reactor
Solid electrolyte membrane

supports the electrodes,
conducts ions, and achieves
the reactions on its surface
Transfer of heat
Immobilizing the liquid

reaction medium
Examples
Reactions in ow-through membrane
systems (pore ow-through
reactors)
Solid electrolyte membranes such as
H and O2 conductors in fuel cells
Membranes coupling endo- and

exothermic reaction zones (e.g.,
hydrogenationdehydrogenation)
Supported liquid membranes (SLM) for
homogeneous catalytic processes
Source: Ref. 64.
industrial-scale applications of adsorptive reactors remain to be seen. Challenges

involve materials development of catalysts/adsorbents and matching of process
conditions (same temperature) for both reaction and adsorption so that high yields/
selectivities can be achieved. Reactive adsorption processes investigated in the
bench or pilot scale are numerous, as shown in Table 3.
One of the more promising types of adsorptive reactors is the so-called gas
solidsolid trickle-ow reactor (GSSTFR), in which ne adsorbent trickles through
the xed bed of catalyst (Figure 4), removing selectively in situ one or more of
the products from the reaction zone. In the case of methanol synthesis this led to
conversions signicantly exceeding the equilibrium conversions under the given
conditions (98). The economics of the methanol process based on the gassolid
solid trickle-ow reactor was evaluated and compared with the conventional lowpressure Lurgi process (99). For the production scale of 1000 tons per day, the new
technology offered considerable reductions in cooling water consumption (50%),
recirculation energy (70%), raw materials (12%), and catalyst amount (70%).
Further improvement of the GSSTFR concept could be seen in applying a moving bed of adsorbent through straight, parallel channels of a monolithic catalyst,
similar to the one shown in Figure 23 of Chapter 6.
2.4.
Reactive Extraction
Similar to reactive adsorption, the reactive extraction can be applied primarily in

multireaction systems, for improvement in yields and selectivities to desired products. The combination of reaction with liquidliquid extraction can also be used
TABLE 3 Processes Investigated in Reactive Adsorption Systems

Process
Selected refs.
Reactor type
Esterication of glycerin with acetic acid
68
Methyl tert-butyl ether (MTBE) synthesis

Hydrolysis of methyl formate
Oxidative coupling of methane
Enzymatic production of L-amino acids
Oxidation of phenols
Ethyl acetate from ethanol and acetic acid
Enzymatic inversion of sucrose
69,70
71
67,72
73
74
75
76
77
Dehydroisomerization of n-butane
to isobutene
Mesitylene hydrogenation
Hydrogenation of 1,3,5-trimethylbenzene
Biosynthesis of dextran polymer
from sucrose
Dissociation of dicyclopentadiene
Dehydrogenation of cyclohexane
78
Simulated moving bed chromatographic reactor

(SMBCR)
SMBCR
Discontinuous chromatographic reactor
SMBCR
Centrifugal partition chromatographic reactor
Chromatographic reactor
Chromatographic reactor
SMBCR
Rotating cylindrical annulus chromatographic
reactor (RCACR)
Chromatographic pulse reactor
72
79,80
81
SMBCR
SMBCR
82,83
84
85
86
87
SMBCR
RCACR
SMBCR
SMBCR
88
Batch and xed-bed adsorptive

reactors
Ascorbic acid synthesis

Regioselective enzymatic
diol esterication
TABLE 3 (cont.)
Process
Oxidation of lean VOC mixtures
Hydrolysis of methyl formate
Enzymatic production of lactosucrose
from sucrose and lactose
Diethylacetal from ethanol and
acetaldehyde
Steam methane reforming
Propene metathesis to ethene
and 2-butene
1-Butene dehydrogenation to
1,3-butadiene
Sulfur from H2S (Claus process)
HCN from carbon monoxide
and ammonia
6-Aminopenicillanic acid from
penicillin G
Methanol synthesis
Selected refs.
Reactor type
89
90
91
SMBCR
RCACR
SMBCR
92
Fixed-bed adsorptive reactor
93
94
Pressure-swing adsorptive reactor (PSAR)

PSAR
95
Rapid PSAR
96
96
Reverse-ow adsorptive reactor

Reverse-ow adsorptive reactor
97
Trickle-ow uidized-bed reactor
98,99
Gassolidsolid trickle-ow reactor (GSSTFR)
FIGURE 4 Gassolidsolid trickle-ow reactor. (From Ref. 98.)
for the separation of waste by-products that are hard to separate using conventional techniques (100,101). An overview of processes studied in reactive extraction systems is shown in Table 4.
In 2002, an interesting concept was proposed for coupling a CO2-based
supercritical extraction with air oxidation in order to remove and decompose pollutants from gases or liquids (134). An exemplary process scheme according to
this preliminary concept is shown in Figure 5. Possible (future) environmental
applications of such an integrated supercritical extraction-reaction system include
treatment of liquid efuents, regeneration of catalysts and adsorption materials,
and soil decontamination.
2.5.
Reactive Crystallization/Precipitation
Reactive crystallization/precipitation plays a role in a number of industrially

relevant processes, such as liquid-phase oxidation of para-xylene to produce
technical-grade terephthalic acid, the acidic hydrolysis of sodium salicylate to
salicylic acid, and the absorption of ammonia in aqueous sulfuric acid to form
ammonium sulfate (135). Reactive crystallization/precipitation is also widely
applied in the pharmaceutical industry, to facilitate the resolution of the enantiomers (diastereomeric crystallization). Here, the racemate is reacted with a specic optically active material (resolving agent) to produce two diastereomeric
derivatives (usually salts) that are easily separated by crystallization:
( DL )-A ( L )- ( D)-A ( L )- ( L )-A ( L )-
racemate
resolving agent
n-salt
p-salt
TABLE 4 Some Processes Studied in Reactive Extraction Systems

Product/process
Penicillin G recovery
Downstream separation of 1,3-propanediol
Separation of lactic acid
Separation of organic acids from the products of
partial oxidation of parafns
Separation of salicylic acid
Separation of D,L-phenylalanine
Separation of citric acid
Separation of aspartic acid
Cephalosporin C recovery
Separation of metals (e.g., zinc)
Phenolic wastewater treatment
Separation of dicarboxylic acids (e.g., oxalic, malonic,
succinic, adipic acid)
Recovery of gallium from coal y ash
Recovery of palladium, platinum, rodium from
leaching solutions
Fractionation of amino acids
Recovery of 7-ACA (7-aminocephalosporanic acid)
Recovery of erythromycin
Removal of toxic heavy metals from wastewater streams
Production of dioxolane from aldehyde
Recovery of aldehydes and ketones from hydrocarbon
mixtures
Production of cyclic ester oligomers from linear polyesters
Selected refs.
102106
107
108111
112
113,114
113,115
116
117
118
119121
122
123
124
125
126
127
128
129,130
131
132
133
FIGURE 5 Countercurrent supercritical extraction coupled with air oxidation

to remove and decompose pollutants from gases and liquids. (From Ref.
134.)
Diastereomeric crystallization is commonly used in the production of a number

of pharmaceuticals, such as ampicillin, ethambutol, chloramphenicol, diltiazem,
fosfomycin, and naproxen (136).
Somewhat similar are the so-called adductive crystallization processes,
often (wrongly) called extractive crystallization, where reactions of complex/
adduct formation are used to separate compounds that are otherwise difcult to
separate. Examples of adductive crystallization include separation of p- and mcresols (137), separation of o- and p-nitrochlorobenzenes (138), separation of
quinaldine and isoquinoline (139), separation of nonaromatic compounds from
naphtha-cracking rafnate (140), and separation of p-cresol from 2,6-xylenol
(141). Other examples of reactive crystallization/precipitation reported in the literature are listed in Table 5.
Reactive crystallization/precipitation can also be conducted in high-gravity
(Higee) elds using rotating equipment. In China this technique has been used
successfully for the production of nano-size particles of CaCO3. Ultrane particles
with the mean size of 1540 nm and a very narrow size distribution were produced by carbonation of a lime suspension in a rotating packed-bed reactor (RPBR)
(158). The reaction times in RPBR were 4- to 10-fold shorter than the corresponding reaction times in a conventional stirred-tank unit. A similar technique was
used for the production of nanobrils of aluminum hydroxide with a diameter of
110 nm and 50300 nm long as well as nanoparticles of SrCO3 with a mean size
of 40 nm (159).
2.6.
Reactive Absorption/Stripping
Reactive absorption is very old as a processing technique and has been used for
production purposes in a number of classical bulk-chemical technologies, such as
nitric or sulfuric acid. The Raschig process for the production of hydroxylamine,
an important intermediate in classical caprolactam technologies (Stamicarbon,
Inventa), is also an example of a multistep reactive absorption process. Here,
water, ammonia, and carbon dioxide react together in an absorption column to
give a solution of ammonium carbonate, which subsequently forms an alkaline
TABLE 5 Examples of Reactive Crystallization/Precipitation

Product
Selected
refs.
Calcium carbonate
142,143
Methyl -methoximino
acetoacetate
Magnesium hydroxide
Calcium phosphate
Magnesium ammonium
phosphate
144
Lead sulfate
Magnesium carbonate
Nickel hydroxide
ZiprasidoneHClH2O
150
151
152
153
Barium carbonate
154
Boric acid
155
Procaine benzylpenicillin
Sulfamic acid
156
157
145,146
147,148
149
Remarks
Liquidliquid and gasliquid
reaction systems
Removal of ammonium and

phosphate ions from
wastewater
Conducted in impinging
uid jet stream system
To remove CO2 from waste
gas
Reaction of borax solution
with solid oxalic acid
From urea and fuming H2SO4
solution of ammonium nitrite by reactive absorption of nitrous oxide at low temperature. In a further step, the ammonium nitrite is converted to hydroxylamine
disulfonate with sulfur dioxide. The hydroxylamine disulfonate solution is drawn
off and the salt is hydrolyzed and neutralized to give hydroxylamine sulfate and
ammonium sulfate as coproduct.
Carbon dioxide removal by reactive absorption in amine solutions is also
applied on the commercial scale, for instance, in the treatment of ue gas (see
later in this chapter). Another possible application eld of the technique is gas
desulfurization, in which H2S is removed and converted to sulfur by means of
reactive absorption. Aqueous solutions of ferric chelates (160162) as well as
tetramethylene sulfone, pyridine, quinoline, and polyglycol ether solutions of
SO2 (163,164) have been proposed as solvents. Reactive absorption can also be
used for NOx reduction and removal from ue or exhaust gases (165,166). The
separation of light olens and parafns by means of a reversible chemical complexation of olens with Ag(I) or Cu(I) compounds in aqueous and nonaqueous
solutions is another very interesting example of reactive absorption, one that
could possibly replace the conventional cryogenic distillation technology (167).
3.
HYBRID SEPARATIONS
Generally speaking, hybrid separations can be described as processing methods that

integrate two or more different separation techniques in a single operation, making
use of the synergy between them. The industrially most important (or promising)
hybrid separations include:
Extractive distillation
Adsorptive distillation
Membrane distillation
Membrane absorption/stripping
Adsorptive membranes (membrane chromatography)
Membrane extraction
3.1.
Extractive Distillation
Extractive distillation is probably the oldest and most widely applied type of
hybrid separation, particularly useful in close-boiling-point problems or in systems in which components form azeotropes. In the method, an extra component
(solvent) is added to the system, which does not form azeotropes with feed components. The solvent alters the relative volatility of original feed components,
allowing one to distill overhead. The solvent leaves the column with the bottom
products and is separated in a binary column. Energy savings represent the most
important advantage of extractive distillation over the conventional (nonhybrid)
separation methods (168,169).
FIGURE 6 Scheme of aromatics separation via extractive distillation in the

BTX process of the GTC Technology Corp.
Originally, extractive distillation was limited to two-component problems.

However, recent developments in solvent technology enabled applications of
this hybrid separation in multicomponent systems as well. An example of such
application is the BTX process of the GTC Technology Corp., shown in Figure 6,
in which extractive distillation replaced the conventional liquidliquid extraction
to separate aromatics from catalytic reformate or pyrolysis gasoline. This led to a
ca. 25% lower capital cost and a ca. 15% decrease in energy consumption (170).
Some other examples of existing and potential applications of the extractive distillations are listed in Table 6.
Solvents used for extractive distillation vary considerably, but in almost all
cases solvent selection presents a trade-off between its selectivity and solvency
(194). The effectivity of the solvent can sometimes be improved by the addition
of a salt (195).
3.2.
Adsorptive Distillation
Although considered by some authors a novel process, adsorptive distillation is

a relatively old hybrid separation, originating in the early 1950s (196). It is a
TABLE 6 Reported (Potential) Applications of Extractive Distillation

Separation process
High-purity cyclohexane
from petroleum
Benzene and toluene
from nonaromatics
Isopropyl ether from acetone
Methyl acetate from
methanol
Anhydrous ethanol from
fermentation broth
Ethyl acetate from
ethanol/water
Ternary acetatealcoholwater
systems (propyl, butyl,
amyl, hexyl)
m-Xylene from o-xylene
MTBE from impurities
Binary mixtures of
lower-boiling alcohols
Binary mixtures of
phenolic compounds
(chlorophenol, phenol,
cresol, xylenol)
Acetone from water
Ethanol dehydration
C2 alcohols from water
Cyclohexane-cyclohexenebenzene
MTBE from ethanol
Methylcyclohexane from
toluene
Anhydrous ethanol recovery
from wastewater streams
Propylene from propane
1-Butene from 1,3-butadiene
Selected
refs.
Remarks
171
Close-boiling-point problem
172,173
174
175
Azeotrope problem
Azeotrope problem
176
Azeotrope problem
177
Azeotrope problem
178
Azeotrope problem
179
180
181
182,183
184
185
186
187
Azeotrope problem
Azeotrope problem
Azeotrope problem
188
189
Azeotrope problem
190
Azeotrope problem
191
192,193
three-phase mass transfer operation in which distillation is carried in presence of

a solid selective adsorbent. The adsorbent usually consists of a ne powder (particle size in the 10-m range), uidized and circulated by an inert carrier. The
process is typically carried in two columns: an adsorptive distillation column for
increasing separation ability, and a distillative desorption column for enhancing
the regeneration of the adsorbent. As in the case of extractive distillation, adsorptive distillation also can be used for the separation of mixtures containing closeboiling components or to bypass the azeotrope. Another interesting potential
application eld is the removal of trace impurities in the production of ne chemicals. The simplest scheme of an adsorptive distillation system for separating a
binary mixture of azeotrope-forming components is shown in Figure 7. Here,
adsorbent S carried by an inert uid carrier enters the adsorptive distillation column, selectively adsorbs component B from the feed, and ows to the desorption
(stripping) column, in which separation and enrichment of B takes place. Figure 8
shows another variant of adsorptive distillation, as proposed in a patent by Shell
(197), for improved separation of closely-boiling hydrocarbon mixtures. Here an
extra stripping medium (e.g., pentane) is used to remove the adsorbate in the
stripping column.
Despite an almost 50-year history, no large-scale commercial processes
using adsorptive distillation have been reported so far. Some potential application
elds for this hybrid separation are listed in Table 7.
FIGURE 7 Scheme of an adsorptive distillation system for the separation of

azeotrope-forming components A and B (Sadsorbent).
FIGURE 8 Simplied scheme of an adsorptive distillationbased separation

of closely boiling hydrocarbon mixtures. (From Ref. 197.)
3.3.
Membrane Distillation
Membrane distillation is considered a promising separation method applicable primarily in environmental technologies. In membrane distillation a microporous and
hydrophobic membrane separates aqueous solutions at different temperatures and
compositions, as shown in Figure 9. The temperature difference existing across the
membrane results in a vapor pressure difference. The molecules are transported
through the pores of the membrane from the high-vapor-pressure side to the lowvapor-pressure side. At least one side of the membrane remains in contact with the
liquid phase. Benets offered by membrane distillation include (202):
100% (theoretical) rejection of ions, macromolecules, colloids, cells, and
other nonvolatiles
Lower operating temperatures than conventional distillation
Lower operating pressures than conventional pressure-driven membrane
separation
Reduced chemical interaction between membrane and process solutions
Less demanding membrane mechanical property requirements
Reduced vapor spaces compared to conventional distillation
Membrane distillation systems may be classied into four different categories (203):
Direct contact membrane distillation (DCMD), in which the membrane is
in direct contact with the liquid phase on both sides
Air-gap membrane distillation (AGMD), in which an air gap is interposed
between the membrane and the condensation surface
Vacuum membrane distillation (VMD), in which the vapor phase is evacuated from the liquid through the membrane and the condensation takes
place in a separate apparatus
Sweeping-gas membrane distillation (SGMD), in which a stripping gas,
instead of vacuum, is used as a carrier
Currently, the most important application area for membrane distillation is
water desalination technology. Figure 10 shows one of the water desalination
processes developed by a Japanese organization, the Water Re-Use Promotion
Center, in cooperation with Takenaka Corporation and Organo Corporation (204).
The process uses solar energy and can therefore be installed at locations without
an electricity supply. Other application areas for membrane distillation reported
in the literature are summarized in Table 8.
In 2002, the TNO Environment, Energy and Process Innovation institute
in the Netherlands developed a membrane-based distillation concept that radically
improves the economy and ecology of existing desalination technology for
TABLE 7 Potential Application Fields of Adsorptive Distillation Reported
in the Literature
System
Toluenemethylcyclohexane
mixtures and other
closely boiling
hydrocarbons
Naphtha reformate and
other close-boiling
hydrocarbons
o-Xylenem-xylene mixture
Ethanolwater and ethyl
acetatewatern-butanol
mixtures
p-Xylenem-xylene mixture
Selected
refs.
196
197
198
199,200
201
Remarks
Suitable adsorbents: silica gel,
activated carbon, coconut
charcoal, bauxite,
activated alumina
Silica gel as adsorbent
Modeling study
Zeolite (4A molecular sieve)
as adsorbent, glycol as
carrier
Zeolite (NaY molecular sieve)
as adsorbent, n-decane as
carrier
FIGURE 9 Scheme of a membrane distillation process.
seawater and brackish water. This so-called Memstill technology (Figure 11a)
combines multistage ash and multieffect distillation modes into one membrane
module. Since the Memstill module houses a continuum of evaporation stages
in an almost ideal countercurrent ow conguration, a very high recovery of the
evaporation heat is possible. The economic advantage of the Memstill technology, compared to the classical desalination techniques, is shown in Figure 11b.
An academic-industrial consortium is currently developing and improving the
Memstill process concept and module design (226). The same TNO Institute
has also developed a concept of another membrane-based distillation technology
for fractionation of non-water-based systems (227). The technology, called
MEMFRAC, offers high energy efciency in compact equipment. The study carried out for fractionation of benzene from toluene showed that with MEMFRAC
technology a HETP between 5 and 10 cm could be obtained. Additional advantages of the MEMFRAC technology include: lack of entrainment, ooding, foaming, or channeling (due to indirect gasliquid contact), independent gas/liquid
control, and the possibility for modular plant design. Such a modular MEMFRAC
distillation unit is schematically presented in Figure 12.
On the other hand, a pervaporation membrane can be coupled with a conventional distillation column, resulting in a hybrid membrane/distillation process
(228,229). Some of the investigated applications of such hybrid pervaporation
membrane/distillation systems are shown in Table 9. In hybrid pervaporation/
distillation systems, the membrane units can be installed on the overhead vapor
of the distillation column, as shown in Figure 13a for the case of propylene/
propane splitting (234), or they can be installed on the feed to the distillation column,
FIGURE 10 Scheme of the demonstration test plant for water desalination using solar energy and membrane distillation.
(Courtesy: CADDET, Center for Renewable Energy, Harwell, UK).
TABLE 8 Application Areas of Membrane Distillation

System/process
Selected
refs.
Concentration of H2SO4,
H3PO4, NaOH, HNO3, and
HCl solutions
Concentration of 2,3-butanediol
from fermentation broths
Wastewater treatment in
the textile industry
205207
Radioactive wastewater
treatment
210
Removal of benzene traces

from water
Concentration of protein solutions
Removal of halogenated VOCs
Concentration of oilwater
emulsions
Concentration of sugar/sucrose
solutions
Separation of water and glycols
Ethanolwater separation
Acetone and ethanol removal
from aqueous solutions
Propanone removal from
aqueous streams
Acetonebutanolethanol
(ABE) solvent recovery
Fermentative ethanol
production
211
Concentration and purication

of uosilicic acid
Removal of trichloroethylene
Remarks
208
VMD process
209
Integrated reverse
osmosis/membrane
distillation process
Integrated reverse
osmosis/membrane
distillation process
VMD process
212
213
214
215,216
VMD process
217
218
219
DCMD and AGMD

processes
DCMD process
AGMD process
AGMD process
220
AGMD process
221
AGMD process
222,223
Integration of MD in
fermentation resulted
in ca. 2 increase of
production rate
224
225
VMD process
FIGURE 11 Memstill technology of seawater desalination developed at the TNO institute: (a) principle of the
process; (b) cost comparison with other desalination techniques. (From Ref. 226.)
FIGURE 12 Scheme of a modular MEMFRAC distillation unit for fractionation

of non-water-based systems, developed at the TNO Institute. (From Ref. 227.)
as shown in Figure 13b for the case of aromatic/aliphatic hydrocarbon separation

(235). Shortcut design methods for hybrid pervaporation/distillation processes
can be found in Ref. 236.
3.4.
Membrane Absorption/Stripping
Membrane absorption is one of the processes that Mother Nature had invented long
before engineers did. Human lungs and intestines present perfect examples of
membrane absorption systems. In the simplest case a gaseous component is selectively transported via a membrane and dissolved in the absorbing liquid, as shown
in Figure 14. It is also possible to carry a membrane-based absorption-desorption
process, with two liquids on both sides of the membrane (237), or a membrane
stripping process, in which selected components are removed from the liquid phase
through the membrane by a stripping gas (238). An important characteristic feature
of membrane absorption is that it proceeds without creating a real gasliquid interface in the form of bubbles. Such a bubbleless gasliquid mass transfer can be of
advantage in certain processes, for instance, in shear-sensitive biological systems.
One of the most important application areas of the membrane absorption is
the capture of CO2 from ue gas. Kvrner has recently developed a membrane
absorptionbased technology for the removal of CO2 from turbine exhaust gases in
offshore applications (239). The process, based on membrane-facilitated CO2
absorption in amine, followed by membrane-facilitated stripping with steam, is
schematically shown in Figure 15. The expected cost reduction, in comparison with
a conventional amine separation process, ranges between 30 and 40%, for both
investment and operating costs. The new membrane-based process also offers a very
signicant reduction in the weight and size of equipment (7075% and 65%, respectively; see Figure 16), a great advantage in the case of offshore technology. Some
other possible applications of membrane absorption/stripping are shown in Table 10.
3.5.
Membrane Chromatography (Adsorptive Membranes)
Membrane chromatography is a separation technique used almost exclusively in

the downstream processing of proteins. Traditionally, most chromatographic
purication steps in the downstream processing of proteins take place in columns
packed with bead-shaped particles. Membrane chromatography presents a hybrid
combination of liquid chromatography and membrane ltration based on microporous or macroporous membranes that contain functional ligands attached to
their inner pore structure, which act as adsorbents. The main feature and advantage of this technique, compared to the conventional ones, is the absence of pore
TABLE 9 Possible Applications of Hybrid Pervaporation/Distillation
Systems
System/process
investigated
Selected
refs.
Benzenecyclohexane
separation
230
Ethanol dehydration
231
Propylene/propane
splitting
Propylene/propane
splitting
232
233
Remarks/effects
Combination of extractive distillation
and one-stage pervaporation;
high-purity (99.299.5%) products;
estimated cost savings of 20%
Simulation study; 50% cost
reduction in comparison with
conventional azeotropic distillation
Pilot-plant studies; 2050% savings
on operating costs
2630% savings on capital
investment
FIGURE 13 Combined distillation/pervaporation systems for (a) propylene/ propane splitting and (b) aromatic/aliphatic
hydrocarbon separation. (Part a from Ref. 234; part b from Ref. 235.)
FIGURE 14 Membrane absorption.
diffusion, which is the main transport resistance in traditional chromatography.

Dissolved molecules are carried directly to the adsorptive sites in the membranes
by convective ow (Figure 17), which increases the throughput of the process.
Membrane chromatography presents a process-intensive option for the protein A,
G, or L afnity chromatography (247253), as well as for metal afnity, ionexchange, hydrophobic interaction or reversed-phase chromatography (254258).
In recent years some new potential application elds for membrane chromatography have been demonstrated. Those are listed in Table 11.
FIGURE 15 Membrane absorptionbased technology for removal of CO2

from turbine exhaust gases, developed by Kvrner Process Systems.
(Courtesy: Kvrner.)
FIGURE 16 Plant-size reduction in Kvrners technology for CO2 removal

from exhaust gases: (a) conventional process; (b) membrane absorption
process. (Courtesy: Kvrner.)
3.6.
Membrane Extraction
In membrane extraction, the treated solution and the extractant/solvent are separated from each other by means of a solid or liquid membrane. The technique is
applied primarily in three areas: wastewater treatment (e.g., removal of pollutants
or recovery of trace components), biotechnology (e.g., removal of products from
fermentation broths or separation of enantiomers), and analytical chemistry (e.g.,
online monitoring of pollutant concentrations in wastewater). Figure 18a shows
schematically an industrial hollow berbased pertraction unit for water treatment, according to the TNO technology (263). The unit can be integrated with a
lm evaporator to enable the release of pollutants in pure form (Figure 18b).
Other more promising possible applications of membrane extraction, reported in

the literature, are listed in Table 12.
3.7.
Other Hybrid Separations
In extractive crystallization (nonadductive), the driving force for the separation

process is created by altering the solidliquid phase relationships via the addition
of a third component (usually liquid solvent) to the system. The solvent is chosen
in such a way that it binds strongly at the crystallization temperature but separates
easily at another temperature, where it is usually regenerated via distillation.
Examples of such dened extractive distillations include separation of m- and pcresols using acetic acid as the solvent (297), separation of o- and p-nitrochlorobenzenes using p-dichlorobenzene (298), separation of lithium sulfate and lithium
formate using n-butanol or 2-propanol (299), and separation of p-xylene from
m-xylene using pentene (300).
TABLE 10 Reported Possible Applications of Membrane Absorption/
Stripping
System/process
investigated
Ammonia absorption/
desorption from
ammonia water
CO2 and/or SO2 removal
Selected
refs.
240
241
Cyanide recovery from

wastewater
242
H2S removal from gas

streams
243
CO2 production for the

horticultural industry
(greenhouses)
H2S and SO2 removal
244
VOC removal from

wastewater
245
246
Remarks/effects
Pilot-plant study in a polypropylene
hollow-ber column; ammonia is
absorbed in diluted sulfuric acid
Absorption in NaOH, K2CO3,
alkanolamines, and Na2SO3 using
hydrophobic microporous hollowber modules
Recovery via a gas-lled membrane
(GFM) placed between the wastewater and a chemical stripping
solution
Asymmetric hollow-ber modules
coupled with concentrated
alkaline solution
Possible energy saving of more
than 30% reported
Polyvinylidene uoride (PVDF)
hollow bers and concentrated
NaOH solution used
Air stripping process via a
polypropylene hollow-ber module
FIGURE 17 Comparison of transport mechanisms in (a) conventional chromatography and in (b) membrane chromatography.
Smith, Bryson, and Valsaray (301,302) investigated solvent sublation, an

adsorptive bubble process, combining the transport mechanisms of liquid/liquid
extraction and gas stripping. The technique exploits the surface-active nature of
organic compounds in their removal from water systems. The mechanism of solvent
sublation is shown in Figure 19a. Gas bubbles are used to transport adsorbed solute
from the bulk solution to the solvent layer. Solvent sublation is particularly promising in the removal of (hydrophobic) organic compounds from wastewater streams.
An exemplary process scheme is shown in Figure 19b. An important advantage of
the method is that the intimate contact between the extracting solvent and the wastewater is prevented (no problem of residual solvent in the treated water).
Zeitsch (303) conducted a preliminary research on the removal of acetic
acid from the vapor stream of furfural reactors by means of extractive condensation. It is a hybrid vapor-phase extraction process, in which solvent (triethylamine, TEA) forms a high-boiling complex with acetic acid. As a result, a fog
fraction is formed that can be separated via a coalescence lter or an electrostatic

separator. The technique is reported to be highly selective.
In 2002, Drioli and coworkers (304) investigated a process for obtaining
protein crystals by means of membrane crystallization, which actually combines
membrane distillation and crystallization techniques. The solvent evaporates at
the membrane interface, migrates through the pores of the membrane, and condenses on the opposite side of the membrane. The reported preliminary results
indicate interesting potentialities of this new method with respect to macromolecular crystallization.
4.
BARRIERS AND FUTURE PROSPECTS
Despite many ongoing research activities in the eld and a number of successful
commercializations, there still exist numerous technical and nontechnical barriers
that hinder a wider introduction of reactive and hybrid separations into industrial
practice. Two workshops held in 1998 by the Center for Waste Reduction
Technologies of AIChE (305) identied some of the barriers for reactive separations and divided them into three categories:
a. Technical gaps, such as lack of simulation and scale-up capability, lack
of validated thermodynamic and kinetic data, lack of materials (e.g.,
TABLE 11 Reported New Potential Applications of Membrane
Chromatography
System/process investigated
Selected
refs.
Separation of polynucleotides
259
Separation of oligonucleotides
and peptides
Separation of small
hydrophobic molecules
260
260
Enantiomeric separation
261
Separation of trace metals
262
Remarks/effects
Supercoiled plasmid DNA
investigated as model
Benzene, toluene, homologues

of 4-hydroxybenzoate
investigated
Racemic mixtures of
tryptophan and thiophenal
investigated in microuidicbased membrane
chromatography
La-Ce-Pr-Nd-Sm separation
and Zr-Hf separation
investigated
FIGURE 18 Pertraction technology for wastewater treatment from the TNO

Institute: (a) scheme of the hollow-ber pertraction unit; (b) integration of
pertraction with lm evaporation. (Courtesy: TNO.)
Selected
refs.
Separation of acetic acid from aqueous solution
264
Separation of (S)-naproxen from racemic

naproxen thioesters
Separation of D,L-alanine and D,L-phenylalanine
racemic mixtures
Removal of sulfanilic acid from wastewater
Lactic acid purication and concentration
Enrichment of bisphenol A
Phenol recovery from aqueous solutions
Zinc(II) recovery from HCl solution
Hydrogen separation from methane steam
conversion products
Separation of liquid olen/parafn mixtures
Removal of 2-chlorophenol
Ethanol removal from aqueous solutions
Separation of cephalosporin C from
fermentation broth
Separation of penicillin G
from aqueous streams
Enrichment of amino acids
Separation of cephalexin from a mixture of 7-ADCA
Separation of butyric acid from fermentation broth
265
TABLE 12 Reported Potential Applications of Membrane Extraction

Remarks
266,267
Microporous polypropylene membrane,

MIBK as solvent
Reactive extraction via hollow-ber
membrane
Hollow-ber zeolite membrane
268
269
270
271,272
273
274
Hollow-ber modules
Emulsion liquid membranes (ELMs)
Liquid membrane
Various liquid and solid membranes
Bulk liquid and hollow-ber membranes
Palladium alloy membranes
275
276
277
278
Nonporous polymeric membranes

Liquid membrane from aqueous solutions
Microporous polypropylene membrane
Bulk and emulsion liquid membranes
279
Supported liquid membrane

(Amberlite LA-2)
Supported liquid membrane (Aliquat 336)
Supported liquid membrane (Aliquat 336)
Liquid membrane
280
281
282
(continued)
TABLE 12 (cont.)
Selected
refs.
Remarks
Separation of propionic and acetic acid from

fermentation broth
Separation of citric acid from fermentation broth
Separation of lactic acid from fermentation broth
Production of acetone, butanol, and ethanol
(ABE) from potato wastes
Separation of long-chain unsaturated fatty acids
283
Polymeric membranes
284
285
286
Liquid membrane
Emulsion liquid membrane
Polypropylene membrane
287
(Heavy) metals recovery from wastewater

Removal of organic contaminants from wastewater
288292
293296
Microporous membrane, MeCN

and n-heptane as solvents
Various membranes
Various membranes
FIGURE 19 Solvent sublation: (a) process mechanism and (b) an exemplary

process scheme. (From Refs. 301 and 302.)
integrated catalysts/sorbents, membrane materials), and lack of highlevel process synthesis methodology
b. Technology transfer barriers, such as lack of multidisciplinary team
approaches to process integration, lack of commonality of problems (technology is application-specic) and lack of demonstrations/
prototypes on a reasonable scale (reactive and hybrid separations are
still regarded more as a science than a technology)
c. General barriers, such as higher standards, to which new technologies
must be held, compared to conventional technologies, lack of information on process economics (early economic and process evaluation),
and fear of risk in using new technologies.
Most of these barriers also hold for hybrid separations. Two more factors
that clearly play a hindering role in the commercial application of many reactive
and hybrid separations are: the already-mentioned small feasible operation windows and the reduction of the degree of freedom caused by the integration of reaction and separation or by the coupling of two separations in one processing unit.
Figure 20 shows an example of how the integration of reaction and membrane
separation reduces the degree of freedom in a membrane reactor, resulting in
decreased operational exibility (306).
FIGURE 20 Degree of integration versus degree of freedom, in an example of

a membrane reactor. (From Ref. 306.)
Despite the existing barriers, the coming years are expected to bring a signicant increase in the number of industrially applied reactive and hybrid separation technologies. In particular, progress can be expected in the application of
reactive distillation, reactive adsorption, and membrane-based operations. In
hybrid separations, expansion of research activities on new product/process areas
has already been seen. Reactive and hybrid separations have enormous potential
for process intensication. Making full use of that potential will lead to substantially smaller, cleaner, and more energy-efcient chemical and biochemical
plants.
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9
Reactive Separations in Fluid Systems
E.Y. Kenig and A. Grak
University of Dortmund, Dortmund, Germany
H.-J. Bart
University of Kaiserslautern, Kaiserslautern, Germany
1. INTRODUCTION: AN OVERVIEW OF
REACTIVE SEPARATIONS
Chemical manufacturing companies produce materials based on chemical reactions
between selected feed stocks. In many cases the completion of the chemical reactions is limited by the equilibrium between feed and product. The process must then
include the separation of this equilibrium mixture and recycling of the reactants.
The fundamental process steps of bringing material together, causing them to react,
and then separating products from reactants are common to many processes.
Conventionally, each unit operationwhether mixing or absorption, distillation, evaporation, crystallization, in fact, any of the heat-, mass-, and momentumtransfer operations so familiar to chemical engineersis typically performed in
individual items of equipment, which, when arranged together in sequence, make
up the complete process plant. As reaction and separation stages are carried out
in discrete equipment units, equipment and energy costs are added up from these
major steps. However, this historical view of plant design is now being challenged
by the combination of two or more unit operations into one plant unit. The potential for capital cost savings is obvious, but there are often many other process
advantages that accrue from such combinations (1).
In recent decades, a combination of separation and reaction inside a single

unit has become more and more popular. This combination has been recognized
by chemical process industries as having favorable economics for carrying out
reaction simultaneously with separation for certain classes of reacting systems,
and many new processes (called reactive separations) have been invented based
on this technology (29). Reactive separation units may also be treated as a kind
of multifunctional reactor in which the functionalities of several processes are
combined to generate the new reactor concept (Figure 1).
The most important examples of reactive separation processes (RSPs) are
reactive distillation (RD), reactive absorption (RA), and reactive extraction (RE). In
RD, reaction and distillation take place within the same zone of a distillation column.
Reactants are converted to products, with simultaneous separation of the products
and recycling of unused reactants. The RD process can be efcient in both size and
cost of capital equipment and in energy used to achieve a complete conversion of
reactants. Since reactor costs are often less than 10% of the capital investment, the
combination of a relatively cheap reactor with a distillation column offers great
potential for overall savings. Among suitable RD processes are etherications, nitrations, esterications, transesterications, condensations, and alcylations (2).
FIGURE 1 Reactive separation units as multifunctional reactors. (Inspired by

Ref. 4.)
Similarly, in RA, reactions occur simultaneously with the component transport and absorptive separation, in the same column zone. These processes are
used predominantly for the production of basic chemicals, e.g., sulphuric or nitric
acids, and for the removal of components from gas and liquid streams. This can be
either the cleanup of process gas streams or the removal of toxic or harmful substances in ue gases. Absorbers or scrubbers where RA is performed are often
considered gasliquid reactors (10). If more attention is paid to the mass transport, these apparatuses are instead treated as absorption units.
Reactive extraction uses liquid ion exchangers that promote a selective
reaction or separation. The solutes are very often ionic species (metal ions or
organic/inorganic acids) or intermediates (furfural phenols, etc.), and the extraction chemistry is discussed elsewhere (1113). Reactive extraction can be used for
separation/ purication or enrichment or conversion of salts (14). A 2001 review
on reactive phase equilibria, kinetics, and mass transfer and apparative techniques
is given in Ref. 8. Reactive extraction equipment is discussed in detail in Ref. 15,
and recent advances are given in Ref. 16.
Reactive absorption, distillation, and extraction have much in common.
First of all, they involve at least one liquid phase, and therefore the properties of
the liquid state become signicant. Second, they occur in moving systems; thus
the process hydrodynamics plays an important part. Third, these processes are
based on the contact of at least two phases, and therefore the interfacial transport
phenomena have to be considered. Further common features are multicomponent
interactions of mixture components, a tricky interplay of mass transport and
chemical reactions, and complex process chemistry and thermodynamics.
On the other hand, RD, RA, and RE have a number of specic features that
should be considered with care and described by different approaches. Before
going into detail, it is worthy to note that the operating window of reactive separations may be somewhat limited, since these operations are feasible only if they
allow for both separation and reaction within the same range of temperature and
pressure and, on the other hand, for the safe operation from the constructional
point of view (Figure 2).
1.1.
Reactive Absorption
The main purposes of absorption processes are the removal of one or more components from the gas phase, production of particular substances in the liquid
phase, and gas mixture separation (3). Industrial absorption operations are usually
realized by combining absorption and desorption units.
The example given in Figure 3 illustrates this combination of two processes.
In an absorber, one or several gas components are absorbed by a lean solvent,
either physically or chemically. A rich solvent, after preheating in heat exchangers H1 and H3, is transported to the top of a desorption unit, which usually operates
FIGURE 2 Feasibility of reactive separation, depending on mechanical

design, chemical reaction, and separation performance.
under a pressure lower than that in the absorber. Part of the gas absorbed by the
rich solvent is desorbed due to ashing and heating. The other part has to be desorbed in the stripper via countercurrent contact of liquid with the inert gas or
steam. The lean solvent then ows through heat exchanger H1 to recover heat necessary for heating the reach solvent, passes through heat exchanger H2 to cool
down to a desired temperature, and nally enters the absorber (3).
Usually a small amount of fresh solvent should be added to the column in
order to equalize the solvent loss due to evaporation in the desorber or to irreversible chemical reactions occurring in the whole system (3).
Reactive absorption represents a process in which a selective solution of
gaseous species by a liquid solvent phase is combined with chemical reactions.
As compared to purely physical absorption, RA does not necessarily require elevated pressure and high solubility of absorbed components; because of the chemical reaction, the equilibrium state can be shifted favorably, resulting in enhanced
solution capacity (17). Most RA processes involve reactions in the liquid phase
only; in some of them, both liquid and gas reactions occur (18,19).
Usually the effect of chemical reactions in RA processes is advantageous
only in the region of low gas-phase concentrations, due to limitations stemming
from the reaction stoichiometry or equilibrium (20). Further difculties of RA
applications may be caused by the reaction heat through exothermic reactions and
by relatively difcult solvent regeneration (21,22). Most RA processes are
steady-state operations, either homogeneously catalyzed or auto-catalyzed. Some

important industrial applications of RA are given in Table 1.
Reactive absorption can be realized in a variety of equipment types, e.g., in
lm absorbers, plate columns, packed units, or bubble columns. This process is characterized by independent ow of both phases, which is different from distillation and
permits both cocurrent (downow and upow) and countercurrent regimes.
Reactive absorption is essentially an old process, known since the foundation of modern industry. This is a very important process, too, being the basic
operation in many technological chains. More recently, the role of RA as a key
environmental protection process has grown up signicantly.
Despite the clear importance of RA, its behavior is still not properly understood. This can be attributed to a very complex combination of process thermodynamics and kinetics, with intricate reaction schemes including ionic species, reaction
rates varying over a wide range, and complex mass transfer and reaction coupling.
As compared to distillation, RA is a fully rate-controlled process, and it denitely
occurs far from the equilibrium state. Therefore, practitioners and theoreticians are
highly interested in establishing a proper rate-based description of this process.
1.2.
Reactive Distillation
Reactive distillation is a combination of chemical reactions and distillation

(Figure 4b). This operation provides promising process alternatives to traditional
FIGURE 3 Scheme of an absorberdesorber link. (Adapted from Ref. 3.)
TABLE 1 Applications of RA Processes

Aim of the process
Example
Application area
Refs.
Removal of harmful
substances
Coke oven
gas purication,
amine washing
Solvent
regeneration
Gas purication
2325
Gas separation
26
Manufacture of
sulphuric acid,
formaldehyde
preparation,
manufacture of
soda ash
Manufacture of
nitrogenous
fertilizers
Water removal
from natural
gas, air drying
Synthesis gas
conditioning
Chemical
synthesis
2729
Fertilizer
industry
30
Gas drying
31,32
Gas separation/
gas purication
26
Retrieval/regeneration
of valuable substances
or nonreacted reactants
Production/preparation
of particular products
Water removal
Conditioning of
gas streams
sequential operations, shown in Figure 4a. Among potential advantages of

RD are:
New, less expensive products
Higher efciency because of overcoming thermodynamic and kinetic
limitations
Better selectivity due to suppressing of undesired reactions
Higher raw material conversion
Avoiding of hot spots
Savings due to smaller equipment
Less environmental pollution
One can distinguish between homogeneously and heterogeneously catalyzed RD; the latter is often called catalytic distillation (CD).
The applicability of the RD process is highly dependent on the properties
of the chemical system at hand. A classical example for which RD is recommended may be the reaction in which the products are generated by a reversible
reaction, e.g., in the production of methyl acetate. This system is very complex
because of the occurrence of several azeotropes between reactants and products.
FIGURE 4 Reactive distillation (b) as alternative to the sequential operation (a).
A usual solution in this case is a sequence of a reactor and several separation units
(Figure 5). Another wayan integrated RD process such as shown in Figure 6
allows for simultaneous formation of methyl acetate in the reaction zone, extractive distillation and product enrichment in the upper part of the column, and
methanol separation in the stripping zone. The production of esters such as
methyl acetate, ethyl acetate, and butyl acetate has for years been an interesting
RD application.
The most important application of RD today seems to be the production of
ethers such as methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether
(ETBE), and tertiary amyl methyl ether (TAME), which are widely used as modern gasoline components. Figure 7, upper part, shows a traditional process for
MTBE production, which is a strongly exothermic reaction. The disadvantages of
that process can be avoided if the reaction and separation take place within the
same zone of the reactor (Figure 7, lower part).
Table 2 gives a short overview of possible RD applications.
The design of RD is currently based on expensive and time-consuming
sequences of laboratory and pilot-plant experiments, since there is no commercially available software adequately describing all relevant features of reactions
(catalyst, kinetics, holdup) and distillation (VLE, thermodynamics, plate and packing behavior) as well as their combination in RD. There is also a need to improve
catalysts and column internals for RD applications (1,51). Figures 8 and 9 show
some examples of catalytic internals, applied for reactive distillation.
1.3.
Reactive Extraction
Liquidliquid extraction is based on partial miscibility of liquids. In the simplest

extraction system, two compounds have to be separated. This can be done by
extracting with a carefully selected solvent, in which one compound (solute) easily
dissolves whereas the other (nonsolute) does not. The solvent has to be recovered
FIGURE 5 Methyl acetate synthesis: conventional scheme. (From Ref. 33.)
FIGURE 6 Methyl acetate synthesis: reactive distillation scheme. (From Ref. 33.)
FIGURE 7 MTBE synthesis: conventional scheme (above) and reactive distillation scheme (below).
from the extract for recycling. In countercurrent extraction processes, there is a

light phase and a heavy phase, with one phase dispersed in the other. Which phase
has to be dispersed is an important question in the design of the process.
In reactive extraction, the use of liquid ion exchangers is recommended in
order to extract ionic solutes. These exchangers can be applied to manifold extraction processes in the chemical industry (e.g., extraction of furfural, organic, and inorganic acids), biochemical and pharmaceutical productions (e.g., penicillin, amino
acids), hydrometallurgy (e.g., mining of metals), and all related environmental applications. These last are especially attractive, since liquid ion exchangers react very
selectively and have an advantageous performance at very low feed concentrations.
For practical purposes, an ion exchanger is usually diluted in a nonaromatic,
high-boiling diluent (boiling point about 500 K) that is immiscible with water.
This prevents solvent losses and toxic problems and gives the organic phase the
required physical properties (high interfacial tension, low viscosity, low density),
since most liquid ion exchangers are highly viscous or even solid. In some cases
a modier, usually a long-chain alcohol, is added to help in the solubilization of
the soluteion exchanger complex. At very high solute loadings, a split of the
organic phase in a solvent-rich and a solvent-poor fraction may occur, especially
when using aliphatic diluents. The organic phase in RE is thus not a single substance,
as in physical extraction systems in which such three-phase liquid systems are not
encountered. Re-extraction is usually performed with chemicals, for instance,
with strong mineral acids.
All liquid ion exchangers can be mixed together in order to generate synergistic effects. As a special case, an equimolar mixture of cation and anion
exchangers gives a mixed extraction system, which can extract salts or acids. In
this case the re-extraction occurs by shift of either temperature, aqueous ionic
strength, or acidity/basicidity.
Equilibrium and selectivity constitute important aspects of reactive and
nonreactive extraction processes. Another important factor is the reaction kinetics, which has to be reasonably fast. Most RE processes are close to equilibrium
in less than ve minutes. Many ion exchangers need reaction times of less than
one minute, and thus diffusion of the solute complex in the organic phase is the
rate-determining step.
The cation and anion exchangers are amphiphilic substances that are adsorbed at the interface. The latter is then rigid and independent of the droplet
diameter, since friction forces are shielded. This is similar to physical extraction
systems, in which an analogous behavior is caused by surfactants in the aqueous
feed accumulated at the interface.
The problems concerning reaction equilibrium and kinetics description
based on chemical potentials rather than on concentrations are extensively discussed in Refs. 54 and 55, using the zinc system. The latter is recommended as a
reactive liquidliquid reference extraction test system by the European Federation of
TABLE 2 Applications of RD Processes

Reaction type
Esterication
Transesterication
Hydrolysis
Etherication
Alcylation
Condensation
Dismutation
Hydration
Nitration
Synthesis
Methyl acetate from
methanol and acetic acid
Methyl acetate from
methanol and acetic acid
Ethyl acetate from
ethanol and acetic acid
Butyl acetate from
butanol and acetic acid
Ethyl acetate from
ethanol and butyl acetate
Diethyl carbonate from
ethanol and dimethyl
carbonate
Acetic acid and
methanol from methyl
acetate and water
MTBE from isobutene
and methanol
ETBE from isobutene
and ethanol
TAME from
isoamylene and methanol
Cumene from
propylene and benzene
Diacetone alcohol
from acetone
Bisphenol-A from
phenol and acetone
Monosilane from
trichlorsilane
Mono ethylene glycol
from ethylene oxide
and water
4-Nitrochlorobenzene
from chlorobenzene
and nitric acid
Catalysta
hom.
33
het.
34,35
no data
36
hom.
37
hom.
38
het.
39
het.
40
het.
41,42
het.
43
het.
44
het.
45
het.
46
no data
47
het.
48
hom.
49
hom.
50
hom.: homogeneously catalyzed, het.: heterogeneously catalyzed.
Refs.
FIGURE 8 (a) Schematic of an RD column lled with catalytic internals CD TECH

(1catalytic balls, 2feed, 3distillate, 4bottom product, 5sieve tray) and
(b) catalytic structured packing Sulzer Katapak-S. (Part a from Ref. 52.)
Chemical Engineering (EFCE) and is thus well documented (http://www.icheme.uk/

learning/ or http://www.dechema.de/extraktion).
The selection of the right solvent is the key to successful separation by nonreactive and reactive liquidliquid extraction. In this respect, different criteria
should be taken into account, e.g.,
Selectivity
Capacity
Recoverability of solvent
Density
Viscosity and melting point
Insolubility of solvent
Interfacial tension
Toxicity and ammability
Corrosivity
Thermal and chemical stability
Availability and costs
Environmental impact.
Some of these criteria are crucial, while others are desirable properties improving
separation and/or making it more economical. Solvent selectivity, recoverability, and
a large density difference in respect to the rafnate are essential. Some of the requirements on the solvent can be in conict, and thus a compromise may be necessary.
Because aromatic diluents are more expensive and more toxic than aliphatic ones, the latter are preferably used in industrial practice (see earlier). Aromatic
diluents, with equivalent molecular weights comparable to those of aliphatic
ones, are more polar and thus more water soluble. The degradation of the diluent
is usually negligible in comparison with that of the ion exchanger. The latter one
can be chemically and thermally degrading and also can be poisoned by an irreversibly extracted compound.
Reactive extraction is closely related to the droplet phenomena, and thus
most theoretical models are based on droplet consideration. Their experimental
evaluation can be done using either a rising (falling) droplet apparatus (Figure 10a)
for short residence times or a Venturi tube for long contact times (Figure 10b) (56).
FIGURE 9 (a) Catalytic structured packing Montz Multipak and (b) an example of reactive trays. (Part b from Ref. 53.)
FIGURE 10 (a) Rising-droplet apparatus and (b) Venturi tube for droplet mass
transfer experiments. (1feed storage, 2metering pump, 3double-ow
valve, 4, 5pumps, 6heat exchanger, 7collecting funnel, 8stream to
analysis, 9valve).
Monodispersed droplets can be produced and in the latter case captured by the
counterowing continuous phase in the conus of the Venturi tube (see Figure 10b).
The RE process proceeds in three major types of equipment: mixer-settler
systems, column extractors, and centrifugal extractors. Countercurrent column
extractors can be further subdivided into nonagitated nonproprietary columns and
agitated proprietary extractors. Agitating the liquidliquid system breaks up
droplets and increases the interfacial area to improve the mass transfer and
column efciency. Various forms of energy input are used, e.g., rotation of propellers, impellers, and discs; pulsation, vibration, and ultrasonic devices; and centrifugal devices.
Some examples of mechanically agitated contactors are the rotating-disk
contactor (RDC), Karr, OldshueRushton, Scheibel, and Khni columns shown
in Figure 11.
There are three types of nonproprietary nonagitated types of extraction
columns (see Figure 12). The spray columns are the simplest type of extractors,
containing only distributors for the feed (often through perforated pipes). This
FIGURE 11 Agitated extractors. Left to right: RDC, Karr, OldshueRushton,

Scheibel, Khni extraction columns.
makes them cheap; however, they are limited in use due to signicant axial mixing in the column and the fact that the phases are not coalesced and redistributed.
This often results in low efciencies, which are comparable to one or two
theoretical equilibrium stages. Packed columns are much more efcient since the
packing reduces back-mixing and enhances drop reformation. The packing types
that can be used are the same as those for normal distillation operations (e.g.,
rings, saddles, or slightly modied structured packings of corrugated metal
sheets). Compared to packed beds, structured packings need a reduced crosssectional area for liquid ow, resulting in smaller column diameters. Sieve-tray
columns resemble the distillation column design, except that there is no weir. In
FIGURE 12 Nonagitated extractors. Left to right: spray, packed, sieve-tray

(light), sieve-tray (heavy) column.
an extraction process, either phase, the light or the heavy one, can be dispersed.
This means that there are also two sieve-tray designs in respect to downcomer and
top- or bottom-settler/distributor design.
Generally, the selection of a specic RE contactor is complicated due to the
large number of types available and the number of design parameters. The practical handling and design of a reactive solvent extraction processes can be found
elsewhere (see, e.g., Refs. 12 and 13).
2.
2.1.
FUNDAMENTALS OF PROCESS MODELING

General
As already mentioned, all three considered RSPs reveal signicant similarity, and
hence their modeling methods are based largely on the same framework.
Because of their multicomponent nature, RSPs are affected by a complex
thermodynamic and diffusional coupling, which, in turn, is accompanied by simultaneous chemical reactions (5759). To describe such phenomena adequately,
specially developed mathematical models capable of taking into consideration column hydrodynamics, mass transfer resistances, and reaction kinetics are required.
Homogeneously catalyzed RD, with a liquid catalyst acting as a mixture
component, and auto-catalyzed RD present essentially a combination of transport
phenomena and reactions taking place in a two-phase system with an interface. In
this respect they are very similar to RA and RE, and, generally, reaction has to be
considered both in the bulk and in the lm region. For slow reactions, a reaction
account exclusively in the bulk phase is usually sufcient.
For heterogeneous systems (CD), it is generally necessary to consider additionally the phenomena in the solid catalyst phase. In this case, very detailed
models using intrinsic kinetics and covering mass transport inside the porous catalyst arise (see, e.g., Refs. 6062). However, it is often assumed that all internal
(inside the porous medium) and external mass transfer resistances can be lumped
together (35,63,64). In this case each catalytically active site is in contact with the
liquid bulk, i.e., the catalyst surface is totally exposed to the liquid bulk phase and
can be completely described by the bulk variables (9,64). This results in the socalled pseudo-homogeneous models. If the reaction (either homogeneous or heterogeneous) is very fast, it does not depend on the reaction kinetics and thus can
be described using the data on chemical equilibrium only.
Modeling of hydrodynamics in gas/vapor/liquidliquid contactors includes
an appropriate description of axial dispersion, liquid holdup, and pressure drop. The
correlations giving such a description have been published in numerous papers and
are collected in several reviews and textbooks (e.g., Refs. 65 and 66). Nevertheless,
there is still a need for a better description of the hydrodynamics in catalytic column internals; this is being reected by research activities in progress (67).
The description of thermodynamics and chemical properties of the RSP is

very process specic, and hence its general detailed discussion would constitute
a separate issue. Therefore, we will give only a brief discussion of these topics in
the context of the following case studies (Section 3). Further related details can
be found in Refs. 6874.
In order to model large industrial reactive separation units, a proper subdivision of a column apparatus into smaller elements is usually necessary. These
elements (the so-called stages) are identied with real trays or segments of a
packed column. They can be described using different theoretical concepts, with
a wide range of physicochemical assumptions and accuracy.
2.2.
Equilibrium-Stage Model
In recent decades, the modeling and design of RSPs has usually been based on
the equilibrium-stage model. Since 1893, when the rst equilibrium-stage model
was published by Sorel (75), numerous publications discussing various aspects of
model development, application, and solution have appeared in the literature (76).
The equilibrium-stage model assumes that each gas/vapor/liquid stream leaving a
tray is in thermodynamic equilibrium with the corresponding liquid stream leaving the same tray. For the packed columns, the idea of the height equivalent to the
theoretical stage (HETS) is used. In case of RSPs, the chemical reaction has to be
additionally taken into account, either via reaction equilibrium equations or via
rate expressions integrated into the mass and energy balances.
In this respect, much depends on the relation between the mass transfer and
reaction rates in a particular RSP. The denition of the Hatta number representing the reaction rate in reference to that of the mass transfer helps to discriminate
between very fast, fast, average, and slow chemical reactions (68,77).
If a fast reaction system is considered, the RSP can be satisfactory
described assuming a reaction equilibrium. Here, a proper modeling approach is
based on the nonreactive equilibrium-stage model, extended by simultaneously
using the chemical equilibrium relationship.
Such descriptions can be appropriate enough for instantaneous reactions
and those close to them. In contrast, if the chemical reaction is slow, the reaction
rate dominates the whole process, and therefore, a reaction kinetics expression
has to be integrated into the mass and energy balances. This concept has been
used in a number of studies, for RA (e.g., Refs. 78 and 79), RD (e.g., Refs. 80
and 81), and RE (e.g., Refs. 8 and 12) process simulations.
In practice, RSPs rarely operate at thermodynamic equilibrium. Therefore,
some correlation parameters, such as tray efciencies or HETS values, have been
introduced to adjust the equilibrium-based theoretical description to reality. For
multicomponent mixtures, however, this concept often fails, since diffusion interactions of several components result in unusual phenomena such as osmotic or reverse
diffusion and mass transfer barrier (82,83). These effects cause a strange behavior of
the efciency factors, which are different for each component, vary along the column
height, and show a strong dependency on the component concentration (57,83,84).
The acceleration of mass transfer due to chemical reactions in the interfacial region is often accounted for via the so-called enhancement factors
(27,68,69). They are either obtained by tting experimental results or derived theoretically on the grounds of simplied model assumptions. It is not possible to
derive the enhancement factors properly from binary experiments, and signicant
problems arise if reversible, parallel, or consecutive reactions take place.
The equilibrium-stage model seems to be suitable for esterication reaction
in CD processes (see Refs. 35 and 74). However, it cannot be recommended for
all reaction types, especially those with higher reaction rates.
2.3.
Rate-Based Approach
A more physically consistent way to describe a column stage is known as the ratebased approach (57,85,86). This approach implies that actual rates of multicomponent mass and heat transfer and chemical reactions are taken into account
directly.
Considering homogeneous RSPs, mass transfer at the gas/vapor/liquid
liquid interface can be described using different theoretical concepts (57,59). Most
often the two-lm model (87) or the penetration/surface renewal model (27,88) is
used, in which the model parameters are estimated via experimental correlations.
In this respect the two-lm model is advantageous since there is a broad spectrum
of correlations available in the literature, for all types of internals and systems.
For the penetration/surface renewal model, such a choice is limited.
In the two-lm model (Figure 13), it is assumed that all of the resistance to
mass transfer is concentrated in thin stagnant lms adjacent to the phase interface
and that transfer occurs within these lms by steady-state molecular diffusion
alone. Outside the lms, in the bulk uid phases, the level of mixing is so high
that there is no composition gradient at all. This means that in the lm region,
only one-dimensional diffusion transport normal to the interface takes place.
Multicomponent diffusion in the lms is described by the MaxwellStefan
equations, which can be derived from the kinetic theory of gases (89). The
MaxwellStefan equations connect diffusion uxes of the components with the
gradients of their chemical potential. With some modication these equations
take a generalized form in which they can be used for the description of real gases
and liquids (57):
n
di
j1
xi N Lj x j N Li
c Lt Dij
i 1, . . . , n
(1)
FIGURE 13 Two-lm model.
where di is the generalized driving force:

di
xi di
T dz
i 1, . . . , n
(2)
Similar equations can be also written for the gas/vapor phase.

Thus the gas/vapor/liquidliquid mass transfer is modeled as a combination
of the two-lm model and the MaxwellStefan diffusion description. In this stage
model, the equilibrium state exists only at the interface.
The lm thickness represents a model parameter that can be estimated
using mass transfer coefcient correlations. These correlations reect the mass
transport dependence on physical properties and process hydrodynamics and are
available from the literature (see, e.g., Refs. 57, 68 and 90).
The two-lm model representation can serve as a basis for more complicated models used to describe heterogeneously catalyzed RSPs or systems containing suspended solids. In these processes a third solid phase is present, and
thus the two-lm model is combined with the description of this third phase. This
can be done using different levels of model complexity, from quasi-homogeneous
description up to the four-lm presentations that provide a very detailed description of both vapor/gas/liquidliquid and solid/liquid interfaces (see, e.g., Refs. 62,
68 and 91). A comparative study of the modeling complexity is given in Ref. 64
for fuel ether synthesis of MTBE and TAME by CD.
2.4.
Computational Fluid Dynamics
Every separation unit operation is governed by the continuum conservation laws,

and thus, in principle, everything meaningful to know in the continuum for any
process can be determined with computational uid dynamics (CFD) (92). In
recent years there have been signicant academic and industrial efforts to enable
the use of CFD for the design, scale-up, and optimal operation of a variety of
chemical process equipment.
Special attention has been given to the CFD modeling of two-phase ows. The
most frequently encountered computational techniques for calculating multiphase
ows are EulerLagrange and EulerEuler methods. EulerLagrange models are
applicable to dispersed ows (93). In these models the ow of the so-called carrier
phase is simulated by solving continuum-ow equations. The motion of individual
particles (or group of particles) of the dispersed phase is tracked through the ow
domain using the calculated carrier-phase ow eld as input; afterwards, mass,
momentum, and energy transfer between the two phases are computed and applied to
the carrier-phase ow eld prediction. This procedure requires several iterations (94).
EulerEuler models assume interpenetrating continua to derive averaged
continuum equations for both phases. The probability that a phase exists at a certain position at a certain time is given by a phase indicator function, which, for
steady-state processes, is equivalent to the volume of fraction of the correspondent phase (volume-of-uid technique). The phase-averaging process introduces
further unknowns into the basic conservation equations; their description requires
empirical and problem-dependent input (94). In principal, EulerEuler models
are applicable to all multiphase ows. Advantages and disadvantages of both
methods are compared, e.g., in Refs. 95 and 96.
The volume-of-uid technique can be used for a priori determination of the
morphology and rise characteristics of single bubbles rising in a liquid (97,98).
Considerable progress has been made in CFD modeling of bubbling gassolid
uidized beds by adoption of the Eulerian framework for both the dilute (bubbles)
and dense (emulsion) phases (99102). The use of CFD models for gasliquid
bubble columns has also aroused signicant interest in recent years, and both
EulerEuler and EulerLagrange methods have been employed for the description
of the gas and liquid phases (9496,103113).
There are also some attempts available in the literature to model tray hydrodynamics using CFD (114119).
Despite considerable success in some elds of application, the CFD simulations are still not fully mastered, especially where the considered processes
reveal clearly nonhomogeneous, segregated uid ow patterns. The latter are usually the basic phenomenon in packed or lmlike units used in reactive and nonreactive separations.
One of the important issues with RSPs is the development of efcient column internals. Such internals have to enhance both separation and reaction and
maintain a sound balance between them. This is valid for both homogeneously
and heterogeneously catalyzed processes, being especially important for CD. An
understanding of the complex, multiphase ow on the internals interrelated with the
mass transport and chemical reaction constitutes a very important challenge for the
future. Some rst steps in this respect have been done concerning the performance
of SULZER packings KATAPAK-S and SULZER BX and OPTIFLOW

(67,120122) as well as trays on which chemical reaction occurs (119).
Recently, a substantial effort has been made to optimize column internals
for reactive separations and to reduce the number of expensive hydrodynamics
experiments via the CFD simulations (67,119,122). Such simulations can be
regarded as virtual experiments carried out in order to predict the performance of
the internals by varying geometrical and structural parameters, thus reducing the
optimization time.
Necessary new hydrodynamic models have to be formulated and tested for
three-dimensional description of two-phase ow through the internals. Since
accurate resolution of the trickle-ow scale is not feasible at the moment, such
ow details have to be simplied and are subject to the subgrid modeling supported by experimental investigations of small-scale phenomena.
The CFD simulations should be linked with the rate-based process simulator, providing important information on the process hydrodynamics in the form of
correlations for mass transfer coefcients, specic contact area, liquid holdup,
residence time distribution, and pressure drop. An ability to obtain these correlation
via the purely theoretical way rather than by the traditional experimental one should
be considered a signicant advantage, because this brings a principal opportunity to
virtually prototyping of new optimized internals for reactive separations.
The local aspects of liquidliquid two-phase ow in RE has been the focus
of CFD analysis by different research groups (123126). In principle, all aspects
concerning single-phase ow phenomena (residence time distribution, impeller
discharge ow rate, etc.) can be tackled, even with complex geometries. However,
the two-phase CFD is still a challenge, and the droplet interactions (breakup and
coalescence) and mass transfer are not implemented in commercially available
codes. Thus these issues constitute an open area for further research and development (127).
3.
CASE STUDIES
3.1.
3.1.1.
Absorption of NOx
Chemical System
The reactive system considered is a basic one in the production of nitric acid as
well as in some other industrial processes (19). It consists of 10 components,
including air (N2, O2), water (H2O), oxyacids of nitrogen (HNO2, HNO3), and
nitrogen oxides (NO, NO2, N2O, N2O3, N2O4). The components are involved in
simultaneous, parallel, and consecutive reactions occurring in both phases. The
reactions are of high orders and most of them are exothermic.
Reaction kinetics is described by the scheme suggested in Ref. 128 and
modied in Ref. 129. This scheme involves eight reactions and can be regarded
as the most extensive reaction system so far. The gas-phase reactions are governed by the following equations:
2NO O 2 2 NO 2
H R0 114 kJ/mol
(R1)
NO NO 2 N 2 O 3
H R0 39.9 kJ/mol
(R2)
2NO 2 N 2 O 4
H R0 57.2 kJ/mol
(R3)
3NO 2 H 2 O 2HNO 3 NO
H R0 35.4 kJ/mol
(R4)
whereas the corresponding equations for the liquid phase are

2 NO 2 H 2 O HNO 2 HNO 3
H R0 10.72 kJ/mol
(R5)
N 2 O 3 H 2 O 2HNO 2
H R0 3.99 kJ/mol
(R6)
N 2 O 4 H 2 O HNO 2 HNO 3
H R0 5.03 kJ/mol
(R7)
3HNO 2 HNO 3 H 2 O 2NO
H R0 7.17 kJ/mol
(R8)
The liquid-phase reactions are valid for nitric acid concentrations below
34 wt %. In the case of higher nitric acid concentrations, Reactions (R5) to (R7)
become reversible. The oxidation of NO (Reaction (R1)) is the slowest reaction in
this system. Therefore, the total gas-phase holdup in absorbers can be determined
using the kinetic data for this reaction (130). The other gas-phase reactions are
instantaneous equilibrium reactions.
3.1.2.
Process Setup
Measurements of an industrial NOx absorption process, schematically shown in

Figure 14, were described in Ref. 131. The absorption plant constitutes a sequence
of four units used for the removal of nitrogen oxides from the waste gas of an adipin
acid factory. Each unit is separated by a metal plate into two sections. In fact there
are eight columns joined together as a countercurrent absorption plant. This plant
is operated at atmospheric pressure. Columns 17 have a pump around for cooling
of the liquid. The diameter of each column is 2.2 m; the height is 7 m. The packing
height is 3.2 m. The packing consists of 35 mm INTALOX ceramic saddles.
FIGURE 14 Absorption plant consisting of four units (eight columns).
The liquid feeds entering columns 7 and 8 are low-concentration nitric

acids. The liquid product has a HNO3 concentration of about 35 wt %. The gas
feed has a concentration of NOx of about 60,000 vppm. A quarter of NOx is NO;
the rest is NO2.
3.1.3.
Results and Discussion
The sensitivity analysis performed in Ref. 129 shows that the suggested model
provides concentration proles that are qualitatively correct. For the simulation of
the industrial absorption process shown in Figure 14, the following correlations
ensuring the most reliable results are selected:
The rate constant of Reaction (R1) (the slowest and hence the most important reaction in the system) according to Ref. 132
The liquid-side mass transfer coefcient according to Ref. 133
The gas-side mass transfer coefcient according to Wehmeier (see Ref. 134)
Figures 15 and 16 give an illustration of the model quality. Figure 15 shows
a comparison of the simulated and measured gas-phase concentrations of NO and
NO2 throughout the whole absorption plant, whereas in Figure 16, experimental
and simulated liquid-phase concentrations of HNO3 and HNO2 are demonstrated.
FIGURE 15 Experimental and simulated gas-phase concentrations of NO and

NO2 throughout the absorption plant.
The zigzag form of the simulated concentration proles results from switching
different sections of each single column (see Ref. 135). Good agreement between
experimental and simulation results can be readily observed, except for the rst
two columns. Here the larger deviations between experiments and simulated
results can be attributed to the fact that at high concentration of HNO3 Reactions
(R5) to (R7), assumed to be irreversible reactions, convert to reversible ones; the
data on their rate constants are lacking.
3.2.
Coke Gas Purication
3.2.1.
Chemical System
Coke oven gas consists mainly of a mixture of carbon monoxide, hydrogen,

methane, and carbon dioxide. It is contaminated with a variety of organic and
inorganic compounds that have to be separated in absorption columns before its
further use as a synthesis gas. The selective absorption of coke plant gas contamination results from a complex system of parallel liquid-phase reactions.
Instantaneous reversible reactions:
NH 3 H 2 O NH4 OH
( R9)
H 2 S H 2 O HS H 3O
( R10)
HCN H 2 O CN H 3O
( R11)
HCO3 H 2 O CO 32 H 3O
( R12)
H 3O OH 2 H 2 O
( R13)
Finite-rate reversible reactions:

CO 2 OH HCO3
( R14)
CO 2 2H 2 O HCO3 H 3O
( R15)
CO 2 NH 3 H 2 O H 2 NCOO H 3O
( R16)
The reactions including CO2 obey rst- and second-order kinetics, whereas the other reversible reactions are based on simple proton transfers and are
therefore regarded as instantaneous by the corresponding mass action law equations. The formation of bicarbonate ions (HCO3) takes place via two different
FIGURE 16 Experimental and simulated liquid-phase concentrations of HNO3

and HNO2 throughout the absorption plant.
mechanisms. The rate of the direct reaction between carbon dioxide and hydroxyl
ions (the most important step) is taken from Ref. 28.
Usually the reaction between CO2 and water is very slow and hardly contributes to the total rate of reaction of carbon dioxide. Nevertheless, in this work
it was considered of the rst order with respect to CO2, since the reaction kinetics depends on the carbonation ratio (136).
The absorption rate of carbon dioxide increases in the presence of amines
or ammonia. Therefore, the reaction kinetics of NH3 and CO2 has been considered in the model equations, too. The rate constant as a function of the temperature
has been determined according to Ref. 136. The coefcients for the calculation of
the chemical equilibrium constants in this system of volatile weak electrolytes are
taken from Ref. 137.
The CO2 absorption is hindered by a slow chemical reaction by which the
dissolved carbon dioxide molecules are converted into the more reactive ionic
species. Therefore, when gases containing H2S, NH3, and CO2 contact water, the
H2S and ammonia are absorbed much more rapidly than CO2, and this selectivity
can be accentuated by optimizing the operating conditions (23). Nevertheless, all
chemical reactions are coupled by hydronium ions, and additional CO2 absorption
leads to the desorption of hydrogen sulde and decreases the scrubber efciency.
3.2.2.
Process Setup
Todays coke plant gas purication processes are mostly carried out under atmospheric pressure, employing a circulated ammonia-based absorbent. The consumption of the external solvent is reduced via the use of ammonia available in
the coke gas (138). An example of innovative purication processes is the ammonia hydrogen sulde circulation scrubbing (ASCS) (Figure 17), in which the
ammonia contained in the raw gas dissolves in the NH3 absorber and then the
absorbent saturated with the ammonia passes through the H2S absorber to selectively absorb the H2S and HCN components from the coke gas. The next step is the
thermal regeneration of the absorbent with the steam in a two-step desorption plant,
whereas a part of the deacidied water is fed back into the H2S absorber (25).
Pilot-plant experiments have been carried out at real process conditions in
the coke plant August Thyssen (Duisburg, Germany). The DN 100 pilot column
(Figure 17) was made of stainless steel and equipped with about 4 m of structured
packing (Sulzer MELLAPAK 350Y), three liquid distributors, and a digital control system. Several steady-state experiments have been compared with the simulation results and supported the design optimization of the coke gas purication
process (25).
3.2.3.
A number of steady-state simulations have been performed with the aim of analyzing the inuence of numerical and physicochemical parameters, beginning
FIGURE 17 Ammonia hydrogen sulde circulation scrubbing process for the coke oven gas purication
(right) and H2S absorber (left).
with a single stage and ending with a simulation of a column. Different lm and
packing section discretizations, several mass transfer and hydrodynamic correlations, and different driving forces and diffusion models have been thoroughly
tested (Figure 18).
The most sensitive components appeared to be those involved in nite-rate
reactions, especially CO2. Furthermore, the impact of electrical forces enhances
the absorption of the strong electrolytes H2S and HCN by 35%, while the CO2
absorption rate is dominated by the reaction in the lm (139,140). Signicant
changes in the concentration proles and the component absorption rates due to
the lm reaction have been established (141,142).
Single-stage simulations reveal that intermolecular friction forces do not
lead to reverse diffusion effects, and thus the molar uxes calculated with the
effective diffusion approach differ only slightly from those obtained via the
MaxwellStefan equations without the consideration of generalized driving
forces. This result is as expected for dilute solutions and allows one to reduce
model complexity for the process studied (143).
As a further model simplication, a linearization of the lm concentration
proles has been studied. This causes no signicant changes in the simulation
results and at the same time reduces the total number of equations by half and stabilizes the numerical solution (142). The assumption of chemical equilibrium in
FIGURE 18 Absorption rates calculated with different model assumptions

concerning reaction consideration.
FIGURE 19 Liquid-phase axial concentration proles for the H2S scrubber:

comparison between experimental and simulation results based on different
model approaches.
the liquid bulk phase does not change the absorption rates signicantly, which
indicates fast conversion. Therefore, neglecting the lm reaction unrealistically
reduces the absorption rates. On the other hand, neglecting the reaction kinetics
within the lm results in completely different orders of magnitude for the calculated absorption degree. As a consequence, the reactions of carbon dioxide should
not be regarded as instantaneous, although the corresponding Hatta number of
about 7 characterizes the reaction as very fast (3).
The model optimized with respect to the numerical parameters and physicochemical properties has been validated against experimental data, whereas the
axial concentration and temperature proles for both phases demonstrated good
agreement (Figure 19). It has also been found that the simulations of the scrubber
based on the equilibrium-stage model extended by the chemical reaction kinetics
yield results completely inconsistent with the experimental studies; namely, the
selectivity toward H2S and HCN absorption cannot be reected (Figure 19). In
this case, the lm reaction represents an essential element of the rate-based
approach that has to be considered in the model. As a result, the only feasible simplication is represented by a linearization of the lm concentration proles,
including the implementation of the average reaction kinetics in the liquid lm
region (143).
3.2.4.
Dynamic Modeling
Steady-state modeling is not sufcient if one faces various disturbances in RA operations (e.g., feed variation) or tries to optimize the startup and shutdown phases of
the process. In this case, a knowledge of dynamic process behavior is necessary.
Further areas where the dynamic information is crucial are the process control as
well as safety issues and training. Dynamic modeling can also be considered as the
next step toward the deep process analysis that follows the steady-state modeling
and is based on its results.
The dynamic formulation of the model equations requires a careful analysis of the whole system in order to prevent high-index problems during the
numerical solution (144). As a consequence, a consistent set of initial conditions
for the dynamic simulations and suitable descriptions of the hydrodynamics have
to be introduced. For instance, pressure drop and liquid holdup must be correlated with the gas and liquid ows.
The model optimized based on steady-state analysis allows for a dynamic
real-time simulation of the entire absorption process. Because dynamic behavior is
determined mainly by process hydraulics, it is necessary to consider those elements
of the column periphery that lead to larger time constants than the column itself.
Therefore, major elements of the column periphery, such as distributors, stirred
tanks, and pipelines, have been additionally implemented into the dynamic model.
The dynamic behavior of the coke gas purication process has been investigated systematically (139,140,145). For instance, local perturbations of the gas
load and its composition have been analyzed. A signicant dynamic parameter is
represented by the liquid holdup. Figure 20 demonstrates the changes of the solvent composition after a decrease of the gas-ow rate from 67 m3/h to 36.4 m3/h
and a simultaneous small increase in the liquid-ow rate.
The liquid holdup of the packing section decreases, which leads to a lower
conversion of the kinetically controlled reactions of CO2 and a reduction in the
CO2 absorption rate. As a consequence, the solvent mole fractions of HCO3 and
carbamate decreases whereas the relative fraction of HS increases. The selectivity of the absorption process toward the H2S and HCN reduction is enhanced by
minimizing the liquid holdup of the column. At the same time, a larger interfacial
area improves the performance of the plant. Therefore, modern industrial sour gas
scrubbers should be equipped with structured packings.
Figure 21 illustrates the system response after a sudden increase in the gas
ow by 20% and its H2S load by 100%. As expected, the H2S load increases
everywhere along the column height in the gas phase. The change is more signicant in the lower part of the absorber than at the top because some additional
hydrogen sulde is absorbed. The new steady state is already achieved after
30 minutes, which justies the implementation of dynamic models for the column
periphery.
FIGURE 20 Dynamic change of solvent composition after a sudden signicant decrease in the gas-ow
rate and a simultaneous small increase in the liquid-ow rate.
FIGURE 21 Dynamic change of the H2S gas-phase concentration along the

column after a sudden increase in the gas ow and its H2S load.
3.3.
Methyl Acetate Synthesis, Batch Distillation
3.3.1.
Chemical System
The synthesis of methyl acetate from methanol and acetic acid is a slightly
exothermic equilibrium-limited liquid-phase reaction:
CH 3OH (CH 3 )COOH (CH 3 )COO(CH 3 ) H 2 O
H R0 4.2 kJ/mol
(R17)
The low equilibrium constant and the strongly nonideal behavior that causes the
forming of the binary azeotropes methyl acetate/methanol and methyl acetate/
water make this reaction system interesting as a possible RD application (33).
Therefore, methyl acetate synthesis has been chosen as a test system and investigated in a semibatch RD column. Since the process is carried out under atmospheric pressure, no side reactions in the liquid phase occur (146).
3.3.2.
Process Setup and Operation
The catalytic packing MULTIPAK (147) applied in this case study consists of
corrugated wire gauze sheets and catalyst bags of the same material assembled
in alternate sequence. Sufcient mass transfer between gas and liquid phase is
guaranteed by segmentation of the catalyst bags and numerous contact spots with
the wire gauze sheets. The packing was equipped with the acid ion exchange resin
known as an effective catalyst for esterication processes (34,148).
A batch distillation column with a diameter of 100 mm and a reactive packing height of 2 m (MULTIPAK I) in the bottom section and an additional meter
of conventional packing (ROMBOPAK 6M) in the top section was used. The
ow sheet of the column is shown in Figure 22.
At rst, the distillation still was charged with methanolthe low-boiling
reactantand heated under total reux until steady-state conditions were achieved.
At that moment, acetic acidthe high-boiling reactantwas fed above the reaction
zone to the second distributor. After 30 min the reux ratio was changed from
innity to 2 and the product withdrawal at the top of the column began. During the
FIGURE 22 Reactive distillation column, batch operation.
column operations, the liquid-phase concentration proles along the column and
the temperature proles were measured. For the determination of the liquid-phase
composition, two methods were applied simultaneously. On the one hand, samples
were taken and analyzed by gas chromatography. On the other hand, an online
NIR spectrometer was used to determine the concentration without taking any
samples (149).
3.3.3.
Figures 23 and 24 show the liquid-phase compositions for, respectively, the

reboiler and condenser as functions of time. After column startup, the concentration of methanol decreases continuously whereas the distillate mole fraction of
methyl acetate reaches about 90%. A comparison of the rate-based simulation
(with the MaxwellStefan diffusion equations) and experimental results for the
liquid-phase composition at the column top and in the column reboiler demonstrates
their satisfactory agreement (Figures 23 and 24). Figure 25 shows the simulation
FIGURE 23 Liquid mole fractions in the column reboiler: lines, simulations;

dots, experiments.
FIGURE 24 Liquid mole fractions in the column condenser: lines, simulations; dots, experiments.
results obtained with different modeling approaches, after an operation time of

10,000 s. The reference model employs the rate-based approach and the Maxwell
Stefan diffusion equations. Another rate-based model assumes effective diffusion
coefcients instead of the MaxwellStefan equations. The third model used is an
equilibrium-based one. Both the reference model and effective-diffusion model
show similar results. The equilibrium-stage model is only able to describe the
process behavior qualitatively. This is in contrast to the reactive absorption
processes (see Sections 3.1 and 3.2) and can be explained by the low reaction rate,
which dominates the whole process kinetics.
3.4.
Methyl Acetate Synthesis, Steady-State Distillation
3.4.1.
Chemical System
The synthesis of methyl acetate from methanol and acetic acid analyzed in this
case study is the same as described by Reaction (R17):
CH 3OH (CH 3 )COOH (CH 3 )COO(CH 3 ) H 2 O
FIGURE 25 Axial concentration profiles for the semibatch column

(t 10,000 s ) .
3.4.2.
Process Setup
The column (35) has an inner diameter of 50 mm and a total packing height of
4 m composed of a reactive section of 2 m and two nonreactive sections of 1 m
each, below and above the reactive part of the column (Figure 26). The acetic acid
feed is located above the catalytic packing, while methanol is fed to the column
below the reactive section. A similar column design was presented in Ref. 150.
3.4.3.
A series of experiments have been performed with a stoichiometric feed ratio of

acetic acid and methanol. The reux ratio was kept constant at a value of 2.0, the
feed ow rate at a value of 3.0 kg/h, while the heat duty to the reboiler was varied
over a wide range. A comparison of experimental results and model prediction for
the liquid-phase composition proles along the column is given in Figure 27 for
different reboiler duties (151). The theoretical values are displayed with continuous lines and empty symbols, whereas the experimental data measured along the
column are shown by the relevant lled symbols. It can be seen that the process
behavior is reected by the simulations with high accuracy. A maximum concentration of methanol and acetic acid can be observed at the respective feed locations, while methyl acetate is enriched toward the top and water toward the
bottom of the column.
3.5.
Synthesis of Methyl Tertiary Butyl Ether
3.5.1.
Chemical System
The synthesis of methyl tertiary butyl ether (MTBE) is one of the most important
applications of RD. MTBE is produced via an acid-catalyzed reaction between
methanol and isobutylene:
CH 3OH C(CH 3 ) 2 CH 2 C(CH 3 )3 OCH 3
H R0 37.7 kJ/mol
(R18)
This reaction has been extensively studied by several authors, e.g., Refs. 152154.
3.5.2.
Process Setup
MTBE synthesis was investigated both theoretically and experimentally. Here,

some results for a pilot-scale RD column at Neste Oy Engineering, Finland, are
FIGURE 26 Reactive distillation column, steady-state operation.
FIGURE 27 Liquid-phase composition proles along the 50-mm-diameter

catalytic distillation column for methyl acetate synthesis at reux ratio of 2.0
and different reboiler duties: (a) 295W (b) 873W (c) 1161W.
presented (155). The column (used as an example here) has a catalytic section in the
middle part. This catalytic section may consist either of a packed bed of catalytically active rings (91) or of structured catalytic packing (147). The rectifying and stripping sections are lled with Intalox Metal Tower Packing. The methanol feed is
introduced just above the catalyst section of the column and the hydrocarbon feed
just below.
3.5.3.
Figure 28 demonstrates the simulated and measured concentration proles for the
pilot test made in the column, with the reactive section lled with catalytically
active rings. In the simulations four componentsmethanol, isobutene, MTBE,

and 1-butenewere chosen to describe the system under consideration. Here,
segment 1 corresponds to the reboiler. A satisfactory agreement between calculated and measured values can be clearly observed. In Figure 29, the simulation
results for the column with different reactive internals, catalytic packing
MULTIPAK, are shown. Here, 16 components were considered. Again, the
liquid bulk composition proles demonstrated in Figure 29 agree well with the
experimental data.
3.6.
3.6.1.
Reactive Extraction of Zinc

Chemical System
The extraction of zinc with the cation exchanger di(2-ethylhexyl)phosphoric acid,

RH, is recommended by the EFCE as a test system for RE. Physical properties,
handling, equilibrium data, etc. are documented on the internet (http:// www.
dechema.de/Extraction, http://www.icheme.org/learning).
In brief, the ion exchanger is dimeric, R 2 H 2 , in aliphatic diluents (156),
and the overall reaction is then
aZn 2 b R 2 H 2 Zn a R 2 a (RH)2 b2 a 2 H
(R19)
At low concentrations, polynuclear complexes do not exist (157); thus a 1:

Zn 2 b R 2 H 2 ZnR 2 (RH)2 b2 2 H
(R20)
FIGURE 28 Calculated and experimental liquid compositions for experiments

with catalytically active rings.
FIGURE 29 Calculated and experimental liquid compositions for experiments with catalytic
structured packing.
The mass action law on the basis of concentrations then yields

K eq
[ ZnR 2 ( RH) 2 b2 ][H ]2

[H ]2
D

Zn
[ Zn 2 ][ R 2 H 2 ]b
[ R 2 H 2 ]b
(3)
where DZn denotes the partition coefcient of zinc between the organic and the
aqueous phase (bar indicates organic species). In logarithmic form, the stoichiometry of the complex, b, is determined by slope analysis:
log DZn b log([R 2 H 2 ]) 2 pH log K eq
(4)
As can be seen, the partition increases with increasing ion exchanger concentraeq
tion, R 2 H 2 , and with pH. The determination of the equilibrium constant, K , is
discussed, e.g., in Ref. 158.
3.6.2.
Process Setup
Apart from the nuclear industry, the most frequently installed pieces of process
equipment are mixer-settler cascades. The advantage is the easy control of each
stage regarding the pH value, selection of the phase to be dispersed, etc. (12,15).
The disadvantages are the high investment costs and large solvent inventory.
Nowadays, modern designed extractants (with fast kinetics) allow a process
design with highly efcient extraction columns (159). Applications are found in
the chemical industry, e.g., with sulfonic acid extraction (160). The rst application on a big scale in hydrometallurgy was reported in 1997 at WMC Olympic
Dam, Australia, where 10 pulsed Batman columns (0.5 to 3 m in diameter and
35 m tall) were used for uranium recovery. An increased recovery (from 90% to
97%) was found after replacing the formerly used mixer-settler units.
The RE of zinc is reported in detail when using an RDC, including the discussion of the stripping process to regenerate the ion exchanger for cyclic reuse
(161163).
3.6.3.
A comparison of predicted and experimental mass transfer coefcients is given in

Figure 30. The simulated overall mass transfer coefcient originates from a
model that is a combination of the microkinetic reaction according to Eq. (B9)
and eddy diffusion according to Eq. (B11) (see Appendix B). Figure 30 shows
that the mass transfer coefcient at higher concentrations is generally underestimated, thus including some safety value for the process design. As discussed in
detail in Ref. 56, combinations of microkinetics [Eq. (B9)] with other eddy diffusion correlations instead of Eq. (B11) (e.g., Refs. 164 and 165) are also appropriate to describe the system. In contrast to this, the combination of microkinetics
with molecular diffusion concepts fails, and the same is true when the equilibrium
FIGURE 30 Comparison of experimental and simulated overall mass transfer

coefcients at different initial zinc concentrations and droplet diameters
(1, 2, or 3 mm ) .
approach is used neglecting the kinetics rate law. The results of the column simulations are discussed in Refs. 162 and 163, and a special discussion on contamination effects is given in Ref. 166.
4.
SUMMARY AND OUTLOOK
This chapter concerns the most important reactive separation processes: reactive
absorption, reactive distillation, and reactive extraction. These operations combining the separation and reaction steps inside a single column are advantageous as
compared to traditional unit operations. The three considered processes are similar
and at the same time very different. Therefore, their common modeling basis is discussed and their peculiarities are illustrated with a number of industrially relevant
case studies. The theoretical description is supported by the results of laboratory-,
pilot-, and industrial-scale experimental investigations. Both steady-state and
dynamic issues are treated; in addition, the design of column internals is addressed.
Reactive absorption, reactive distillation, and reactive extraction occur in
multicomponent multiphase uid systems, and thus a single modeling framework
for these processes is desirable. In this respect, different possible ways to build such
a framework are discussed, and it is advocated that the rate-based approach provides the most rigorous and appropriate way. By this approach, direct consideration
of the diffusional and reaction kinetics is realized. Special attention is paid to the
application of CFD, which could become a powerful theoretical tool to predict the
ow behavior for different column units and internals geometries for engineering
applications. In particular, CFD can play an outstanding role in the development of
the column internals for reactive separations. Fundamental advances in the understanding of the underlying physicochemical phenomena when coupled with CFD
would go a long way toward support of reactive separation technology.
The modeling of RA is illustrated by the absorption of NOx and by the
coke gas purication process. The rst case is modeled by using an analytical treatment of the lm phenomena, whereas the second one is solved by a purely numerical technique. The simulation results are compared with the experimental data
obtained at an industrial absorption plant consisting of eight units with
pump around (NOx) and at a pilot column for the ammonia hydrogen sulde
circulation scrubbing process (coke gas purication). For the latter case, both
steady-state and dynamic conditions are considered. The comparison results, on the
one hand, demonstrate a good agreement between the rate-based simulations and
experimental data, and, on the other hand, warn of using the equilibrium approach,
which appears completely inappropriate in the case of complex nite-rate reactions.
The modeling of RD processes is illustrated with the heterogenously catalyzed
synthesis of methyl acetate and MTBE. The complex character of reactive distillation processes requires a detailed mathematical description of the interaction of
mass transfer and chemical reaction and the dynamic column behavior. The most
detailed model is based on a rigorous dynamic rate-based approach that takes into
account diffusional interactions via the MaxwellStefan equations and overall reaction kinetics for the determination of the total conversion. All major inuences of the
column internals and the periphery can be considered by this approach.
As an application example, the dynamic model was used for the simulation
of the steady-state and semibatch production of methyl acetate, performed in a
packed column with a catalytic packing. For the model validation, several experiments were carried out in a pilot-plant column. For the investigated operation
range, the simulation results are in good agreement with the experimental data.
The use of this model for model-based process control calls for suitable
model reductions without a signicant decrease in the predictivity. For the methyl
acetate process, a simplied description of the mass transfer using effective diffusion coefcients and neglecting diffusional interactions seems to be sufcient.
On the other hand, a detailed description of the reaction, including the specic
phenomena of the heterogeneous catalysis by an adequate consideration of the solid
phase, is required for the predictive simulation of even more complex systems,
including side and consecutive reactions. Optimal functioning of reactive distillation depends on careful process design, with appropriately selected column
internals, feed locations, and catalyst placement. Greater understanding of the
general and particular features of the process behavior is equally essential.
The modeling of RE processes is strongly related to the knowledge of the

reaction equilibrium and kinetics and mass transfer regime. The latter is decisive for
column simulations, whereas eddy diffusivity concepts often have to be used. The
parameters can easily be obtained in small-scale laboratory devices, with a minimum
of substance involved. A real challenge is the correct hydrodynamic description of
the two-phase ow. The assumption of plug ow gives acceptable results with column diameters smaller than 0.1 m. The commonly applied axial dispersion model
or back-mixing model uses one parameter to account for nonideal ow in each
phase. Here the dispersed phase is considered to be pseudo-continuous and
monodisperse. Droplet population models taking into account the dynamic processes of coalescence and breakup of droplets should give a more realistic picture
and thus a more rm design of a process. The use of CFD calculations in liquid
liquid dispersed-phase ow is limited to single-droplet ow or low column holdup.
The simulation of large industrial columns especially is not feasible nowadays.
Some important general aspects of rate-based modeling as well as further
peculiarities of the specic process applications and the different solution strategies are given in Appendices A and B.
The key reactive separation topics to be addressed in the near future are a
proper hydrodynamic modeling for catalytic internals, including residence time
distribution account and scale-up methodology. Further studies on the hydrodynamics of catalytic internals are essential for a better understanding of RSP behavior
and the availability of optimally designed catalytic column internals for them. In
this regard, the methods of computational uid dynamics appear very helpful.
The development of new methodologies enabling the creation of intelligent,
tailor-made column internals and consequent RSP optimization constitutes one
of the burning present-day challenges. Such a development is already in progress
in some European research projects.
Despite the recent rapid development of computer technology and numerical methods, the rate-based approach in its current realization still often requires
a signicant computational effort, with related numerical difculties. This is one
of the reasons the application of rate-based models to industrial tasks is rather
limited. Therefore, further work is required in order to bridge this gap and provide chemical engineers with reliable, consistent, robust, and comfortable simulation tools for reactive separation processes.
ACKNOWLEDGMENTS
We would like to thank our colleagues at the Chair of Fluid Separation Processes,
Dortmund University, and all other project partners who have been involved
in the research activities. We are also grateful to the German Research Foundation (DFG, Grants No. Schm 808/5-1, Ba 1569/2-1 2-2, Ba 1569/6-1), the
Volkswagen Foundation (Project No. I/70 875, 876, 877), the European
Commission (BRITE-EURAM program, CEC Project No. BE95-1335), the

German Federal Ministry of Education and Research (BMBF, Project No.
03C0306), the Foundation Rheinland-Pfalz fr Innovation (836-386261/193),
as well as BASF AG, Bayer AG, Axiva GmbH, Degussa.
NOMENCLATURE
aI
As
B
c
CIP
dC
di
dp
D
Dax
Deff
DZn
E
E
F
FC
G
h
H R0
ky
Ki
Keq
[K]
l
L
n
Ni
Q
R
R

Re
Sc
Sh
t
T
uL
U
specic gasliquid interfacial area

column cross section
liquid load
molar concentration
adjustable parameter, Eq. (B10)
column diameter
generalized driving force for component i
droplet diameter
MaxwellStefan diffusion coefcient
axial dispersion coefcient
effective diffusion coefcient
partition coefcient of zinc
length-specic energy holdup
dimensionless residence time distribution
Faradays constant
gas capacity factor
gas molar ow rate
molar enthalpy
reaction enthalpy
overall mass transfer coefcients
distribution coefcient
equilibrium constant
reaction matrix [Eq. (B1)]
axial coordinate
liquid molar ow rate
number of components of mixture
molar ux of component i
heat ux
total component reaction rate
column vector with elements Ri
gas constant
Reynolds number
Schmidt number
Sherwood number
time
temperature
liquid velocity
length-specic molar holdup
m2/m3
m2
m3/(m2s)
mol/m3
m
1/m
m
m2/s
m2/s
m2/s
J/m
9.65 104 C/mol
Pa0.5
mol/s
J/mol
J/mol
m/s
1/s
m
mol/s
mol/(m2s)
W/m2
mol/m3s
mol/m3s
8.3144 J /(mol K)
s
K
m/s
mol/m
w
xi
x
yi
z
zi
terminal velocity
rst uid-phase (liquid) mole fraction
of component i
column vector with elements xi
second uid-phase (gas, vapor, or liquid)
mole fraction of component i
lm coordinate
ionic charge of component i
m/s
mol/mol
mol/mol
mol/mol
m
Greek Letters

r

c
d

lm thickness
dimensionless lm coordinate
forward-reaction constant
backward-reaction constant
thermal conductivity
chemical potential
dynamic viscosity of continuous phase
dynamic viscosity of dispersed phase
volumetric holdup
electrical potential
Subscripts
G
i, j
L
t
gas or second uid phase

component/reaction indices
liquid phase
mixture property
Superscripts
B
I
bulk phase
phase interface
Abbreviations
ADM
CD
PDE
RA
RD
RE
RH
RSP
axial dispersion model

catalytic distillation
piston ow model with axial
dispersion and mass exchange
reactive absorption
reactive distillation
reactive extraction
di(2-ethylhexyl) phosphoric acid
reactive separation process
m
m3/2/(mol1/2s)
s1
W/(m K)
J/mol
Pa s
Pa s
m3/m3
V
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APPENDIX A. A DETAILED DESCRIPTION OF

RATE-BASED MODELING
A.1.
Balance Equations
The mass balance equations of the traditional multicomponent rate-based model

(see, e.g., Refs. 57 and 58) are written separately for each phase. In order to give
a common description to all three considered RSPs (where it is possible, of
course) we will use the notion of two contacting uid phases. The rst one is
always the liquid phase, whereas the second uid phase represents the gas phase
for RA, the vapor phase for RD and the liquid phase for RE. Considering homogeneous chemical reactions taking place in the uid phases, the steady-state balance equations should include the reaction source terms:
0
0
d
( LxiB ) ( N LiB a I RLiB L ) As
dl
d
(GyiB ) ( NGiB a I RGiB G ) As
dl
i 1, . . . , n
i 1, . . . , n
(A1)
(A2)
If chemical reactions take place in the (rst) liquid phase only (this is
valid for most of RD processes), the phase balances for the second uid phase
simplify to
0
d
(GyiB ) NGiB a I As
dl
i 1, . . . , n
(A3)
The bulk-phase balances are completed by the summation equation for the
liquid and second uid bulk mole fractions:
n
B
i
1
i1
(A4)
y 1
B
i
(A5)
i1
The volumetric liquid holdup, L, depends on the gas/vapor and liquid
ows and is calculated via empirical correlations (e.g., Ref. 65). For the determination of axial temperature proles, differential energy balances are formulated,
including the product of the liquid molar holdup and the specic enthalpy as
energy capacity. The energy balances written for continuous systems are as
follows:
0
0
d
0
( LhLB ) (QLB a I RLB L H RL
) As
dl
(A6)
d
0
(GhGB ) (QGB a I RGBG H RG
) As
dl
(A7)
In the dynamic rate-based stage model, molar holdup terms have to be considered in the mass balance equations, whereas the changes in both the specic
molar component holdup and the total molar holdup are taken into account. For
the liquid phase, these equations are as follows:
U Li ( LxiB ) ( N LiB a I RLiB L ) As

t
l
U Li xiBU Lt xiB ( L c Lt As )
i 1, . . . , n
i 1, . . . , n
(A8)
(A9)
The gas/vapor holdup can often be neglected due to the low gas-phase
density, and the component balance equation reduces to Eq. (A2) (see also
Ref. 139).
A.2.
Mass Transfer and Reaction Coupling in Fluid Films
The component uxes NiB entering into Eqs. (A1)(A3) are determined based on
the mass transport in the lm region. Because the key assumptions of the lm
model result in the one-dimensional mass transport normal to the interface, the
differential component balance equations including simultaneous mass transfer
and reaction in the lm are as follows:
dNLi
RLi 0
dz
i 1, . . . , n
(A10)
Equations (A10), which are generally valid for both liquid and second uid
phases, represent nothing but differential mass balances for the lm region, with the
account of the source term due to the reaction. To link these balances to process
variables like component concentrations, some additional relationships, often called
constitutive relations (see Ref. 57), are necessary. For the component uxes Ni,
these constitutive relations result from the multicomponent diffusion description
[Eqs. (1) and (2)] and, for the source terms, from the reaction kinetics description.
The latter strongly depends on the specic reaction mechanism, the stoichiometry, and the presence or absence of parallel reaction schemes (69). The rate
expressions for Ri usually represent nonlinear dependences on the mixture composition and temperature. Specically for the coupled reactionmass transfer
problems, such as Eqs. (A10), it is always essential as to whether or not the reaction rate is comparable to that of diffusion (68,77). Equations (A10) should be
completed by the boundary conditions relevant to the lm model. These conditions
specify the values of the mixture composition at both lm boundaries. For example, for the liquid phase:
xi ( z 0) xiI ,
xi ( z L ) xiB
i 1, . . . , n
(A11)
Combining Eqs. (A10) with the boundary conditions (A11) written in vector form and using constitutive relations such as Eqs. (1) and (2), we obtain a
vector-type boundary-value problem, which permits the component concentration
proles to be obtained as functions of the lm coordinate. These concentration
proles, in turn, allow one to determine the component uxes. Thus the boundaryvalue problem describing the lm phenomena has to be solved in conjunction
with all other model equations.
The composition boundary values entering into Eqs. (A11) represent external values for Eqs. (A10). With some further assumptions concerning the diffusion and reaction terms, this allows an analytical solution of the boundary-value
problem [Eqs. (A10) and (A11)] in a closed matrix form (see Refs. 58 and 135).
On the other hand, the boundary values need to be determined from the total system of equations describing the process. The bulk values in both phases are found
from the balance relations, Eqs. (A1) and (A2). The interfacial liquid-phase concentrations xiI are related to the relevant concentrations of the second uid phase,
yiI , by the thermodynamic equilibrium relationships and by the continuity condition for the molar uxes at the interface (57,135).
Due to the chemical conversion in the liquid lm, the molar uxes at the
interface and at the boundary between the lm and the bulk of the phase differ.
The system of equations is completed by the conservation equations for the mass
and energy uxes at the phase interface and the necessary linking conditions
between the bulk and lm phases (see Refs. 57, 59, and 84).
Generally all these considerations are also valid for the second uid lm
phase, provided that reactions occur there (135). Both analytical and numerical
solutions of the coupled diffusion-reaction lm problem are analyzed at full
length in Ref. 167; their particular applications are considered in Section 3.
A.3.
Nonideal Flow Behavior in Catalytic Column Internals
The mass balances [Eqs. (A1) and (A2)] assume plug-ow behavior for both the
gas/vapor and liquid phases. However, real ow behavior is much more complex
and constitutes a fundamental issue in multiphase reactor design. It has a strong
inuence on the reactor performance, for example, due to back-mixing of both
phases, which is responsible for signicant effects on the reaction rates and product selectivity. Possible development of stagnant zones results in secondary undesired reactions. To ensure an optimum model development for CD processes,
experimental studies on the nonideal ow behavior in the catalytic packing
MULTIPAK are performed (168).
The experimental results conrm that the uid ow in MULTIPAK deviates from plug-ow behavior (Figure 31). Calculated axial dispersion coefcients
are about 104102 m2/s, which are several orders of magnitude larger than that
for molecular diffusion (Figure 32). Therefore, in the investigated operating
range, nonideal mixing effects are caused by hydrodynamic rather than molecular diffusion effects. Calculated Bodenstein numbers are one order of magnitude
FIGURE 31 Comparison between the experimental RTD curve for the catalytic packing MULTIPAK (dC 0.1 m), the ADM model, and the PDE model.
FIGURE 32 Axial dispersion coefcients for the catalytic packing MULTIPAK

(dC 0.1 m ) , calculated based on the ADM model.
smaller than those for xed-bed reactors, which may be caused by two effects: the
occurrence of stagnant zones in the catalyst layer, and liquid bypassing due to the
hybrid structure of the catalytic packing (168).
The rate-based models suggested up to now do not take liquid back-mixing
into consideration. The only exception is the nonequilibrium-cell model for
multicomponent reactive distillation in tray columns presented in Ref. 169. In this
work a single distillation tray is treated by a series of cells along the vapor and
liquid ow paths, whereas each cell is described by the two-lm model (see
Section 2.3). Using different numbers of cells in both ow paths allows one to
describe various ow patterns. However, a consistent experimental determination
of necessary model parameters (e.g., cell lm thickness) appears difcult, whereas the complex iterative character of the calculation procedure in the dynamic
case limits the applicability of the nonequilibrium cell model.
A far more promising approach is represented by the so-called differential
models, such as the axial dispersion model (ADM) (170) as well as the pistonow model with axial dispersion and mass exchange (PDE) (171). Experimental
studies (168) show that the ADM gives an appropriate description of the nonideal
flow behavior of the liquid phase in catalytic packings (see Figure 31). Considering
the nonideal ow behavior via the ADM, the dynamic mass balances [cf. Eqs.
(A8)] take the following form:
D 2
ULi ax 2 ( LxiB ) ( LxiB ) ( N LiB a I RLiB L ) As

u L l
t
l
i 1, . . . , n (A12)
A thorough investigation of the inuence of the ow nonideality in catalytic

packings on the dynamic process behavior of specic CD processes is an objective of some current studies (172).
Equation (A12) is widely used in RE, but it does not account for the specic interactions of the dispersed phase. In this respect current research is focused
on drop population balance models, which account for the different rising velocities of the different-size droplets and their interactions, such as droplet breakup
and coalescence (173180).
APPENDIX B. MODELING PECULIARITIES AND
MODEL PARAMETERS FOR THE CASE STUDIES
B.1.
Absorption of NOx
In terms of the concentration vector, Eq. (A10) is a nonlinear differential equation of the second order. The boundary-value problem [Eqs. (A10) and (A11)] is
usually solved numerically. However, it is also possible to linearize the reaction
term using the method suggested in Ref. 181:
R [ K ] x
(B1)
Equation (B1) provides a satisfactory representation for many processes over the
entire reaction range and is a good linear approximation for most systems in a sufciently small range (see, e.g., Refs. 68 and 182184). Equation (B1) has gained
widespread acceptance in various chemical and reactor engineering areas (185) and
is recommended for use in the modeling of reactive separation operations (59,184).
The approximation of Eq. (B1) allows one to reduce Eqs. (A10) and (A11)
to a linearized boundary-value problem (183,184,186). The latter can then be
solved analytically and yields a compact matrix-form solution for the concentration proles in the lm region [58]. Such a solution gives simple analytical
expressions for the component uxes with regard to the homogeneous reaction in
the uid lms (see Ref. 135), which can be of particular value when large industrial reactive separation units are considered and designed.
The methods of determination of the reaction matrix [K] are considered in
Refs. 167, 181, 183, 184 and 186. Another important matrix parameter entering
into the linearized lm mass transport equation is the multicomponent diffusion
matrix [D]. The latter results from the transformation of the MaxwellStefan Eqs. (1)
to the form of the generalized Ficks law (83). Matrix [D] is generally a function of
the mixture composition and it is assumed constant along the diffusion path (83).
The direct expressions for the elements of the diffusion matrix [D] can be found,
for example, in Ref. 57.
The linearization of the initial lm mass transport equation and its analytical
solution were applied to simulate the industrial NOx absorption process considered.
In order to calculate the multicomponent diffusion matrices [D], the binary
diffusivities in both phases should be known. The lm thickness representing an
important model parameter is estimated via the mass transfer coefcients (57,83).
The binary diffusivities and mass transfer coefcients were calculated from the
correlations summarized in Table 3.
The correlations of Billet (66) and Onda et al. (187) are valid for various
mixtures and packings and cover both absorption and distillation processes. The
correlation of Kolev (133) is obtained for RA and certain random packings. In
general, the mass transfer coefcient correlations need to be compared to one
another and validated using experimental data. This shows, in particular, the way
the mass transfer correlations inuence the concentration proles of the components and other relevant process characteristics.
Nitric acid is a strong electrolyte. Therefore, the solubilities of nitrogen
oxides in water given in Ref. 191 and based on Henrys law are utilized and further corrected by using the method of van Krevelen and Hoftijzer (77) for electrolyte solutions. The chemical equilibrium is calculated in terms of liquid-phase
activities. The local composition model of Engels (192), based on the UNIQUAC
model, is used for the calculation of vapor pressures and activity coefcients of
water and nitric acid. Multicomponent diffusion coefcients in the liquid phase
are corrected for the nonideality, as suggested in Ref. 57.
TABLE 3 Binary Diffusion Coefcients and Mass Transfer

Coefcients
Phase
Binary diffusion
coefcient
Gas
Ref. 188
Liquid
Ref. 189
Mass transfer
coefcient
correlation
Ref. 187
Ref. 66
Wehmeier (see
Ref. 134)
Ref. 187
Ref. 66
Ref. 133
Ref. 190
B.2.
Coke Gas Purication
In Ref. 139 a purely numerical approach to the solution of the considered complex RA problem was suggested. The liquid lm is treated as an additional balance region, in which reaction and mass transfer occur simultaneously. Therefore,
the reactions are considered both in the liquid-bulk-phase mass balances, Eq. (A1),
and in the differential balances for the liquid lm, Eq. (A10).
To be able to describe the presence of electrolytes in the system, the electrical driving force also needs to be taken into account (57). Therefore, the gradient of the electrical potential is introduced into the generalized driving force
di [cf. Eq. (2)]:
di
xi 1 i
F 1 d
x i zi
T L
T L d
i 1, . . . , n
(B2)
In dilute electrolyte systems, the diffusional interactions can usually be

neglected, and the generalized MaxwellStefan equations are reduced to the
NernstPlanck equations (B3):
N Li
c Lt DLi, eff dxi

F d
x i zi
xi N Ln
L
T d
d
i 1, . . . , n 1
(B3)
where n is the solvent index. The consideration of the electrical potential requires
an additional condition, the electroneutrality, which has to be met in each point
of the liquid phase:
n
x z 0
i i
(B4)
i1
Thermodynamic nonidealities are considered both in the transport equations

(A10) and in the equilibrium relationships at the phase interface. Because electrolytes are present in the system, the liquid-phase diffusion coefcients should be
corrected to account for the specic transport properties of electrolyte solutions.
The thermodynamic equilibrium at the gasliquid interface is described as
follows:
yiI Ki xiI
i 1, . . . , n
(B5)
where the distribution coefcient Ki comprises fugacities in both phases and

activity coefcients in the liquid phase. For the system considered, the values of
Ki, Eq. (B5), are determined from the electrolyte NRTL method (70,71).
The liquid-phase diffusion coefcients are found with the NernstHartley
equation (193), which describes the transport properties in weak electrolyte
systems. The gas-phase diffusion coefcients are estimated according to the
ChapmanEnskogWilkeLee model (72). The correlations for the mass transfer

coefcients are taken from Ref. 194.
B.3.
Methyl Acetate System, Batch Distillation
The rate-based models usually use the two-lm theory and comprise the material and energy balances of a differential element of the two-phase volume in the
packing (148). The classical two-lm model shown in Figure 13 is extended here
to consider the catalyst phase (Figure 33). A pseudo-homogeneous approach is
chosen for the catalyzed reaction (see also Section 2.1), and the corresponding
overall reaction kinetics is determined by xed-bed experiments (34). This
macroscopic kinetics includes the inuence of the liquid distribution and mass
transfer resistances at the liquidsolid interface as well as diffusional transport
phenomena inside the porous catalyst.
For the determination of conversion corresponding to the average residence
time, the reaction kinetics is integrated into the mass balances, and the liquid
FIGURE 33 Film model for a differential packing segment with heterogeneous catalyst.
holdup, as the accumulation term, is accounted for simultaneously, as in Eqs. (A8)

and (A9). Because of low vapor-phase density, the vapor holdup is neglected, and
the vapor-phase-component balance equation reduces to Eq. (A2).
Ranzi et al. [195] found that the full energy balances, including the accumulation term, have to be considered in order to predict correct dynamic process
behavior. Therefore, the differential dynamic energy balance for the liquid phase
is applied as follows:
0
) As
EL ( LhLB ) (QLB a I RLB L H RL
t
l

Q L (TLB T I )
L
B
L
N h
Li Li
(B6)
i 1, . . . , n
i1
where
EL hLB ( L c Lt As )
(B7)
Similar to the mass balance equation, the vapor-phase energy balance simplies
to Eq. (A7).
Experimental studies were carried out to derive correlations for mass transfer coefcients, reaction kinetics, liquid holdup, and pressure drop for the packing MULTIPAK (35). Suitable correlations for ROMBOPAK 6M are taken from
Refs. 90 and 196. The nonideal thermodynamic behavior of the investigated multicomponent system was described by the NRTL model for activity coefcients
concerning nonidealities caused by the dimerisation (see Ref. 72).
Binary diffusion coefcients for the vapor phase and for the liquid phase
were estimated via the method proposed by Fuller et al. and Tyn and Calus,
respectively (see Ref. 72). Physical properties such as densities, viscosities, and
thermal conductivities were calculated from the methods given in Ref. 72. Heat
losses through the column wall were measured at pilot scale.
B.4.
Methyl Acetate System, Steady-State Distillation
The model is based on the lm theory and comprises the material and energy balances of a differential element of the two-phase volume in the packing. Each element
consists of an ideally mixed vapor and liquid bulk phase and a vapor lm region
adjacent to the interface, as shown in Figure 33. A rst guess of the bulk phase
compositions and temperatures was provided by the solution of an equilibriumstage model without reactions, as suggested in Ref. 198. The catalyzed reaction
is described by the quasi-homogeneous approach of Ref. 197, since the concentration of acid sites has been determined as aCat 4.7 molH/gCat for dry Lewatit
K2621, which is close to the data of Ref. 197 given for Amberlyst 15.
In order to determine the model parameters, several experiments were performed at laboratory scale. Pressure drop experiments were carried out in glass
columns, with a total packing height of 1 m at ambient pressure. Air/water was used
as a test system, with a circulating liquid phase set at a constant temperature of 20C.
The experimental data cover a wide range of possible column loads. The gas
load for the column with 100-mm diameter was restricted to 1.7 Pa0.5. Therefore,
the liquid load was increased to higher values to reach the ooding region of the
catalytic packing. Two different ow regimes similar to those of conventional
structured packings can be observed. Flooding of the packing can be observed at
a pressure drop above 103 Pa/m. The possible column loads for MULTIPAK are
very similar to those reported in Refs. 199 and 200 for KATAPAK-S.
The number of theoretical stages per meter of the catalytic packing was
determined as a function of the gas capacity factor. For the whole range of column
loads, the separation efciency is at least four theoretical stages per meter. Moritz
and Hasse (200) determined an NTSM value of 3 for the laboratory-scale
KATAPAK-S. The separation efciency remains constant for a wide loading
range of the packing. For lower column loads, the NTSM value increases to 6, a
phenomenon already reported in Ref. 90 for the conventional structured packing
Montzpak A3-500. A simple transfer-unit concept assuming all mass transfer
resistance in the vapor phase was used to determine the vapor-side mass transfer
coefcients (201). The mass transfer correlation
Sh G 0.009 Re G0.92 Sc1/3
(B8)
represents all experimental data with an accuracy of 13%. A comparison with

experimental data is shown in Figure 34.
B.5.
Synthesis of Methyl Tertiary Butyl Ether
The mathematical description considered in Section 2.3 and Appendix A was

used as a modeling basis for the specially developed completely rate-based
simulator DESIGNER (155). This tool consists of several blocks, including
model libraries for physical properties, mass and heat transfer, reaction kinetics,
and equilibrium, as well as a specic hybrid solver and thermodynamic package.
DESIGNER also contains different hydrodynamic models (e.g., completely
mixed liquidcompletely mixed vapor, completely mixed liquidvapor plug ow,
mixed pool model, eddy diffusion model) and a model library of hydrodynamic
correlations for the mass transfer coefcients, interfacial area, pressure drop,
holdup, weeping, and entrainment that cover a number of different column internals and ow conditions.
In DESIGNER, different ways of taking account of heterogeneous reaction
kinetics are available, depending on the reaction rate and character. One further possibility is to use a detailed model for the heterogeneous catalyst mass transfer
efciency based on the approach of Ref. 91. When applying this type of kinetic
model, the intrinsic kinetics data are needed. Another way is the pseudo-homogeneous approach, with effective kinetic expressions, by which the kinetics description
is introduced as source terms into the balance equations [cf. Eqs. (A1) and (A2)].
For the system considered here, the reaction is slow as compared to the
mass transfer rate. For this reason the pseudo-homogeneous approach is used, the
reaction being accounted for in the liquid bulk only.
Basically, DESIGNER can use different physical property packages that are
easy to interchange with commercial owsheet simulators. For the case considered, the vaporliquid equilibrium description is based on the UNIQUAC model.
The liquid-phase binary diffusivities are determined using the method of Tyn and
Calus (see Ref. 72) for the diluted mixtures, corrected by the Vignes equation
(57), to account for nite concentrations. The vapor-phase diffusion coefcients
are assumed constant. The reaction kinetics parameters taken from Ref. 202 are
implemented directly in the DESIGNER code.
B.6.
Reactive Extraction of Zinc
In conventional RE processes, the diffusive resistance is concentrated mainly inside

the droplet, whereas the aqueous-side resistance can be neglected. This has been
proven in Ref. 203 using the laser-induced-uorescence (LIF) technique. Usually
the organic phase is more viscous and the diffusion coefcients of the organic complexes are larger than those at the aqueous side, which supports this nding.
The mass transfer within a rigid droplet is determined by the Maxwell
Stefan diffusion. The appropriate diffusion coefcients experimentally determined
FIGURE 34 Sherwood number correlation for MULTIPAK.
TABLE 4 Ternary Fick Diffusion Coefcients for the System

ZnR2 ( RH ) (1), RH (2), and Diluent (3) at 298.15 K .
Isododecane (3)
D11
D12
D21
D22
1.01
0.11
4.11
2.79

0.30 1010
0.10 1010
0.80 1010
0.30 1010
Toluene (3)
m2/s
m2/s
m2/s
m2/s
3.60 1.10 1010 m2/s

0.35 0.42 1010 m2/s
0.16 3.50 1010 m2/s
7.68 0.21 1010 m2/s
for this zinc extraction system in Ref. 204 are presented in Table 4. With nonrigid
droplets, a mass transfer enhancement by internal convection has to be considered. However, with industrial feed solutions there are always impurities present
that may dampen the mass transfer (8). In contrast, there also might be a mass
transfer increase due to Marangoni effects (205,206). Therefore, for a nal design
of a column, mass transfer measurements are recommended.
The macrokinetics of zinc extraction is discussed in detail in Ref. 8. It is a
combination of a reaction kinetics term (55) with the MaxwellStefan (54) or
eddy diffusion (56). The rate law is as follows:
d[ Zn 2 ]
dt
[ R2 H2 ] (B9)
[ R2 H2 ]1.5 [ Zn 2 ] r [ H ]2 [ ZnR2 ( RH )]
v

C [ R H ]
[ R2 H2 ]1.5 C1 [ H ]2
2
2
2
where C1, C2, , and r, are the estimated kinetics parameter (see EFCE test
systems discussed earlier).
The rate constant for the backward reaction, r, can be replaced by the thermodynamic equilibrium constant:
K eq
v
r
(B10)
The species concentrations are formulated in activities using the Pitzer

model (207) for the aqueous phase and the HildebrandScott solubility parameter (208) for the organic phase.
The effective diffusion coefcient is calculated according to the model of
Ref. 209, which accounts for interfacial instabilities. This model includes a
HandlosBaron-like correlation (210) and one adjustable parameter, CIP :
Deff
w dp

2048 CIP 1 d
c
(B11)
10
Multifunctional Reactors:
Integration of Reaction and Heat Transfer
David W. Agar
University of Dortmund, Dortmund, Germany
1.
INTRODUCTION
Reaction engineers devote a lot of time and ingenuity to enhancing reactor performance by attempting to follow an optimal trajectory for the reaction system (1)
and by overcoming the limitations imposed by the accompanying heat and mass
transfer processes. These objectives are often interrelated: Achieving the concentration and temperature proles required to maximize conversion rates and minimize by-product formation, for example, dictates the absence of gradients that
might lead to local deviations from these values.
Process intensication can be considered to be the use of measures to increase
the volume-specic rates of reaction, heat transfer, and mass transfer and thus to
enable the chemical system or catalyst to realize its full potential (2). Catalysis
itself is an example of process intensication in its broadest sense. The use of
special reaction media, such as ionic liquids or supercritical uids, high-density
energy sources, such as microwaves or ultrasonics, the exploitation of centrifugal
elds, the use of microstructured reactors with very high specic surface areas,
and the periodic reactor operation all fall under this denition of process intensication, and the list given is by no means exhaustive.
Reactor performance is dictated by the inputs, by the contacting pattern,
i.e., how and when individual elements pass through the reactor and contact one
FIGURE 1 Basic strategies for manipulating temperature and concentration

profiles in chemical reactors.
another and how long they retain their identity, and by the cumulative kinetics and
thermodynamics to which elements are exposed along their reaction trajectory (3).
Identifying the most suitable reactor conguration, e.g., an ideal plug ow, is a
well-established procedure in chemical reaction engineering. Less appreciated
are the full range of possibilities available in manipulating the local rates of reaction by imposing favorable temperature, concentration, and activity proles along
a catalytic reactor. While the rst option has received extensive attention, the last
two have been somewhat neglected, although they often offer a more selective
intervention in the progress of the reaction and complement the more common
tailoring of the temperature prole.
In general, temperature and concentration proles may be externally inuenced by convective or recuperative and, less commonly, regenerative or reactive
strategies (Figure 1). The convective addition or withdrawal of side streams
along the reactor represents a simple technique for temperature control or for
improving selectivity by restricting availability of one reactant. In a recuperative
process, examples of which are provided by the cooled tubular reactor and the
membrane reactor, heat or material is exchanged, in the latter case usually in a
selective manner, via diffusive transport processes, such as heat conduction, with
spatially distinct external sources and sinks. Regeneration exploits the storage of
heat and mass, by adsorption, for example, on reactor internalsusually a xed
bedto yield benecial temperature and concentration proles that could not
arise under steady-state operation. Regenerative processes are inherently unsteady
state in nature and entail a chronologically separate recharging of the storage
capacity drawn down during the reaction phase. The use of a supplementary reaction to supply or consume heat and/or reactants or products, as encountered in
oxydehydrogenations, is a method requiring considerable nesse and almost perfect compatibility between the individual reactions.
2.
CONVECTIVE HEAT TRANSFER
Each of these approaches has its pros and cons, as can be illustrated for convective cooling in a cold-shot reactor, employed in ammonia synthesis, for example.
Plotting conversion against temperature for a reversible exothermic reaction
(Figure 2a) shows that intermittent cooling by the discrete introduction of cold
feed along the reactor enables one to circumvent the equilibrium limitation
imposed on adiabatic operation but also that the cooling effect desired is accompanied by a less welcome loss in conversion. Furthermore, as the slope of the
cooling line approaches that of the adiabatic reaction path, the efcacy of cooling
and its benets diminish. A possible solution to this problem of limited cooling
capacity is to employ an inert side stream in place of feedstock (Figure 2b) as
coolant (3). However, this would result in dilution of the reactor product stream
and complicate the downstream processing steps. A process intensication technique to overcome the difculties indicated is, for gaseous systems, to inject inert
liquid between adiabatic reactor stages. Exploiting the heat of evaporation means
that much lower quantities of inert are needed than with a gaseous coolant.
3.
RECUPERATIVE HEAT TRANSFER
The best-known recuperative reactorthe multitubular reactor used in the partial

oxidation of hydrocarbons, for instanceis a ubiquitous piece of equipment in
the chemical processing industry (4). This should not blind one to the fact that it
exhibits several serious shortcomings: The reactors are costly, and, despite the use
of up to 25,000 tubes in a single reactor to provide a suitably extensive area for
heat transfer (100 m2/m3), one often observes large temperature excursions
from the desired temperature levelso-called hot spotsin both the axial and
radial directions (Figure 3). These hot spots arise due to a bottleneck in the heat
removal process, arising from a combination of the locally accelerated reaction
rates and poor heat transport through the catalyst bed (100 W/m2K)an order
of magnitude smaller than what the coolant side is capable of providing.
FIGURE 2 Interstage convective cooling of an exothermic equilibrium reaction through introduction of (a) cold-shot
feed by-pass and (b) cold-shot inert side-stream between adiabatic stages.
FIGURE 3 Schematic of temperature proles and hot spot formation in a multitubular reactor.
Hot spots usually dictate the attainable reactor performance in terms of conversion, selectivity, safety issues, operating lifetimes, and materials of construction,
since most of the critical processes are conned to the immediate vicinity of the
temperature maximum.
3.1.
Catalyst Dilution
The elimination of reactor hot spots has also attracted considerable interest over
the years. Because a panacea remains elusive, a variety of countermeasures have
been adopted reecting different compromises between the demands of the reaction, heat removal, and pressure drop (Figure 4). Perhaps the simplest procedure
for avoiding the formation of pronounced hot spots is to dilute the catalyst at the
endangered locations (5). In this manner, the reaction is spread more evenly over
the length of the reactor, and a better harmonization between the heat production
by the reaction and the heat removal via the reactor wall is realized (Figure 5).
The resultant reactors are, of course, larger, and the inclusion of inert packing
leads to increased pressure drops. But the technique is reliable and involves no
additional developments. Interestingly, the precise activity prole employed is
seldom decisive for the improvement in performance; i.e., simple arrangements
sufce.
FIGURE 4 Various measures for the harmonization of reaction, heat transport, and pressure drop in chemical reactors benchmarked against a multitubular reactor.
3.2.
Linde Isothermal Reactor
An alternative solution is to pack still more heat exchange surface into the catalyst bed and to try to augment the heat transfer coefcients modestly by inducing
a greater degree of turbulence for the gas ow over the cooling surface. The
so-called Linde isothermal reactor (6) inverts the situation in the conventional
multitubular reactor by operating with the coolantnormally pressurized boiling
waterwithin the tubes and the catalyst outside (Figure 6). The tubes are also no
longer parallel but assume a convoluted spiral geometry that raises the specic
surface area and increases heat transfer coefcients by an order of 50%. Use of
the reactor is conned to temperatures below 550 K, since the pressure required
for evaporative cooling above this value becomes exorbitant, and molten salt
cooling is not an option due to the high pressure drop in the cooling circuit. In
addition, the removal of the catalyst from such reactors, e.g., for regeneration or
replacement, may present problems owing to arch formation between cooling
tubes. In economic terms, the greater compactness of the Linde isothermal reactor must be set against its increased construction complexity.
3.3.
Fluidized Beds
An extremely effective means of enhancing heat removal from a reactor is to make

use of uidized-bed technology (3). Heat transfer coefcients for gaseous systems
are increased to values of around 600 W/m2K or more by virtue of the very efcient
convective-regenerative particle transport mechanism of heat transfer. Further
advantages include lower resistances to mass transfer (particle size 100 m) and
facile catalyst exchange for regeneration purposes if necessary. Less favorable
aspects of uidized beds include the high degree of back-mixing that occurs, the limited range of hydrodynamic loading, and the uncertainty involved in scale-up.
Moreover, the catalyst must be very mechanically resilient, and adapting catalysts
for uidized-bed operation can be a time-consuming and frustrating exercise.
3.4.
Catalytic Microreactors
A measure that has been the subject of extensive publication is that of microreactors with catalytically coated walls (7,8). A microreactor has been dened as:
a miniaturized reaction vessel with characteristic dimensions in the range
10300 m which has been fabricated using state-of-the-art high-precision engineering (7). Such reactors exhibit well-dened laminar-ow patterns and permit
facile scale-up by simple numbering up of the number of channels and exible
FIGURE 5 Hot spot reduction using spatially structured catalyst dilution.

Selectivity proles for base case with constant coolant temperature, cocurrent coolant strategy and axially proled catalyst activity strategy. The base
case chosen in the calculations is the one in which the coolant temperature
is constant and the activity prole along the length of the reactor is at the
level unity. (From Ref. 5.)
FIGURE 6 Linde isothermal reactor for intensified cooling of strongly exothermic reactions. (From Ref. 6.)
arrangements of individual modules. Furthermore, they have extremely low

holdups and, as a consequence, comparatively short dynamic response times.
Most importantly, they enable one to operate under isothermal conditions with
even the most exothermic reactions. The list of applications for which microreactors are suitable includes the reaction engineering for fuel cell hydrogen production, the synthesis of hazardous chemicals, high-throughput screening for
chemicals and catalysts, as instruments for obtaining insights into chemical reaction mechanisms, and as components of intelligent chemical sensors.
The excellent heat transfer characteristics of microreactors result not
only from their considerably enhanced specic heat exchange surface areas of
30,000 m2/m3a value roughly 300 times higher than that in a conventional multitubular reactorbut also from the rapid lateral heat transfer across the channels.
For the small microchannel dimensions involved (Figure 7), conductive heat
transfer plays an important role, augmenting the heat transfer coefcients by a
factor of 5 or more to values in the vicinity of 700 W/m2K. This phenomenon is
also responsible for good transverse mixing, counteracting the negative effects of
laminar-ow proles.
Less advantageous are the high unit production costs for microreactors and
the complexities involved in their manufacture. The basic material of construction
is usually metal or plastic, which has restricted heterogeneous catalytic applications to metallic catalysts or often unsatisfactory metallic-catalytic composites.
FIGURE 7 Structure and typical dimensions of a microreactor. (From Ref. 7.)
Despite the high specic surface areas, the amount of accessible catalyst remains
low due to the limited thickness of the porous catalytic layer dictated by considerations such as the adhesion to the substrate. The susceptibility of the ne channels to blockage with solid impurities or deposits formed in the reaction, together
with the problems of integrating connections with the external macroenvironments and ensuring uniform gas distribution between the individual channels, a
prerequisite for numbering up, represent further questions that have to be
resolved for the industrial application of microreactors to become practicable.
3.4.1.
Catalytic Millireactors
The drawbacks associated with this particular technique of process intensication

may be ameliorated by analyzing the characteristic length scales for the component processes. The chemical activity of a heterogeneous catalyst, for example, is
expressed in its nanostructure, i.e., the pore diameter of 10100 nm reected in
the typical specic surface area of a catalyst, say, 100 m2/g. This scale provides
an adequate number of active sites for the reaction to proceed without imposing
unnecessary limitations on the underlying chemical kinetics. Catalyst systems
lacking this nanostructure will seldom provide sufcient activity and do not permit the catalyst chemistry to realize its full potential. Even in a microreactor, geometric surface areas of catalytic layers fall short of the internal specic pore
surface area by a factor of almost 10,000. The diffusive transport through the pore
system to and from the active sites dictates the maximal thickness of porous catalytic layers. For the diffusion coefcients in gas-phase systems, the conventional
analysis based on the Thiele or Weisz modulus suggests that diffusive mass transfer is sufcient to maintain the reactant ow to the active catalytic sites over distances of about 1 mm. The corresponding value for liquid systems is two orders
of magnitude lower. The validity of this result is conrmed by observing the typical dimensions of industrial catalysts employed for gas- and liquid-phase reactions, respectively.
Considering a typical intrinsic rate of catalytic reaction in an intermediate
temperature range of 1 mmol/kg cats and a strongly exothermic reaction enthalpy
indicates that the rates of heat generation one needs to master can be of the order
of 500 kW/m3 of catalyst. For tolerable temperature gradients (2 K) and characteristic thermal conductivity values for porous catalysts (1 W/mK) one obtains
the result that specic heat exchange surface areas of 1000 m2/m3 should be sufcient to remove the heat of reaction. This analysis thus implies that while the
traditional multitubular reactor with its tube diameters of several centimeters may
well be overtaxed, the microreactor offers an unnecessarily excessive specic
surface area, way beyond the demands actually being imposed by the chemistry
of the catalytic system. The resulting insight is that, in terms of the heat transfer
demands, a reduction of the characteristic dimensions down to the millimeter
scale yields an entirely adequate performance (Figure 8) (9).
FIGURE 8 Analysis of the appropriate characteristic dimensions for specic

heat transfer surface requirements in a chemical reactor exhibiting typical
reaction rates. Da Damkoehler number, NTU number of thermal transfer units, Nu Nusselt number, a thermal diffusivity. (From Ref. 9.)
3.4.2.
Ceramic Catalytic Millireactors
Effective process intensication requires that all superuous bottlenecks be

removed, but only to the extent at which a controlling stepusually the intrinsic
catalytic kineticscan no longer be accelerated further. The considerations presented earlier suggest an optimal reactor structure to meet this criterion. Since the
intrinsic catalytic activity may be expressed only when a suitable nanostructure
provides access to the maximum number of active sites and because the mass of
the catalyst rather than its external surface area determines the total activity, all
microreactor concepts based on bulk metal catalysts or on thin catalytic lms produced by CVD, sol-gel coating, or anodic oxidation on a metallic support are
basically unsuitable because they provide insufcient catalytic material. In addition, the conicting demands inherent in producing a catalytic layer with the
nanostructure thickness and adhesion to the substrate desired often lead to unsatisfactory compromises, and new composite structures must be developed for each
specic catalyst system. Whereas the traditional approach to catalytic microreactors has been to coat a metallic micro-heat exchanger structure with catalyst, a
superior technique might be to produce a heat exchanger out of the proven catalytic material itself or something similar, i.e., to utilize a nanoporous ceramic
substrate. For the small dimensions involved, the use of slightly more poorly
conducting ceramic leads to no deterioration in performance in comparison to
metallic walls and can even be advantageous for thermal efciency by maintaining axial temperature gradients without conductive short-circuiting.
FIGURE 9 Monolithic catalyst modied to serve as a heat exchanger.
The use of proven catalyst recipes would greatly curtail development times,
and the absence of extraneous material avoids unwanted catalytic effects and
enhances thermal stability. The xation of catalyst on ceramic substrates such as
washcoats is a well-known, reliable, and relatively straightforward procedure.
The fabrication of complex small-scale ceramic structures is, however, more awkward than for metals or plastics, and they exhibit relatively poor mechanical
strength. Furthermore, the porous ceramic nanostructure must be sealed to prevent contact between the reaction medium and coolant.
In the past, the principles described have been implicitly recognized in several attempts to convert monolithic catalysts into catalytic heat exchangers. While
the use of millimeter dimensions and nanoporous ceramic supports meets the primary criteria already mentioned, the parallel channel structure of monoliths is not
ideally tailored for heat exchanger applications, and complex header structures
are required to uniformly distribute and collect reaction medium and coolant to
and from the individual channels (Figure 9). The unsatisfactory interface between
the milli- and macroscale has been a major weakness of such concepts.
3.4.3.
Ceramic Catalytic-Plate Heat Exchanger
An existing item of chemical processing equipmentthe plate heat exchanger

suggests a possible solution to this drawback. The integration of manifolds into
the plate stack arrangement means that one can dispense with special headers for
uid distribution. Furthermore, internal structures on the plates can be used to
provide intermittent mixing and induce secondary ows, thus overcoming the
principle shortcomings of simple laminar-ow conditions. A variety of techniques, including an efcient countercurrent CVD method, have been proposed
for sealing porous ceramic structures to prevent the unwanted diffusive slip
between reaction medium and coolant (10).
Although the fragility of ceramic structures probably precludes the application of evaporative cooling or molten salt coolants, the use of oil up to 300C
and gas for higher temperatures is feasible, since the poor performance of gas
coolant can, to some extent anyway, be compensated for using by a favorable
arrangement of the coolant-side geometry to cut the pressure drop. The coolant
pressure in both cases can be adapted to approximate that of the reaction medium, thus reducing to a minimum the mechanical stress on the ceramic plates due
to pressure differentials. One can also select the coolant gas to have good thermal
properties (heat capacity, conductivity) and to be inert, so slight leakages into the
reaction medium can, if necessary, be tolerated. Heat could be withdrawn effectively from the gas coolant circuit using an external inert uidized-bed or other
proven techniques.
The resulting piece of equipment can be referred to as a catalytic plate heat
exchanger, with structure and scale similar to that of a conventional plate heat
exchanger. The plates comprise porous ceramic of 1- to 2-mm thickness and separate alternating reaction and cooling chambers (Figure 10). The detailed channel
prole desired may be introduced on to the plain support by means of an intermediate laser-engraved separating plate. The individuals plates are stacked and
cemented with countercurrent, cocurrent, or crossow cooling congurations, as
specied. More complex temperature proles can also be attained by combining
individual stack modules as required. Special attention must be paid to the uniform distribution of reaction medium and coolant both within and between the
plates, to ensure an approximation to plug-ow behavior despite the usually
unavoidable laminar-ow conditions. Fortunately, such ows are amenable to
precise modeling using computational uid dynamics, enabling one to develop
suitable geometries. Nevertheless, the delusion that numbering-up is a trivial procedure quickly dissipates when one is confronted with the complexity of guaranteeing almost identical ow conditions in each of several ten thousand channels!
In addition to the harmonization of the underlying physical and chemical
processes, the catalytic-plate heat exchanger offers a cost-effective alternative to
both conventional multitubular reactors and catalytic microreactors for industrial
FIGURE 10 Schematic layout of a catalytic plate heat exchanger.
applications. Because it is based on proven catalyst compositions and state-of-the-art

fabrication methods, development costs and times should be low, a feature enhanced
by the nonspecic, generally applicable nature of the concept. The successful
design of such reactors can be ensured by the use of reliable modeling tools and
the exibility available in the reactor architecture and operation. Finally, the
facile regeneration, recycling, or disposal of deactivated catalyst is an additional
advantage over metallic catalyst composites.
4.
REACTIVE-RECUPERATIVE HEAT TRANSFER
A second method of process intensication for recuperative reactors is to enhance

performance by using a reactive coolant or heating medium, since the heat effects
associated with reactions are usually much larger than those available with phase
changes or simpler heating and cooling procedures. The coupling of an exothermic auxiliary heat source reaction with the desired endothermic reaction, or vice
versa, through a double catalytically coated wall has also been attempted in a
modied monolithic catalyst (Figure 11) for the steam reforming reaction, with
the methane combustion reaction being used to supply the heat required (11). The
work done demonstrated that it is extremely difcult to localize the reactions and
regulate the temperatures in the interests of performancethe system tends to
assume a state dictated by the intrinsic kinetics and heat effects of the two reactions. With more passive coolants or heating media, the operator is in a better
position to inuence the reactor behavior and can manipulate temperature proles
to a greater extent.
5.
REGENERATIVE HEAT TRANSFER
Regenerative reactors, that is to say, those exploiting heat storage on xed beds,
remain a somewhat neglected option in reaction engineering. Although the principle of heat regeneration had been utilized previously in the chemical industry,
FIGURE 11 Monolithic catalyst adapted for the thermal coupling of endo- and
exothermic reactions. (From Ref. 11.)
for example, in a process for high-temperature thermal for nitrogen xation (12),
and is a common feature in related process industries, such as power generation
and steel manufacture, its most recent renaissance was brought about the development (13) and renement (14) of the reverse-ow reactor concept (Figure 12),
which has now established itself rmly in the niche of oxidative waste-gas treatment. Additionally, regenerative heat transfer is an important feature of conventional reactor operation, for instance, in the occurrence of the transitional
wrong-way behavior with temperature levels in excess of the adiabatic value
that can arise when a xed-bed reactor is shut down (15).
Regenerative heat exchange in chemical reactors offers clear benets, such
as simplicity, robustness, low costs, and high efciencies, against which must be
set its inherently unsteady-state operation, the limited potential for an exact regulation of temperature proles, and the restriction of its use to gaseous reaction
media.
5.1. Comparison of Regenerative with Convective,
Recuperative, and Reactive Heat Transfer
In the evaluation of the regenerative heat exchange option, it is instructive to consider the heat exchange techniques presently employed in the following chemical
processes: styrene synthesis, steam reforming, and hydrogen cyanide production
(Table 1).
FIGURE 12 Reverse ow reactor concept.
TABLE 1 Heat Exchange Employed for High-Temperature Endothermic Reactions

Ethylbenzene
Dehydrogenation
Steam
Reforming
Hydrogen Cyanide
Manufacture
C8H10 C8H8 H2
CH4 H2O CO 3H2
CH4 NH3 HCN 3H2
600C
900C
1200C
T-Proling
technique
Convection
Badger/Mobil adiabatic
process
Recuperation
BASF isothermal process
conventional primary steam

reforming
Regeneration
Reaction
Degussa BMA
process
?
autothermal reforming
(fuel cell applications)
Andrussov ammonoxidation
process
The moderately endothermic dehydrogenation of ethylbenzene to styrene is

carried out catalytically at temperatures of around 600C. The dominant technology for meeting the heat requirements of this reaction involves the intermediate
introduction of superheated steam as a heating medium between adiabatic reactor stages, i.e., a convective process. Several additional features of the reaction
favor the convective approach: Steam can easily be removed from the products by
a phase separation following condensation, steam acts as an inert dilutant enhancing the equilibrium conversion, and steam also helps to maintain catalytic activity.
An alternative recuperative technology in which combustion gases are used as a
spatially segregated heat source in a multitubular suffers from the low heat transfer coefcients in gasgas recuperative heat exchangers and entails a more costly
reactor construction.
The steam reforming of methane to synthesis gas, a strongly endothermic
reaction carried out catalytically at around 900C, primarily utilizes recuperative
heat transfer. The higher reaction temperature makes the convective supply of
heat problematic, particularly at the preferred operating pressures of about 25 bar.
The heat required can also be supplied reactively by simultaneously carrying out
the exothermic partial oxidation of methane to carbon monoxide and hydrogen.
The main impediment for this so-called autothermal reforming was previously
the rapid deactivation of the catalysts used. In connection with research on the
on-board generation of hydrogen for mobile fuel cell applications, novel noble
metal catalysts have been developed that maintain an adequate activity. Such catalysts are, however, almost certainly too costly for regular industrial purposes.
The prevalent manufacturing process for hydrogen cyanidethe Andrussov
processrepresents the successful industrial application of reactive heat
exchange. In the catalytic ammonoxidation of methane at 1100C, the actual
endothermic synthesis reaction between methane and ammonia is thermal
supported by the oxidation of the hydrogen formed, so no additional heat need
be supplied (Figure 13). Reactive heat transfer of this sort is, of course, very
efcient, in that it entails virtually no temperature gradients, due to the almost
molecular scale at which it occurs. On the other hand, the inclusion of an extra
reactantoxygengives rise to unwanted side reactions, such as the formation
of carbon oxides, and encourages undesirable ammonia decomposition. Furthermore, because it is uneconomic to use pure oxygen in place of air, the nitrogen
introduced into the process results in the need for much larger reactors and downstream units to treat the diluted gas streams. The alternative recuperative BMA
process offers much higher yields, due to the absence of side reactions, and higher
product concentrations with lower ows. Recuperative heat exchange at such
high temperatures necessitates the use of catalytically coated ceramic tubular
reactors, which are costly and lack operational robustness. In addition, only about
half of the heat supplied in the form of combustion gases can actually be utilized
for the reaction.
FIGURE 13 Possible thermal coupling mechanisms between the endothermic

synthesis reaction and the exothermic hydrogen oxidation in hydrogen
cyanide manufacture.
5.2. Regenerative Heat Transfer Process for Hydrogen

Cyanide Manufacture
Although regenerative heat exchange solutions have been proposed for the rst
two examples presented (16), hydrogen cyanide synthesis is, in fact, a more
promising candidate by virtue of the higher and broader temperature range and
the lower operating pressures. A cursory analysis reveals that a regenerative
heat exchange process could in fact combine the most important advantages of
the reactive and recuperative processes while surmounting their shortcomings
(Table 2) (17).
More detailed modeling exposes some weaknesses, for example, the need
to use coarse monolithic catalyst structure to achieve reasonable reheat periods
without excessive pressure drops. The cycle time of approximately 4 minutes is
somewhat short for practical purposes. The cold spot formation in the reaction
phase (Figure 14) and the resultant inability of the reaction to distribute itself over
the catalyst to utilize the stored heat optimally is probably a modeling artefact
caused by too low literature values for the activation energy, possibly reecting
an incorrectly interpreted lm transport limitation.
TABLE 2 Advantages and Disadvantages of Reactive, Recuperative,

and Regenerative Heat Exchange in Hydrogen Cyanide Manufacture
5.3. Desorptive Cooling for Enhanced Regenerative

Heat Transfer
Process intensication measures to extend regenerative cycle times could enable
the reaction engineer to utilize the strengths of this form of heat exchange more
fully. The use of the larger enthalpies associated with phase changes rather than
simple specic heat effects to store thermal energy is a technique already exploited
with evaporative coolants in recuperative processes and in the liquid injection
mentioned earlier in the context of convective processes. The regenerative analogy
to this principle can be illustrated using a technique that can be referred to as
desorptive cooling (18).
If an inert material is initially adsorbed on the xed bed comprising an
appropriate adsorbent and a catalyst, the heat of adsorptionhaving the same
order of magnitude as the latent heat of evaporationwill be released (Figure 15).
Since no reaction takes place in this phase, moderate temperature excursions are
acceptable, and recycle ows over external heat exchangers or injection of liquid
adsorptives may serve as heat sinks. In the subsequent reaction phase, the heat liberated by an exothermic reaction on the catalyst is taken up by the desorption of
the inert from the previously loaded neighboring adsorbent particles. As long as
this desorption occurs, the heat of reaction will not lead to major temperature
increases. Sooner or later, of course, the adsorbent will be depleted and the temperatures will drift upward, at which point the adsorption phase must be repeated.
Such a system yields intensive cooling without the need for an extensive
heat exchange surface within the reactor. The operation of the reactor in the reaction
phase is adiabatic. One can even customize the heat removal process by distributing the adsorbent and catalyst in different ratios along the length of the xed
bed to maximize cycle duration. Furthermore, if the desorption process exhibits
greater sensitivity toward temperature changes than the reaction, the process will
become self-regulating to a certain extent. On the negative side, desorptive cooling is, as are all regenerative processes, inherently unsteady state, space time
yields are diminished by the presence of adsorbent in the xed bed, and the adsorbent-adsorptive system must be compatible, i.e. inert, with respect to the catalytic reaction being conducted.
To demonstrate the potential available, simulations were carried out for the
oxidation of carbon monoxide on a palladium shell catalyst with water desorption
from 3A zeolite as a heat sink, based on experimentally validated model parameters for the individual steps (Figure 16). The calculations indicated that the reaction cycle time could be lengthened by a factor of 10, to a total 20 minutes, in
comparison to a simple regenerative process with a similar amount of inert material instead of adsorbent in the xed bed and for the same threshold for temperature deviation from the initial value.
FIGURE 14 Temperature proles of gas and catalysts in a regenerative process

for hydrogen cyanide manufacture at the start and nish of the reaction cycle.
Cycle duration is 4 minutes and the monolithic catalyst used has the following dimensions: wall thickness 4 mm, channel width 20 mm, length 2000 mm.
FIGURE 15 Operating principle of desorptive cooling.
Experimental measurements yielded only a vefold extension of the reaction cycle time, a difference largely caused by heat storage effects in the smallscale equipment used, which disproportionately enhanced the cooling effect
observed in the inert bed control experiment. Despite this less satisfactory result,
the desorptive cooling concept would still seem to offer potential for dramatic
improvement in performance for regenerative heat exchange processes.
The desorptive cooling principle is effectively equivalent to the distributed
injection of a cooling liquid along the length of a xed-bed reactor into a gaseous
reaction medium undergoing exothermic reaction. An extension of the idea, the
adsorption of a reaction product to both enhance the equilibrium position and
provide some of the heat required for the endothermic reaction, has also been proposed (19). More mundanely, the latent heat effects of wax solidication have
been exploited in temperature-regulating fabrics incorporating microencapsulated
wax particles! A certain analogy can also be drawn with the previously mentioned
use of catalyst bed dilution with inert material to better harmonize recuperative
heat removal with the rate of heat formation due to reaction, even though this
measure must be considered a example of process deintensication in the strictest
sense.
5.4.
Regenerative Heat Transfer in Adsorptive Reactors
The benets obtained by integrating adsorption into regenerative heat exchange

demonstrate the synergies available between these two related processes. Similar
advantages accrue when heat regeneration is incorporated into adsorptive reactors, in which concentration proles are manipulated to improve reactor performance through selective ad- and desorption of components in the reaction
medium.
An example of the potential in this second direction is provided by an innovative regenerative reactor for carrying out the Deacon reaction (20), in which
hydrogen chloride is catalytically oxidized to chlorinean important step in
chlorine recycling for the chemical industry. By resolving the gas-phase reaction
into two sequential gassolid subreactions corresponding to adsorption-desorption
steps (Figure 17), one can overcome the equilibrium thermodynamics that otherwise
FIGURE 16 Simulated temperature proles along a reactor with and without

desorptive cooling at various times for the oxidation of CO on a Pt catalyst
with water vapor desorption from 3A zeolite in a xed bed comprising equal
proportions of catalyst and adsorbent. The solid curves give the simple
regenerative behavior and the dotted curves describe the desorptively
cooled case. Initial reactor temperature is 125C, initial adsorbent loading
0.12 kg/kg, inlet CO-concentration 0.2 mol/l, gas loading 6000 h1.
FIGURE 17 Operating concept of an unsteady-state Deacon process for chlorine recycling.
limit conversion to around 85% and complicate downstream processing of the

resultant partially converted reactor output. In the exothermic chlorination step,
hydrogen chloride reacts with the oxidized form of the catalyst to yield copper
chloride and water vapor. During the following endothermic oxidation stage, this
copper chloride is converted back to its oxidized form, liberating chlorine in the
process. In this manner, one can achieve total conversion and considerably simplify the subsequent processing necessary. In view of the extremely corrosive
nature of the reaction (and catalyst!) system a regenerative transfer of heat
between the two phases is to be preferred over any recuperative alternative. The
use of the xed bed to store both heat and chlorine between the two steps of the
reaction cycle leads to contradictions and bottlenecks in catalyst and reactor
designa common drawback of multifunctionality as a technique for process
intensication. For example, the removal of the excess heat of reaction from the
reactor favors cocurrent operation of the xed bed in its function as a heat regenerator. For optimal utilization of the concentration proles and maximal chlorine
capacity of the xed-bed countercurrent, operation of the two cycle phases is to
be preferred. Despite these difculties, it still proved possible to modify the catalyst and reactor design sufciently to fulll both the adsorptive and the
regenerative function.
6.
ELECTROMAGNETIC HEAT TRANSFER
The use of electromagnetic techniques represents the nal method for process
intensication of heat transfer that will be dealt with here. Developments in the
fuel cell sector hold out the promise of cheap electric power based on surplus
hydrogen in chemical plants. The liberalization of the energy sector has also cut
electricity prices and enhanced the attractiveness of using electricity in connection
with chemical reactors. The precise regulation possible with electrical processes
and their clean, environmentally friendly nature are further inducements for their
application.
Once again it must be said that the use of electricity in chemical reactors is
hardly new. Apart from numerous electrochemical processes, electrothermal
processes are employed for the manufacture of phosphorus, hydrogen cyanide,
and calcium carbide. Furthermore, syntheses based on electric arcs have been
used in the past for the large-scale production of nitric oxide and acetylene and
are still employed today for ozone manufacture or chemical vapor depostion
coating procedures. A major advantage of the electrical heating employed in electrothermal processes that offsets the higher operating costs is the absence of any
limit on the temperature level at which it can be applied, making it particularly
suitable for processes above 1000C, where conventional heat transfer becomes
difcult to realize.
6.1.
Ohmic Heating
Ohmic heating of catalyst is often used as a simple method of igniting the chemical reaction during reactor startup, for instance, in the oxidation of ammonia on
platinum-rhodium gauze catalysts. Another application is the prevention of coldstart emissions from automotive catalysts responsible for much of the residual
pollution still produced from this source (21). The startup times needed for the
catalyst to attain its operating temperature can be cut by a factor of 5 or more
by installing an electrically heated catalyst element with a metallic support
upstream of the main catalyst unit. Direct electrical catalyst heating permits facile
temperature control but requires a well-dened catalyst structure to function
effectively.
6.2.
Dielectric Heating
Much attention has recently also been devoted to dielectric heating of reactors
using microwaves (! 1 cm to 1 m, 30 GHz to 300 MHz) (22). As in domestic applications, the primary attraction lies in the absence of heat exchange surface, and thus of fouling, and local overheating. Dielectric heating is especially
suitable for temperature-sensitive materials for which even slight nonuniformities
or temperature gradients might prove damaging, which explains its use in the
manufacture of ceramics and catalysts and in the sterilization of complex fermentation media. It has also been proposed for the local production of limited
quantities of hazardous chemicals, such as hydrogen cyanide (Figure 18) (23).
The rapid startup and exact temperature regulation possible, even at varying
throughputs, together with the low inventories entailed by such production reactors compensate for the higher costs of the microwave heating. The speed of
microwave heating also makes it a suitable technology for the oxidative regeneration of diesel particulate lters.
Although the efciency of microwave heating is high, the generation of microwaves is by no means free of losses. Specic chemical effects due to microwaves
FIGURE 18 Yields of hydrogen cyanide in catalytic and noncatalytic

microwave-heated reactors. (From Ref. 23.)
remain controversial and are probably of little signicance for industrial purposes.
Questions of scale-up, capacity limits, and materials of construction still need to
be addressed before industrial applications of microwaves in combination with
chemical reactors become more widespread.
An interesting application, derived from the use of microwaves for selective
desorption processes, is the modication of catalyst performance by the imposition of a temperature prole on a catalyst pellet, which is usually dictated by the
interaction between the heat of reaction and the thermal conductivity of the
pellet. Microwave heating together with the use of carrier materials of various
permittivities and conductivities would permit one to regulate the temperature
conditions within the catalyst pellet independently. An extension of this principle
would be the selective thermal activation of one sort of catalyst in a mixed xedbed system. The external switching of catalytic activity in this manner could be
employed expediently to realize multistep syntheses in a single reactor. To prevent
thermal short-circuiting it would be necessary to isolate the individual catalyst
particles from one another in an insulating matrix.
6.3.
Electric Arc Processes
Electric arc processes have been given a new lease on life in the guise of plasma
reactors, especially those involving cold, or nonthermal plasmas, with electron
temperatures of 104105 K and gas temperatures of 102103 K. Plasmas of this
kind can be used to activate and functionalize inert molecules, but usually with
only poor selectivities and low energy yields ( 0.01 mol/kWh!). The use of catalytic additives may offer some potential for improvement, but reactive plasma
processes will probably remain restricted to a few specic applications.
6.4.
Peltier Cooling
A major drawback of the electrical techniques described is that they are, without
exception, heating processes, whereas the reaction engineer is often more interested in reactor cooling. The active cooling of a catalytic surface using the Peltier
effect enables one to achieve almost perfect temperature control, even in the face
of strongly exothermic reaction behavior, but the low efciency of the phenomenon means that a large additional amount of heat also has to be dissipated. As a
Peltier element only pumps heat from one location to another (Figure 19), the
question of the ultimate heat sink must still be resolved. For these reasons such
techniques will probably be restricted to laboratory use in the form of special
microreactors for the foreseeable future.
7. CATALYST MODIFICATION FOR ENHANCED
HEAT TRANSFER
All of the recuperative, regenerative, and electrical methods described for intensifying heat transfer in chemical reactors illustrate the importance of developing
appropriate catalyst systems tailored to the behavior being sought. Improving
catalyst performance in this way by using active multifunctional supports while
leaving the catalytic chemistry unchanged can be referred to as commensal
catalysis, in analogy to the natural relationship between two species that benets
one partner (the catalyst) while being neither advantageous nor disadvantageous
for the other (the carrier). Bifunctional catalysts, with spillover diffusion effects
to reduce coke formation, and zeolitic catalysts with their selective access to
active sites represent two conventional examples of commensal catalysis. However, the support properties can also be modied to enhance interfacial areas, heat
and mass transport, heat and mass storage, mechanical, thermal, or chemical
FIGURE 19 Active electrical reactor cooling using Peltier elements.
TABLE 3 Performance Enhancement Through the Modication of the

Physical Properties of Catalyst Supports
Bifunctional Catalysts
e.g. propene oxidation, Pt-doped zeolites, spillover-oxygen
Supported Catalysts
e.g. impregnated catalysts, SLPC, SAPC
Mass Transport
e.g. zeolites, membrane encapsulation, Aerogel
Heat Transport
e.g. graphite carriers, coated-wall reactors, full metal catalysts
Mass Storage
e.g. active C-carriers, hydride-containing catalysts
Heat Storage
e.g. metallic monoliths
Mechanical Resistance
e.g. protective coat, washcoat, gauzes
Thermal Resistance
e.g. non-oxide ceramics, doped Ba-hexaaluminate
Chemical Resistance
e.g. non-oxide ceramic, silicon dioxide, Al-phosphate
Electromagnetic Properties
e.g. dielectrically heated catalysts, magnetic uidized beds
resistance, and electromagnetic behavior (Table 3). The use of such microstructured hybrid catalysts can make an important contribution to process intensication measures in other areas as well.
8.
SUMMARY
The reaction engineer has a variety of tools at his disposal when attempting to
intensify heat transfer in chemical reactors, ranging from well-established methods to innovative technologies. For recuperative heat transfer, the most dramatic
improvements can be achieved by using catalytic or catalytically coated heat
exchange surfaces and working at the millimeter scale to harmonize the physical
and chemical processes taking place and render the catalytic chemistry the
performance-limiting step. These two measures overcome the most serious bottlenecks in the traditional multitubular reactor.
The operation of regenerative and reactive processes for the manipulation
of temperature proles in chemical reactors is usually more complex than convective and recuperative techniques, due to the inherent dynamics and high sensitivities involved. Regenerative and reactive processes can, however, permit
a more active (self-) regulation of the temperature conditions within the reactor,
which can, in some cases, simplify their implementation.
The full potential of hybrid operation, employing more than one of the fundamental processes for manipulating temperature and concentration proles,
remains to be realized. Special catalysts and reactors must be developed to
accommodate the conicting demands that often arise in the design process.
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11
Process Synthesis/Integration
Patrick Linke and Antonis Kokossis
University of Surrey, Surrey, England
Henk van den Berg

University of Twente, Enschede, The Netherlands, and
Ghent University, Ghent, Belgium
1.
INTRODUCTION
Process synthesis, also referred to as process integration, deals with the systematic
development of process owsheets. The process synthesis activity has been
described as the automatic generation of design alternatives and the selection of
the better ones based on incomplete information (1). Design technology is required
to help the engineer nd novel, improved solutions to process design problems in
the context of the incomplete information available. The ultimate aim of chemical process design is to synthesize a process that enables the production of desired
chemicals in the most cost-effective and environmentally benign manner possible
and is exible as well as easily operated. Ideally, process synthesis tools should
allow one, out of the set of all feasible alternative structural and operational
process design options, to systematically determine the most promising process
designs, those that approach the performance limits of the system closely and
meet the constraints.
An enormous variety of decisions need to be made in order to solve process
design problems. These range from the selection of the most promising process
chemistry (reaction paths and catalysts) to the optimal exploitation of reaction,
mass, and heat transfer interactions at the process level. In order to arrive at
a truly optimal design, all decisions have to be made with respect to the overall
objectives in order to achieve the best balance of process trade-offs. Due to the
complexity of the overall problem, applicabilities of systematic decision-making
technologies are generally conned to closely dened design subproblems. The
onion model (see e.g., Ref. 2) captures a shared view that the process design
problem is best decomposed into a reactor design (the heart of the process) subproblem, a separation system design subproblem, an energy system design subproblem, and a utility system design subproblem. These subproblems appear
challenging for a variety of reasons. Challenges in reactor optimization arise
mainly from the high nonlinearities that need to be addressed. In energy systems
such as heat exchanger networks, on the other hand, the challenge is to search the
vast number of combinatorial design options. Separation system design presents
examples of intermediate complexity in terms of model nonlinearities. Despite the
challenges, the design problem decomposition itself leaves plenty of unanswered
questions to be addressed by future research. Clearly, there is signicant scope for
improvement by looking at a bigger picture and systematically exploiting interactions between solutions to the classical design subproblems. Recent developments
in process synthesis technology aim at giving a more global perspective by solving less conned but more conceptual problems in a variety of areas.
Process synthesis and integration tools are generally developed in academia. Successful technology development requires close collaboration between the
academic and the industrialist to ensure applicability to real-life problems. The
most successful example of process synthesis and integration technology development is pinch analysis (3). After many years of close academiaindustry collaboration, pinch analysis has led to signicant energy savings in the chemical
industries and has become a standard tool employed in most energy system synthesis projects worldwide. In contrast to the simpler techniques for energy systems synthesis that have relatively quickly been taking up applications in
industry, the methods for separation and reaction system synthesis have been slow
in being widely accepted by industrialists. However, these tools have the potential to signicantly help design engineers in their quest to develop new plants
faster and with fewer resources.
The next section will reect on common conceptual process design practices for overall owsheet development. The remainder of this chapter reviews
recent developments in process synthesis methods for reaction and separation
systems that systematically guide the design decision-making process toward
novel and improved designs.
2.
CONVENTIONAL CONCEPTUAL DESIGN PRACTICES
In this section a number of issues of process synthesis and conceptual design will
be reviewed. Based on available textbook knowledge (2,46), a synergistic
approach is discussed that uses project organization, decomposition, process

building, selection of alternatives, and design rounds. Process functions are taken
into account at a level above the unit operations. Due to the importance of project organization (6), management techniques also need to be applied to process
engineering. This section reects on experiences with industrial applications as
well as graduate courses on process design. New aspects on the combination and
arrangement of activities will also be discussed (7).
2.1.
Elements of Conceptual Process Design
This section deals with a number of basic points of process design strategy, cornerstones that have to be applied in a synergistic procedure. The application realizes a synergy of process functional analysis, process synthesis, and project
organization to generate structure and trace alternatives and decisions. This synergy in conceptual process design uses the elements of heuristics, mathematics,
and creativity. Components of conventional design approaches include:
Existing owsheet and technology analysiscollection of know-how.
Flowsheet decomposition into functional sections where tasks prevail over
equipment and unit operations.
A black box approach as the endpoint of the analysis; raw materials and
products, overall process-relevant data (e.g., yields, reactor conditions),
and boundary conditions are given, leading to a rst evaluation of the
overall process; economics are based on raw materials and products.
Formulation of goals for the new design; the black box is the start of the
rebuilding of the process from outside to inside.
Systematic process rebuilding, while including known and creative technologies and breakthroughs and using heuristics, expert systems, and
process simulation.
Application of management tools in the form of tree diagrams (interrelationship of goals and means) and work diagrams (to structure the project
step by step), document alternatives and choices.
The approach has similarities with a bow-tie model: One starts broad and
collects all available process information. A structure is used, e.g., a tree diagram,
to create a format for the information needed and collected. One should concentrate on the essentials and collect all relevant factors that inuence the process,
from the outside to the inside. Setting the boundaries of the process early reduces
rework later on; however, this clearly limits the degree of design novelty that can
be achieved.
Phasing of process design is a normal issue in the process industries. A process
design or substantial modication is done stepwise. Sequential steps in process
design are carried out after management approvals of the process proposals. This
means that project organization is of vital importance to direct activities and to
avoid rework. This aspect is hardly covered in the textbooks for process synthesis. Biegler et al. (5) use several levels or loops in their book, but they are not
linked to the phases of process design. The concept of process owsheet decomposition is used by Douglas (4) and Biegler et al. (5) but needs more emphasis
from the moment a project is started. Flowsheets have to be translated into functional activities so that a critical and systematic analysis can be started early. The
results can be used during the buildup phase after the black (grey) box model
development. Conventional technology is easily used in the buildup phase
because it is mature and has less or no risk, but new technology has to be taken
into consideration to enable step changes in performance improvements and to
avoid copy engineering.
All design textbooks mention that important decisions are made in the early
stages of design and that the know-how to make these decisions is developed
gradually during the design process. The consequences of choices made in early
stages of design cannot be foreseen at the moment of the decision. It is clear that
minor decisions about the type of a centrifugal pump to be used for the reux of
a distillation column are less important in the early stages of design than in the
performance of the reactor. Douglas (4) advocates the application of rejection of
less attractive alternatives and proposes to continue the development of all alternatives that cannot be rejected. The conventional way is to continue with a single
alternative; however, this tends to cause problems later in the project. Biegler
et al. (5) and Seider et al. (6) show how to document alternatives and choices.
Criteria for rejection are, e.g., process yield and selectivity, costs, safety, ecology,
and reliability of equipment. These criteria and the decision process have to be
documented. It must be possible to return to the design path in case the results
have to be rejected and early decisions need to be reconsidered, as shown in
Figure 1.
A systematic process design cannot be done in one step. It is common practice to develop a draft owsheet rst. This will be a feasible, unoptimized owsheet,
FIGURE 1 Alternatives and choices.
where the consequences of the choices made are not yet clear. Biegler et al. (5)
refer to this as the base-case design and propose four sequential rounds to complete the design of the process. The process know-how is extended from round to
round, and the consequences of choices from among alternatives become more
and more clear. In the fourth step Biegler et al. (5) use optimization techniques to
search for design alternatives. Ideally, the project phasing applied in the process
industry and the growing ability of the process engineers to collect and judge
alternatives during the project need to be matched. The next section describes
such an approach.
2.2.
Step-by-Step Conceptual Process Design
This section gives a short description of a step-by-step design strategy that applies
topics treated in the previous section. Assume that the task of a process is to convert raw materials A and B into product C and to minimize by-product or waste
D. The states of materials A, B, C, and D are dened by: mass ow, composition,
phase (vapor, liquid, solid), form (e.g., particle size), temperature, and pressure
(6). The process design has to consider alternatives for raw materials and process
routes that lead to a given product. This is done in step 0 of the design activities.
An early set design basis is often the production capacity (ton/yr). Each process
operation can be viewed as having a role in eliminating one or more of the property differences between the raw materials and the products. The rst step is to
eliminate differences in molecular type by chemical reaction. The function of the
reactor is usually considered the heart of a chemical process. Raw materials are
seldom converted into the desired products at the required purities, so a separation function needs to be dened in Step 2. The need for and task of separation is
often strengthened by the reactor conditions, e.g., excess of a component may be
required inside the reactor. Generally, the reactor outlet needs the separation function to match the product specication. This information is collected in the
decomposition stage of process design. Other functions in the process area that
one needs to take into account are change of phase, phase separation, change of
temperature and pressure, as well as mixing and splitting streams. Each operation
can be viewed as having a role in eliminating one or more of the property difference between raw materials and products. The transition from raw materials to
products is schematically represented in Figure 2, based on the information given
in Seider et al. (6) and Biegler et al. (5). Alternative arrangements of reactors and
separators are considered as a next design action. Both Douglas (4) and Seider
et al. (6) consider the choice between batchwise operation and continuous operation
a rst choice in process design. Our experience is that a black box evaluationa
mass balance and a rst economic evaluationbased on raw material and product ows, yields, and prices can be made without making a choice between batch
and continuous operation.
FIGURE 2 Moving from synthesis steps to process operations.
Connections between process units are created in a third step while considering in detail the following aspects:
From raw materials to reactor: purication and conditioning of feeds (purification, heating, pressure)
From separator to product: nal purication (nishing)
Reactorseparator connections: stream reconditioning (e.g., reduction of
temperature and/or pressure)
Connections of separator outlets: reactor performance, excess components,
recovery
Recycles from separators: connections to, e.g., reactor system
Step 4 consists of dening and matching the mass ows, including, e.g., the
excess of one component required in the reactor. The activity starts with building
preliminary mass balances before other conservation laws, i.e., heat and impulse,
are considered. Other relevant factors that have to be evaluated early in process
design are controllability and safety. The outcome of Step 4 is an overview of
process functions needed to realize the transition of raw materials into products,
including alternative owsheets and unit operations that could be applied. Step 5
considers the combination of unit operations or task integration to develop the
opportunities for process intensication, viz., leading to smaller, more efcient,
and cheaper processes. This step includes screening for options related to heat
integration and reactive separations, among others.
Step 6 consists of the setup of the mass and heat balances, and alternatives
for the reaction and separation functions are considered. The alternatives are documented in a structure such as the one shown in Figure 1 or the synthesis tree proposed by Seider et al. (6). Proceeding with the steps, many process alternatives
are generated form which the most promising ones need to be selected taking
into account prot, process yield, controllability, safety, and ecological aspects.
Criteria for assessing preliminary designs are presented in Ref. 5.
Between the steps, interactions will take place and decisions can create the
need for loops to previous steps, e.g., to reconsider the reactions (Step 1) and separation (Step 2) in more detail. Process design is generally not done in a rst and
single round; a next round is required to reconsider choices made, reduce the
number of alternatives, and select the most promising optionwhile taking into
account best available technology, heuristics, and creative new solutions. A second round, as proposed by Biegler et al. (5), is carried out to create a more
in-depth conceptual design and to extend the process design activities, e.g.,
toward process simulation, heat integration, and equipment design. This is done
in line with the project phases mentioned.
Various industrial applications of the step-by-step design approach have
been reported (see, e.g., Ref. 8). A number of these and other condential projects
have shown the value of the coordinated approach to conceptual process design.
From the foregoing discussion it is clear that the process alternatives are
commonly generated based on intuition and case-based reasoning. This leaves a
strong chance that promising design candidates are not arrived at and that novelty
is not automatically accounted for in the design process. Ideally, a systematic
approach should be able to capture all possible design alternatives and screen for
the design that delivers the best possible performance for the specied performance measure. The following sections describe such technology developments for
reaction system synthesis, separation system synthesis, and integrated reaction
separation systems.
3.
REACTION ENGINEERING
The reactor is undoubtedly the most important ingredient of a chemical process

owsheet, for it is the part where the product value is generated. From a decisionmaking perspective, the reactor design is more of a difcult process design task
than the separation and energy systems design tasks. This is because the reaction,
heat transfer, and mass transfer phenomena tend to occur simultaneously in this
unit. Most reaction models of commercially relevant systems are highly complex,
and the development of both graphical and computational design tools that enable
quick decisionmaking so as to obtain high-performance reactor designs is challenging. Such tools are required to provide performance targets and design suggestions for mixing and operational policies to give maximum decision support
to the designer.
There is an increasing awareness that the commonly employed textbook
knowledge and heuristics (9) is insufcient for the systematic development of
high-performance reactor designs. The result is a lack of innovation, quality, and
efciency in many industrial designs. Researchers from various perspectives are
making efforts to develop systematic optimization tools to improve the performance of chemical reactors. At a conceptual level, the area of reactor network synthesis has resulted in new methods that focus on a systematic and thorough
consideration of the available options. In the remainder of this section, we describe recent developments in reactor network synthesis that provide systematic
decision support for various reactor design aspects. Reactor network synthesis
aims at identifying high-performance reactor design candidates that exploit mixing, feeding, bypassing, recycling, and temperature effects such that the systems
performance is maximized with respect to the objective functions employed.
3.1.
Single-Phase Systems
Virtually all efforts in reactor network synthesis have addressed single-phase systems. Design approaches can be broadly divided into superstructure optimizationbased and graphical synthesis. Achenie and Biegler (1012) were the rst to
synthesize comprehensive reactor superstructures using optimization technology.
They developed superstructures using axial dispersion models, recycle-PFR representations, and environmental reactor models and applied optimization techniques in the form of nonlinear programming (NLP) methods to identify the most
promising design candidates hidden in the them. Kokossis and Floudas (1315)
rst introduced the idea of a reactor network superstructure modeled and optimized as a mixed-integer nonlinear programming (MINLP) formulation. Though
general and inclusive, their representation did not follow previous developments
but made an effort to facilitate the functionalities of the MINLP technology with
the synthesis objectives. With the primary purpose of scoping, optimizing, and
analyzing the reaction process, Kokossis and Floudas replaced detailed models
with simple though generic structures, enough to screen for design options and
estimate the limiting performance of the reaction system. In the same vein,
dynamic components have been replaced with the use of CSTR cascades. A
superstructure of generic elements (ideal CSTRs and PFRs) was postulated to
account for all possible interconnections amongst the units (Figure 3). The representation was modeled and optimized as an MINLP model. Schweiger and
Floudas (16) later revisited the approach and optimized superstructures with the
PFRs, with side streams being replaced by rigorous DSR representations that
avoid the inaccuracies introduced by the use of CSTR cascades.
Around the same time, Glasser et al. (17) retrieved and extended the
insightful methods of Horn (18) and presented graphical procedures known as the
attainable region (AR) method. Their approach requires the graphical construction of the convex hull of the problem and helps to exemplify the need for a systematic and general methodology. In principle, the reactor network with
maximum performance in terms of yield, selectivity, or conversion can be located on the boundary of the AR in the form of DSR and CSTR cascades with
FIGURE 3 Reactor superstructure. (From Ref. 31.)
bypasses. Though useful in two dimensions, in higher dimensions their developments face both graphical and implementation problems. Furthermore, the AR
methods frequently result in complex designs with multiple DSR and CSTR units
and complex feeding and bypassing strategies. Though fundamental limitations
appear evident, persistent efforts to extend the graphical methods have been published (1924). A more promising direction has been pursued by Biegler and
coworkers. The motivation has been to instill better guarantees in the optimization efforts by exploiting ideas and rules established in the construction of the
AR. Applications presented in this area include the work by Balakrishna and
Biegler (25,26) and Lakshmanan and Biegler (2729) and involved mathematical
programming applications in the form of NLP and MINLP formulations.
Hildebrandt and Biegler (30) presented a review of the attainable region
approaches and suggested areas for future development of the concept.
In 1999, Marcoulaki and Kokossis (31) presented a different interpretation
of the synthesis problem. From a practical viewpoint, the nature of a useful
approach for reactor network synthesis should primarily account for solid performance limits for the reaction system (targeting) and the systematic development of design candidates that approach this performance (screening and
scoping). Targeting is particularly useful for the design decision making because
it allows design evaluation in light of the ultimate performance possible for a
given system, provided there is enough condence in the optimization results.
The targets can be used for synthesis and retrot problems because they can provide the incentives to modify the operation and ideas for developing the reactor
design. Because the design equations of chemical reactors feature a signicant
number of nonconvex terms, the importance of condence assumes a signicant
place, and robust optimization technology is called for. On the other hand, the
borders of the attainable region and the strictly optimal solutions assume a relative meaning in reactor design. The reaction kinetics typically involve signicant
uncertainties and approximate models that give little justication for a strict
emphasis on the optimum. In this context, the development of a CSTR-PFRCSTR-PFR-CSTR-PFR layout as an optimal conguration represents an academic exercise of limited interest. A single, slightly inferior CSTR can feature
operational advantages and prove an even better choice in the form of an industrial back-mixed reactor. From a targeting viewpoint, layouts near the targets are
considered equally important. Therefore, solutions in the interior of the attainable
region make valid options as long as they remain close to the targets (31).
Screening and scoping aims at identifying the range of design candidates that perform reasonably close to the targets so as to provide the design engineer with
options on which the decision making can be based.
The nonlinear, discontinuous, and discrete nature of the synthesis problem
formulation considered here is not suitable to be addressed by mathematical programming techniques in the form of the commonly employed (mixed-integer)
nonlinear programs ((MI)NLPs) because the synthesis aim is to establish performance targets in the different synthesis stages. Mathematical programming
searches for local improvements and terminates at the nearest locally optimal
point. For a general case, there is no reason to be condent that the obtained solution cannot be substantially improved. The type of information required from the
targeting stage naturally relates to the results one can obtain with the application
of a stochastic optimization approach to the reactor network superstructure synthesis. The application of stochastic optimization gives one condence in the
optimization results, can yield particularly nonlinear reactor models, and is not
restricted by the dimensionality or the size of the problem. Marcoulaki and
Kokossis have applied stochastic optimization in the form of the simulated
annealing meta-heuristic to the single-phase reactor network synthesis problem (31). They optimize the rich and inclusive superstructures formulated by
Kokossis and Floudas (13) to identify performance targets and to extract numerous design candidates that approach the targets. The implementation of the stochastic search over the superstructure schemes requires venues for the development
and evolution of states, the assessment and acceptance criteria, and the cooling
schedule. The synthesis perspective and the optimization methodology is discussed
in detail in Marcoulaki and Kokossis (31). They found the methodology to systematically converge to the globally optimal domain, i.e., the performance targets of the
system, and to produce numerous design alternatives with performances close to
these targets for the numerous complex systems studied.
To illustrate the methodology, consider the Denbigh reaction system. The
reaction scheme involves ve components and is described by:
2A
1 B,
B
2 C,
A
3 D,
2B
4 E
with the following kinetics:

R [ R1 , R 2 , R 3 , R 4 ] [k1 x A2 , k2 x B , k3 x A , k4 x B2 ]
The data are from Ref. 31. The objective for optimization is the maximization of
the efuent concentration of component B. The performance limit of the system
is identied with each stochastic run requiring an average of only 120 CPU sec
on an HP 9000-C100 workstation. Numerous designs are obtained from the stochastic search that perform close to the performance target, mostly variations of
series arrangements of PFRs and CSTRs. A detailed discussion of this and other
studies is given in Ref. 31.
3.2.
Multiphase Systems
After xed-bed reactors, multiphase reactors are the most widely used reaction
systems in the chemical process Industries. The common industrial practice
employs conventional designs based on empiricism, past experience, and qualitative reasoning on the basis of analogies with similar systems and case studies. The
presence of multiple uid phases in the system represents additional degrees of
freedom that need to be exploited in process synthesis. As compared to the singlephase reactor network design problem, the multiphase case poses additional
challenges in the form of a signicantly larger number of possible network configurations as well as additional modeling complexities arising from the additional
need to model multiple phases and to address mass transfer and hydrodynamic
effects.
Mehta and Kokossis (32) introduced a systematic methodology for the synthesis of multiphase chemical reaction networks that is based on a compact representation of design options. The approach accounts not only for conventional
industrial reactors, such as bubble columns, cocurrent and countercurrent beds,
and agitated reactors, but also for all possible combinations of compartments that
can improve or enhance the performance of a multiphase reaction process. The
representation is described in the form of a superstructure of generic synthesis
units featuring shadow reactor compartments, and the synthesis scheme provides
functionalities that are subjected to optimization. The implementation of the
single-phase reactor network synthesis methodology of Marcoulaki and Kokossis
(31,33) enables the development of targets and screening procedures that can help
the engineer to assess system performance and review promising design options.
The building block of the superstructure representation is the generic reactor
unit, which follows the shadow reactor concept (32). This generic unit is illustrated
in Figure 4. Each generic unit consists of reactor compartments in each phase of the
system, and each processes the reaction. The shadow reactor compartment assumes
a state from the set of homogeneous reactors. The default units in the set include
CSTRs and PFRs with side streams. The interface between a given pair of
FIGURE 4 Generic multiphase reactor unit. (From Ref. 34.)
compartments in contacting phases establishes mass transfer links through which

mass transfer with its shadows in other phases is accounted for. Mixing is accommodated for through links with other compartments of the same phase.
Each generic reactor unit can represent all possible combinations of mixing
and contacting patterns that can be associated with the ideal representations of the
conventional reactor designs. Figure 5 shows the ve possible conventional reactor designs and their counterparts in generic reactor unit instances for a system
comprising two phases. The shadow reactor concept is generic and can be applied
to systems with any number of phases. The modeling equations associated with
the generic units are given in Mehta (34).
The shadow reactor superstructure is generated for a specied number of
generic reactor units by linking the compartments of a particular phase with a
stream network realizing complete connectivity. By a selective combination of
these streams, options related to feed distribution, product removal, bypasses, and
recycles among the generic units in the network can be evaluated for each phase.
The shadow reactor superstructure is illustrated in Figure 6 for a system with two
phases. The ow directions in the compartments, along with the options available
in the stream network, give rise to conventional as well as novel arrangements.
These options can be explored through optimal search of the solution space
dened by the superstructure.
Nonisothermal systems are accounted for by the introduction of temperaturecontrol units into the generic reactor unit representation. These units consist of elements associated with the manipulation of temperature changes and constitute
temperature proles (prole-based approach) and heaters/coolers (unit-based
approach). The assumption of thermal equilibrium between the contacting phases
reduces the need for a single temperature per shadow reactor compartment. The
prole-based system (PBS) nds the optimum proles without considering the
details of heat transfer mechanisms. Because the proles are imposed rather than
developed, the approach adds no further computational difculties as compared

to the isothermal reactor network synthesis. By biasing the prole complexity of
the nal solutions, the proles can be controlled effectively. The solutions
obtained are easy to interpret, and thus the approach helps in understanding of
dominant trade-offs in the problems. Results from the unit-based system (UBS)
provides the target that can be obtained from a network of adiabatic reactors with
consideration of direct and indirect intermediate heat transfer options. The synthesis of nonisothermal homogeneous and multiphase reactor networks is discussed in detail in Mehta and Kokossis (35).
Following a similar reasoning that had led to the choice of an appropriate
optimization technology for the single-phase reactor network synthesis as described
in Section 3.1, stochastic optimization in the form of simulated annealing (SA) is
adapted for the synthesis of the multiphase networks as well. The advantages are
the identication of stochastic optima with condence levels and the provision of a
variety of solutions around the targets that can be reviewed as alternative designs.
The synthesis framework consists of three stages. The targeting stage calculates
performance targets and condence levels using stochastic optimization in the form
of SA. Simulated annealing is based on a randomized evolution of states developed
through stepwise modication. The states are developed using the shadow reactor
superstructure. In the screening and design stage, the results of the targeting stage
are used to develop designs and layouts that feature performances that fall within a
desired distance from the targets. These may consist of designs with the same or a
different number of compartments, layouts with different networks of streams,
FIGURE 5 Conventional reactor designs and generic unit counterparts. (From

Ref. 34.)
FIGURE 6 Shadow reactor superstructure. (From Ref. 34.)
recycles, and bypasses, or variations on the same structure. The stochastic search
produces a multitude of solutions with similar performance, and its function is
exploited as a major advantage. These designs can be improved further with the
application of deterministic methods and more accurate models. The solutions developed from the screening stage are functional models based on the shadow reactor
superstructure model. The analysis and validation stage requires the translation of
these layouts into practical schemes. In general there are several ways to develop
practical schemes from the functional models because one can opt for either physically distinct units or multicompartment reactors.
Consider the reactor design for the production chlorination of butanoic acid
as an example to illustrate the technology developments. A full study is given in
Ref. 34, and only a brief summary of the results is presented here. The chlorination of butanoic acid (BA) involves two reactions in the liquid phase:
1.
BA Cl2
MBA HCl
2.
BA 2Cl2
DBA 2HCl
where MBA and DBA are abbreviations for monochlorobutanoic acid and
dichlorobutanoic acid, respectively. The system involves two phases, a liquid
phase where the reactions occur, and a gas phase consisting of chlorine feed and
hydrogen chloride product. Solubilities are calculated using Henrys law, and
mass transfer rates are modeled according to lm theory. The reaction kinetics
and all model parameters and other problem data used in the study are given in
Ref. 34. The objective of the study was to nd those reactor networks with the
highest possible yield. Initially the study was performed assuming xed phase
holdups in the reactor units; i.e., hydrodynamic effects are neglected.
Conventional reactor designs have been optimized to create a basis for
comparison. The mechanically agitated vessel achieves the highest yield of
74.4%, followed by the bubble column reactor with a yield of 72.9%, and the coas well as the countercurrent reactors both achieving a yield of 69.5%.
Reactor network optimization of a superstructure comprising three generic
units produces a performance target of 99.6% yield of MBA. The selected designs
with performances close to the target value range from simple designs employing
only one reactor unit to designs featuring three units. The simplest solution consists of a single reactor with completely back-mixed gas and liquid phases and a
bypass of fresh chlorine feed. Other, unconventional designs are also found that
consist of two or three generic units, all approaching the target performance
closely. Two of the simple designs are illustrated in Figure 7. For the unconventional designs, see Ref. 34.
Mehta and Kokossis (36) also demonstrate how existing knowledge in the
form of hydrodynamic correlations can be incorporated into the framework while
maintaining the possibility of achieving design novelty. They also show how to
deal with the ranges of application of the different available correlations so as to
nd meaningful results. For the example just described, they found that the performance target of 99.6% remains unchanged if the known hydrodynamic effects
are considered for the reactor units via common correlations available in the literature. However, changes in the reactor designs from a mechanically agitated
FIGURE 7 Reactor design candidates. (From Ref. 34.)
vessel to a bubble column reactor are observed as a result of the higher interfacial
areas available in the bubble column, according to the correlations. The methodology for the design of nonisothermal multiphase reactor networks is presented in
detail in Refs. 35 and 36.
4.
COMPLEX DISTILLATION
Despite advances in other separation technologies, distillation is still the most

widely used operation in chemical processes. Effective screening of separation
systems constitutes a critical stage, for engineers need to review and understand
trade-offs ahead of detailed modeling and simulation. In the separation, it is often
desired to explore the use of complex rather than simple columns because the
complex units reduce mixing losses, use available vapor and liquid more effectively, and improve the separation efciency (37). Despite their recognized potential in energy savings, complex distillation applications are limited due to their
difcult and demanding design-and-synthesis assignment. Synthesis challenges
and operability issues that arise from a more complex dynamic behavior have discouraged wider acceptance in industry. A prohibitive number of congurations
emerge from different allocations of side-rectiers, side-strippers, prefractionators, and side-draw columns. Such options are difcult to enumerate and assess.
The design alternatives increase rapidly, and the trade-offs are impossible to
assess with an exhaustive (implicit or explicit) enumeration of the options.
Previous efforts have focused on the development of shortcut methods
that had a purpose of evaluating fixed configurations and initializing simulation
models. Stupin and Lockhart (38) developed the equivalent arrangements of
simple columns to represent complex congurations. Several other researchers
(37, 3947) extended knowledge from shortcut models as available for simple
columns to evaluate the performance of complex congurations. Tedder and
Rudd (48) performed a parametric analysis for complex designs and identied
optimality regions as functions of the feed composition and the relative volatilities. Glinos and Malone (49) identied dimensionless parameters and proposed
guidelines for the selection of complex distillation schemes. With less emphasis
on xed layouts, thermodynamic methods (5053) produced procedures to assess
energy efciency in the integrated separation.
Mathematical programming approaches promote process novelty with the
use of superstructure development. Sargent and Gaminibandara (54) pioneered a
progressive distillation train that Agrawal (55) later extended with additional connections of vaporliquid streams to include satellite columns. Christiansen et al.
(56) added more connections between component states to include structures with
triangular walls in a single shell. Several researchers (5762) have proposed different superstructures and developed mixed-integer nonlinear programming
(MINLP) models for the synthesis of distillation systems. These superstructures
can be generalized as the combinations of two extreme representations, the state

task network (STN) of Sargent (63) and the stateequipment network (SEN) of
Smith and Pantelides (59). These developments use superstructures of complicated interconnections with a large number of variables to account for the design
options. More often than not, however, the optimization technology required to
process these models is not addressed as a challenge. Researchers simply assume
the technology is readily available and that the models can be solved and optimized robustly. Consequently, reported designs contain conventional rather than
novel and unconventional designs. The development of new mathematical formulations for synthesis problems should not be detached from the optimization
technology required to handle these models. Yeomans and Grossmann (64,65)
have made some progress on a solution strategy using generalized disjunctive
programming models, but their method is still unable to address major difculties
of solving industrial-scale distillation synthesis problems.
Papalexandri and Pistikopoulos (66) propose a representation based on a
superstructure of multipurpose heat and mass transfer modules. The authors refer
to tasks as a more general form of a synthesis unit. They postulate an even more
general (and difcult) problem and propose a detailed modeling framework that
relies on the use of MINLP solvers. In contrast to the work by Papalexandri and
Pistikopoulos, Shah and Kokossis (67,68) use the concept of a task (69) to reduce
rather than enlarge the mathematical model and to simplify rather than complicate
the optimization. In all cases the mathematical models are postulated as small
mixed-integer linear programming (MILP) problems one can solve to global optimality. The remainder of this section gives a description of these developments.
Shah and Kokossis (67,68) present a simultaneously systematic and rigorous
approach for the automated development of optimal designs. The approach is computationally inexpensive, reliable, and very efcient to implement. It provides the
engineer with a selected set of optimal designs on which further attention to
dynamics and operability would yield the nal design. The work embraces conceptual and engineering knowledge. In the past, conceptual knowledge has been
restricted to heuristics and evolutionary approaches, both inappropriate for a systematic search. They typically employ a two-step approach where the best simple
sequence is rst identied. The sequence is next evolved into complex layouts.
Although novelties are not excluded, they are left to coincidence and deprived from
a systematic framework. The challenge is to develop systematic procedures that
overcome the difculties encountered with superstructure approaches. In contrast,
the new synthesis approach is based on a supertask representation. The approach
conceptualizes alternatives using simple tasks and hybrid tasks. The options include
all complex column congurations related to side rectiers, side strippers, prefractionators, Petlyuk columns, and side-draw columns. Furthermore, the representation accounts for sequences with sloppy separations and enables one to bracket
optimum pressure limits. The approach assumes a number of components to be
separated into a predened set of products. Given is the basic information about the
components with respect to its physical and critical properties. The objective is to
determine the appropriate and cost-effective separation schemes ahead of detailed
simulations. In order to address complex systems effectively, Shah and Kokossis
(67,68) replace superstructures with supertasks. The building blocks of the latter
are not unit based, but task-based elements. Apart from simple columns, the synthesis representation is required to embed elementary complex distillation arrangements involving side columns, side-draw columns, and prefractionators. These
complex arrangements are shown in Figure 8. The gure explains the two different
types of side columns: the side-rectier arrangement type (Figure 8a) and the sidestripper arrangement (Figure 8b); two types of side-draw columns: the vapor sidedraw column (Figure 8c) and the liquid side-draw column (Figure 8d); and the two
prefractionator arrangements: with and without thermal coupling (Figures 8e and
8f). The arrangement shown in Figure 8f is known as a Petlyuk column.
FIGURE 8 Commonly used complex column arrangements. (From Ref. 82.)
Unlike simple columns, these complex congurations produce more than

two products and feature more than a single light and heavy key component. A
task-based representation of these schemes is accomplished with the ideas of
hybrids and sloppy splits. Additional tasks are made up of different simple tasks.
They are subsequently termed hybrid tasks and are dened as an ordered combination of simple distillation tasks, as illustrated in Figure 9.
The sloppy separation improves the separation efciency by distributing
components between the lightest and the heaviest ones. Among the different
options to distribute intermediate components (ICs), the maximum efciency is
accomplished by a general sequence of sloppy splits to separate the lightest and
heaviest product at each stage. For an n-product system, a hybrid of order (n 1)
accommodates a sequence of sloppy splits in the supertask representation.
However, it processes each product (n 1) times (for an n-product system) at the
expense of energy and column shells. These factors have an adverse effect on the
capital and operating costs of the separation system. To capitalize on the advantages of the sloppy split, hybrids of a second order (over n-product systems) are
included in arrangements, where sloppy splits are followed by sharp separation.
These schemes combine the higher separation efciency of the sloppy splits while
the recurrent processing of products in the downstream sequence is minimized by
the sharp separations. The sloppy split arrangements are introduced as an additional transformation on each hybrid.
Instances of a task are replicas of the task operating under different conditions. The concept is used to optimize the operating conditions, such as the
column pressure, and assumes the development of an operating range and a discretization scheme. Feasible ranges of pressure are identied by the physical
properties (e.g., critical pressure) of the key components (upper limit) and the
available utility levels (lower limit). The discretization scheme may be either uniform or based on the available utilities. The modeler can use a small or large number of discrete levels to capture associated trade-offs.
The synthesis elements of the supertask representation are translated into
modeling terms that combine available physical properties with design aspects.
Shah and Kokossis (67,68) exploit modeling accomplishments from a variety of
research groups (43,37,70) who have separately addressed the modeling and simulation challenges of complex distillation congurations. The calculations are
used to set up the MILP optimization problem. Each task is assessed and evaluated independently and separately from the performance of the upstream or
downstream units, because the composition and ow rate of the feed and the
products streams are known a priori and only depend on the separation function
of the particular task. Design and performance calculations can use any shortcut,
semirigorous or rigorous method and any property package without inuencing
the constraints and solution strategy of optimization efforts.
FIGURE 9 Illustration of tasks and hybrid tasks. (From Ref. 82.)
The proposed formulation results in a mixed-integer linear programming

problem that is solved using OSL/GAMS (71). The optimization simultaneously
yields the optimal sequence, the optimal hybrids, and the optimal transformations. The formulation guarantees the global optimality in all cases because it
involves only linear expressions of the continuous variables. An industrial application of the methodology is given in Section 6.
5. REACTIONSEPARATION AND REACTIVESEPARATION
SYSTEM SYNTHESIS
Particularly strong and complex interactions prevail among reaction and separation systems that are generally not at all or not fully exploited as a result of the
application of the available synthesis methods for reactor networks and separation systems in isolation. The lack of generality in the synthesis methods is a
tribute to the nonlinear process models required to capture the reaction and
separation phenomena as well as to the vast number of feasible process design
candidates. These complexities even make it difcult to synthesize the decomposed subsystems, which are typically reactor networks, separation systems,
reactorseparatorrecycle systems, and reactive separation systems. The development of reliable synthesis tools for these sub-systems is still an active research
area.
Potentially benecial interactions between reaction and separation are manifold and can result from either separation within the reaction zones of the process
(reactive separation systems), appropriate combinations of separate reaction and
separation equipment (reactorseparator systems), or a combination of these. The
realization of reactive separation options requires the introduction of mass separating options into the reaction equipment and results in additional phases or
states that need to be considered in the process synthesis. Common examples are
the introduction of solvents (reactive extraction, reactive absorption), stripping
agents (reactive distillation), solids (reactive crystallization), and diffusion barriers (membrane reactors). In general reactorseparator systems, a number of separation tasks exist that enable the generation of intermediates or products of a
performance-enhancing nature in the context of a general reacting system. The
optimal separation tasks cannot generally be performed by the same unit operation, and a combination of unit operations is likely to be present in optimal-ow
schemes.
It is obvious that the simultaneous inclusion of all possible reactorreactive
separationseparator design options into an automated design framework quickly
leads to combinatorial explosion. In combination with the nonlinear models used
to describe the reaction, mass, and heat transfer phenomena that occur in the processing units, the resulting synthesis problem is beyond the scope of existing optimization technology, even for relatively small problems. This has led to the
development of synthesis tools, which are constrained to limited reaction and/or

separation options; i.e., the general synthesis problem needs to be reduced in size
signicantly before any systematic synthesis methods can be applied (e.g., Refs. 14,
66, and 7276). This problem-size reduction poses a major challenge: identication of the relevant modeling information. Currently, the design engineer needs to
anticipate the important phenomena that dictate the performance of the system
without the help of systematic screening methods. This demands a thorough
understanding of the effects of component concentration and temperature manipulations on the system performance on the basis of process knowledge available at
the earliest design stage. A typical example is the effect of component addition
and removal to and from the reaction zones and the corresponding introduction of
reactive separation options. Although an experienced designer can spot the relevant trade-offs for simple reacting systems and link them with the physical property differences to be exploited for separation, this task becomes nontrivial for
systems with complex reactions where many components are present. However,
the inclusion of all relevant design options is vital for the synthesis of optimal
process congurations, because any opportunity excluded at this stage will
inevitably lead to an inferior design.
In view of the problem under consideration, Linke and Kokossis (77,78)
propose a design framework that accounts for two synthesis stages: a screening
stage that allows for identication of the dominant design trends in combined
reaction and separation task systems, followed by a design stage that incorporates
the insights gained in the screening stage and allows for the generation of optimal
reactorreactive separationseparation congurations.
The screening stage aims at replacing the early problem decomposition
based on intuition with the introduction of simple separation models that enable
the investigation of major trade-offs in the context of reactor design. This is facilitated by structural optimization of relaxed reactor/separation task network superstructure models. Allowing any separation tasks to be present in the networks, the
most important composition manipulations in the process network can be identied, regardless of separation feasibility. By introducing constraints on specic
separation tasks, sensitivity studies allow one to investigate their impact on the
performance targets and process layouts.
Rather than nal process layouts, the screening stage generates insights into
optimal component separation, removal and recycle policies, along with reactor
mixing and contacting patterns. The obtained process layouts feature reactor and
separation task combinations, and only those important tasks are subsequently
assessed for separation feasibility. The generated process design information is
processed in a design stage by introducing the additional modeling information
required for candidate reactive separation and mass exchange operations into a
rened superstructure network model and by excluding infeasible separation
tasks. In other words, more modeling rigor is added, to give a more detailed
account of the relevant reactive separation and separation options, while the
combinatorial size of the problem is reduced by the irrelevant design options.
The difference in targets between the screening and the design stages reect
potential savings of separation options termed infeasible upon analysis of the
physical properties and give incentives for the investigation of novel separation
techniques for the system under consideration, such as the development of novel
solvents, membranes, or hybrid separation systems. Both synthesis stages allow
for iterations to incorporate the insight gained during the synthesis process.
Reasons for iterations are the identication of additional problem constraints, the
removal of process units without positive impact on the system performance, and
the inclusion of rened process models. Such renements might result from the
limited validity of the available reaction models in optimal design regions. In
order to gain condence about the designs, a wide range of operating conditions
and structural design alternatives needs to be searched in the process synthesis
stage. In many cases, the optimized operating conditions do not coincide with the
regions of model validity, and the model trade-offs might not reect the real system trade-offs. This creates the need for new process models for the operation
regions identied as of interest, which may introduce additional model nonlinearities or an additional set of reactions and components. The proposed synthesis
representation, along with the robust optimization framework, is not limited by
the complexity of such models. The renement of reaction models demands additional experiments to be carried out. The synthesis methodology is efcient in
suggesting the concentration and temperature regions of interest for process
design, which helps to minimize the experimental efforts.
In both synthesis stages, superstructures of generic units are formulated,
and the performance targets as well as a set of design candidates are obtained subsequently via robust stochastic optimization techniques.
5.1.
Unit Representation
The basic elements of the synthesis representation are the generic reactor/mass
exchanger (RMX) units and the separation task units (STUs). The underlying
phenomena exploited in chemical process design are reaction, heat exchange, and
mass exchange. They are generally exploited simultaneously (nonisothermal multiphase reactors and reactive separators), in combinations (nonisothermal homogeneous reactors and mass exchangers), or in isolation (isothermal reactors and
mass exchangers, heat exchangers), depending on the particular system under
investigation and the location of the operation within the owsheet. This work
employs a generic reactor/mass exchanger unit for a exible and compact synthesis representation of all possibilities of phenomena exploitation. The RMX
unit follows the shadow compartment concept developed for nonisothermal multiphase reactor network synthesis (Section 3.2). The unit consists of compartments
in each phase or state present in the system under investigation, and the streams
processed in the different compartments of the generic unit can, by denition,
exchange mass across a physical boundary, which can be either a phase boundary
or a diffusion barrier. Each compartment features a superset of mutually exclusive
mixing patterns through which a compact representation of all possible contacting and mixing pattern combinations between streams of different phases can
be realized within a single generic unit. Along with decisions on the existence of
mass transfer links between compartments of the same generic unit and decisions
on the consideration of reaction phenomena in the different compartments, a single RMX unit enables the representation of a reactor, a mass exchanger, a reactive mass exchanger, or a combination of these. Each compartment receives inlet
streams within its state and corresponds with the compartments in the other states
via diffusional mass exchange links across the state boundaries. The efuents
from the compartments either leave the unit or are recycled within the RMX unit.
Recycles can be present within a given state or across the state boundaries if technically possible, e.g., by reboiling, condensing, throttling, or compression.
Throughout this work, all states that can receive streams from a reference state
are termed adaptable states to the reference state. Mutually exclusive mixing
options considered for the compartments include well-mixed and segregated ow.
In order to avoid a mathematical model with both differential and algebraic equations, segregated ow behavior is approximated with a serial arrangement of
well-mixed units of equal volume with the resulting cell model consisting of only
algebraic equations. In each compartment, all inlet streams are connected to all
mixers prior to the subunits. Each subunit efuent stream is split and connected
to the subsequent subunit as well as to the nal product mixer of the compartment. The recycle streams from the nal product splitter distribute among all
well-mixed units employed in the compartments of the adaptable states.
Temperature effects are accounted for in the compartment models in accordance
with the prole-based and the unit-based synthesis approaches (Section 3.2).
In contrast to the rigorous representation of reaction and mass transfer phenomena by RMX units, the separation task units (STUs) represent venues for
composition manipulations of streams without the need for detailed physical
models. In accordance with the purpose of any separation system, the separation
task units generate a number of outlet streams of different compositions by distributing the components present in the inlet stream among the outlet streams. In
the screening stage, the aim is to identify the separation tasks, which have a positive impact on the performance of the reactionseparation system. Only sharp
separations are considered between component lumps; i.e., each lump can be
present in only a single outlet stream of the separation task unit. Sharp separations
do not impose a limitation in terms of composition attainability, because any nonsharp separation can be obtained by sharp separation followed by stream mixing.
Moreover, potential benets that might arise from nonsharp separations as compared
to sharp separation followed by mixing cannot be quantied, because a particular

separation process is not specied at this synthesis stage. In the design stage, the
separation task unit is adoptable for the representation of separation tasks that
can be performed using particular separation processes. In this case, the possible
distribution policies of component lumps to the outlet streams are constrained by
the separation orders of the separation process. Nonsharp separations arising
from operational constraints on the separation tasks can easily be accomplished.
The separation task unit performs a set of feasible separation tasks according to
the separation order to dene a set of outlet streams. Depending on the order in
which the tasks are performed, a variety of processing alternatives exist for a single unit.
5.2.
Process Representation
The generic synthesis units presented earlier allow for the representation of all
sections of general processes involving reaction and separation, i.e., reaction sections, reactive separation sections, mass exchange sections, and sections performing separation tasks. The aim of the superstructure network generations is to
provide for a venue that enables the simultaneous exploration of all functionalities of the different synthesis units along with all possible interactions among
them. The superstructure formulations evolve in the different synthesis stages
according to the insights into the process obtained at the previous stages. Novelty
is accounted for in the superstructures because the representations are not constrained to conventional process congurations but instead include all possible
novel combinations of the synthesis units. The superstructures feature a number
of generic RMX and separation task units as well as raw material sources and
product sinks, the interconnections among which are realized by two types of
stream networks: Intraphase streams establish connections between the synthesis
units, products, and raw materials of the same state, whereas interphase streams
establish those connections across the state boundaries; i.e., the source and sink
of such a stream belong to adaptable states. The compositions of the streams
remain unchanged on state transition. The transfer of material across the state
boundary potentially requires the addition or removal of energy to or from the
interphase streams. In this case, an energy transfer unit such as a total reboiler or
a total condenser, a throttle or a compressor is associated with those mixers
receiving a stream from a different state.
Superstructures formulated in the design stage facilitate RMX units for representation of the relevant reaction, mass exchange, and reactive separation
options obtained from the screening stage and separation task units associated
with the different unit operations that allow one to perform the desired separation
tasks. This incurs superstructures with additional states resulting from the inclusion of separating agents and diffusion barriers. Figure 10 illustrates two process
congurations that can be obtained by eliminating interphase and intraphase

streams, as well as generic units from a superstructure network featuring two
RMX units and two separation task units in two states. A ow scheme featuring
a catalytic reactive distillation arrangement is shown in Figure 10a. The design
shown in Figure 10b does not feature any interphase connections, and reaction
FIGURE 10 Design instances from the superstructure.
occurs in both RMX units. A separation task unit facilitates the intermediate separation of components in between the RMX units; a plug-ow and a well-mixed
RMX compartment are arranged in series, followed by a separation task unit representing a separation sequence to separate the raw material from the product and
the by-products.
5.3.
Optimization
In order to establish a basis for optimization, the reaction and separation superstructure is formulated as a mathematical model that involves the component
material balances for the RMX units, the mixers prior to the separation task units,
and the product mixers, as well as the energy balances for the RMX units (for the
unit-based nonisothermal representation). The formulation incorporates models
for the reaction kinetics, physical property and mass transfer models, shortcut
models and regression expressions for equipment sizing and costing, and the
objective function. General relationship-modeling terms will introduce nonlinearities into the superstructure network model. As for the reactor network synthesis
problems, the reaction and separation superstructures are optimized using stochastic search techniques. Linke and Kokossis (77,78) have studied the performance of SA and tabu search (TS) for this type of problem. They found robust
performances for both algorithms and TS to be the more efcient search metaheuristic. A detailed description of the implementation of the stochastic search
algorithms is given in Ref. 79.
For illustration purposes, consider the WilliamsOtto owsheeting problem (80). In the conventional design, raw materials A and B are fed to a reactor,
where the following reactions occur:
(1)
AB
(2)
BC
PE
(3)
PC
The reactor efuents are cooled and fed to a decanter for removal of heavy waste
G, which requires further treatment. From the remaining mixture, the desired
product P is removed via distillation. The unreacted raw materials as well as
unwanted byproduct E and a fraction of P are partly recycled back to the reactor.
As components E and P form an azeotrope, an amount of the desired product
equivalent to at least 10% weight fraction of E is lost through the purge, which is
used on site as a fuel. The volatilities i of components i in the system have the
following descending order: P > E > C > B > A > G. The reaction rates of
components A, B, C, P, E, and G respectively are functions of the weight fractions
X and given by the vector
R(X) [k1XAXB; k1XAXB k2XBXC; 2k1XAXB 2k2XBXC k3XPXC;

k2XBXC 0.5k3XPXC; 2k2XBXC; 1.5k3XPXC]
The complete data are given in Ref. 79. The objective of the synthesis exercise is
to nd the designs that maximize the annual prot of the process for a minimum
production rate of 400 kg/h of component P.
5.3.1.
Screening Stage
The stochastic search of superstructures featuring three RMX and three unconstrained separation task units yields an absolute prot target of around $618 k/yr.
A variety of design alternatives exist that can achieve the targets, featuring one,
two, or three reactors and component distributors. The process design requirements as identied in the screening stage can be stated as follows:
Separation and removal of by-products E and G
Separation and removal of desired product P
Separation of components A, B, and C from the reacting mixture and distribution among the reactor units
Excess of component B in the reaction zones minimizes by-product formation (low concentration of product P)
Reaction zones exhibit plug-ow behavior
5.3.2.
Design Stage
Based on the insights gained in the rst design instance, appropriate separation
venues can be identied and included in the search. Distillation enables separation of mixtures according to the order of volatilities and hence allows separation
in support of the raw material and intermediate recovery. To avoid fouling, G
needs to be decanted prior to the operation, which can be achieved at a low cost
in a decanter. However, component P forms an azeotropic mixture with component E, resulting in a loss of desired product to the low-value fuel. A solvent is
available that allows selective extraction of desired product P from the mixture.
The equilibrium relationship and maximum solvent loading are given in Ref. 79.
The design stage therefore considers a superstructure of RMX units and STUs to
capture the reactionextractiondistillationdecanting system.
Stochastic optimization yields a target performance of around $433 k/yr for
the system. Designs with performances close to the target can be grouped into
two main categories according to their use of the solvent: reactive extraction
designs and reactorhybrid separation designs, each achieving performances
close to the target. Two sample designs are illustrated in Figure 11. Designs utilizing the distillationextraction hybrid achieve higher selectivities in the conversion of the raw materials to product P than do the reactive extraction designs,
in which valuable components A, B, and C are lost to the fuel stream. Both
designs achieve a virtually complete recovery of product P. The extraction of the
desired product from the concentrated distillation overheads allows for higher
solvent loadings and consequently a signicantly reduced solvent ow as compared to the reactive extraction case. However, the benets in terms of higher
selectivities and lower solvent ows are offset by the expenditure required for the
distillation operation.
FIGURE 11 Process design candidates from the design stage.
The methodology is illustrated with a further application to the design of

activated sludge process systems in Section 6 and has seen further applications
in multiphase reactionseparation, reactive distillation, and membrane network
synthesis (79).
6.
INDUSTRIAL STUDIES AND REAL-LIFE APPLICATIONS
The methods described in Sections 3 through 5 have been tested on a number of

case studies. This section presents three applications to problems of complexity
typically encountered in industrial practice that have been performed using the
synthesis schemes, partly in collaboration with industrial partners.
6.1. Reactor Design: Ammoxidation of Propylene
to Acrylonitrile
Mehta (34) has carried out a reactor network optimization study to nd improved
designs for the production of acrylonitrile in a collaboration between UMIST and
one of its industrial partners. Most industrial installations employ uidized-bed reactors (BP/Sohio process) with a well-mixed reaction zone. Previous process improvements have mainly resulted from better catalysts, which have produced an increase
in yield from 58% to around 80%. The reaction model employed in the optimization
study is taken from Ref. 81 and considers seven reactions and eight components. Air,
pure oxygen, and propylene are available as raw material streams. The optimization
study assumes negligible pressure drop along the reaction sections, isothermal and
isobaric operation, and negligible mass gassolid transfer effects.
Acrylonitrile yield has been employed as the objective function. Initial targeting has shown that the network yield increases with the catalyst volume
employed and asymptotically approaches a yield of around 90% toward innitely
large catalyst volumes. For very large volumes, the well-mixed reactor achieves
the performance targets. Because only smaller catalyst volumes are relevant in
industrial practice, a targeting study is carried out to develop the performance targets as functions of the catalyst volume utilized. For comparison, the targets for
the conventional well-mixed reactor are developed alongside the targets that can
be realized with reactor designs featuring novel unconventional mixing and feeddistribution policies. The targeting curve is shown in Figure 12. The targeting
curve shows that the performance of the CSTR reactor signicantly degrades
toward smaller catalyst volumes, i.e., toward the industrially more relevant
designs. Only a slight degradation of reactor yields with catalyst volume is
observed for the novel designs. This suggests that the acrylonitrile yield can be
kept high even with signicantly reduced catalyst volumes, provided an appropriate reactor network is selected. When compared to the conventional reactor,
the novel designs showed improvements in yield of up to 17% for practical values
FIGURE 12 Targeting curve for ammoxidation of propylene to acrylonitrile.
of catalyst volume. Mehta (34) observed a change in reactor design pattern

toward smaller catalyst volumes, gradually moving single CSTRs to combinations of PFRs and CSTRs with distributed feed streams.
The study was carried out over a short period of time and resulted in an
impressive enhancement of insights into how an optimal reactor should be
designed for maximum performance at low catalyst volumes. A commercial reactor design has subsequently been developed on the basis of the insights gained in
this study.
6.2.
Complex Distillation
This case study (82,67,68) included a feed containing nine components and that
had to be separated into four products: A (C4 fraction separated as lights), B (isopentane and some n-pentane), C (C6 fraction), and D (heavier components, C7+).
Minimum energy cost is used as the synthesis objective, and the optimization
results are summarized in Table 1. Designs I and II represent the favorable
schemes. Design I separates the lightest product and uses a prefractionator for the
downstream separation in hybrid B/C/D. Design II employs a prefractionator in
hybrid AB/C/D to separate plentiful products, C and D, early in the sequence.
Design III, the best simple sequence, separates the plentiful product, D, rst and
favors difcult separation, B/C, in the end. When simulated rigorously, the ranking of the design candidates remains identical to that from the conceptual design
level. The initial energy costs match very well with the costs from rigorous simulation. An interesting point is that in this example the best simple sequence is close
to an indirect sequence (Design III) but the best complex scheme corresponds to
TABLE 1 Promising Designs for the Industrial Complex Distillation

Case Study
Design
I
II
III
Energy
cost
Design
6.57
6.60
7.60
Column
Pressure
(bar)
Trays
4.9
30
1.8
1.8
82
3.5
3.5
90
4.9
29
1.6
23
4.9
29
1.8
54
a direct sequence (Design I). The lowest pressures are selected for all the tasks in
the designs. This results in the most favorable separation factors. The complex
column congurations require high pressures, and the benets of thermal coupling are counterbalanced by the requirement of higher reux. Pressure effects
were found to dominate the results and to minimize the thermal coupling.
6.3. Combined Reaction and Separation Systems:
The Activated Sludge Process
The reaction and separation synthesis approach of Section 5 has been adopted to
the problem of activated sludge process design (83). The conventional designs as
well as all novel schemes for combined oxidation/denitrication of wastewater
are explored. The process is optimized using a novel methodology for optimal
reaction/separation network synthesis, supplied with a comprehensive kinetic
model (84). The activated sludge process is synthesized using the systematic
reaction/separation network synthesis framework of Section 4 to determine the

optimal biochemical reactor network design along with the sludge separation and
recycle policies. The representation provides for all possible mixing, contacting,
and reaction/separation features, and the superstructures are optimized through
application of the simulated annealing algorithm. Oxygen mass transfer is modeled using lm theory. A weighted objective function is formulated so as to minimize both the efuent COD and total nitrogen content.
An initial optimization study without considering any bounds on the reactor
volumes yields a reference target (lowest value of objective function) of 100%, corresponding to a 96.8% reduction in COD and 84.8% in N. However, the reaction
volumes observed in the designs that achieve the targets are unpractically large. For
this reason, volume bounds are introduced in a subsequent study to achieve the
mean hydraulic residence time of the conventional processes. Surprisingly, the target did not deteriorate signicantly, the new target for the objective value being
101.4%. COD was reduced by 97.4% and N by 84.9%, a performance much better than those attained by any conventional process, especially as far as denitrication is concerned. An inspection of the structures revealed a design pattern: Many
structures did not include an anoxic reactor and yet yielded very good denitrication. Moreover, the system appeared to seek ways to hinder or control the dissolution of oxygen, in contrast to common practice, which aims at dissolving the
maximum amount possible into the oxic reactors. To nd out how such good denitrication could be accomplished without the inclusion of an anoxic reactor, the
detailed oxygen proles within the aerated reactors (mostly PFRs) were examined.
The concentration of oxygen is controlled within extremely low levels (0.10.3
ppm), an order of magnitude less than those currently used in industrial practice
(29 ppm). This leads to the conclusion that both organic matter stabilization and
denitrication processes occur simultaneously in these designs, due to the very low
oxygen concentrationsa policy that seems to achieve maximum efciency when
low volume is required. A schematic design of the system is illustrated in Figure
13. Details on the synthesis study can be found in Ref. 83.
FIGURE 13 Conceptual activated sludge process design.
7.
CONCLUSIONS
The drive to improve processes and to create new process routes continuously
force process engineers and management to develop new technology. Process
synthesis or integration has proven its value to improve processes with reduced
costs, less pollution, and lower energy consumption. Traditionally, most industrial
applications of process integration techniques have been found in developing
energy-efcient systems. After a brief discussion on common conceptual process
design practices, this chapter illustrated recently developed process synthesis
technology for process design problems involving reaction and separation. A
major advantage of the methods is their ability to determine robust performance
targets and to identify a variety of design options with similar close-to-target performances. The design tools offer decision support to the design engineer. This
will allow the inspection of similarities and differences among high-performance
candidates in order to select the most practical novel designs. However, for successful technology development and transfer, close collaboration between academia and industry is essential.
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12
Process Intensication in Industrial Practice:
Methodology and Application
Remko A. Bakker
DSM Fine Chemicals Austria, Linz, Austria
1.
INTRODUCTION
In this chapter a method is explained for how process intensication can be introduced in a commercial company. When one would like to introduce process intensication, certain steps can be followed that increase the chances of success.
One very important aspect is the awareness of the drivers for introducing
process intensication for certain processes and companies: the why of process
intensication. This is explained in Section 3 in some detail, for without the
knowledge of these drivers, one risks introducing process intensication ineffectively and inefciently. After that, a short overview is given of the technologies
available for process intensication, serving as a basis for the real process intensication study. The method of introducing process intensication is then
explained in Section 5, which is the main section: What steps should be incorporated in a process intensication study, what a good group of participants is, and
in what phase of a chemical process the study should be introduced. The chapter
concludes with two concrete examples of process intensication, one in a bulk
chemical process and one in a ne chemical process.
Process intensication can bring many benets regarding business, legislative,
and environmental aspects and is therefore very worthwhile to be implemented.
2. SHORT OVERVIEW OF DEVELOPMENTS

IN PROCESS INTENSIFICATION
As discussed in Chapter 1, process intensication as a way of looking at chemical processes originated in the early 1970s. It was adopted by the ICI New
Science Group in the United Kingdom, where mainly rotational elds were used
for accelerating chemical process steps.
After the rst conferences on process intensication, organized by the
British Hydromechanics Research (BHR) Group (1), the eld became a separately
identiable eld in chemical engineering and spread around the world. The general ideas behind process intensicationimproving a chemical process via stepby-step changescould already be found in various activities of development
groups in chemical engineering (in industry and at universities), though at that
time not all of these activities were called process intensication. By grouping the
activities in this eld under an umbrella name and by organizing meetings and
conferences dedicated to the topic, many new ideas, developments, and applications were discovered, and they are still being discovered. This is one of the reasons the eld of process intensication developed rapidly at the end of the 20th
century.
3. WHY WORK ON THE INTENSIFICATION
OF CHEMICAL PROCESSES?
As with all developing technologies, there is always more risk in introducing
them in commercial plants than in using the well-known, traditional technologies.
Some conservatism in commercial industry is always present. A very good illustration of that can be seen in Figure 1 of Chapter 1, where a 16th century chemical
process is compared with contemporary chemical processing. Why then would
one work on these kinds of developments?
By introducing step-by-step improvements in a process, process intensication offers a strong possibility to fulll the current business, legislative, and
environmental requirements. These aspects are becoming more and more important in contemporary chemical industry.
1. Business aspects are changing due to the expansion of the globalization
of the world economy: There are more potential competitors in this
enlarged market. The best low-cost position is necessary to obtain and
maintain market share. This is true for the ne chemical and pharmaceutical industries, because transportation costs are only a small
amount of total production costs and because the total global market
may in theory be supplied by producers from any place in the world.
On the other hand, for the bulk chemical industry as well, small cost
advantages per kilogram of product can make the difference between

prot and loss.
2. Legislative and environmental aspects are usually strongly linked.
They are getting a lot of attention in discussions on the license to operate (LTO) and sustainable technology (see Chapter 14).
These two aspects are also reected in the visions developed on this issue
in the United States in the so-called Vision 2020 program (see Appendix 1). One
can see that all aspects of introducing step-by-step changes are mentioned. And
in the European Union many current activities are based on the topic of process
intensication, reected, for example, in the European-Supported Research
Projects (see Appendix 2). On the industrial side, a lot of effort is being given to
the topic of process intensication: the European Chemical Industry Council
(CEFIC) has process intensication as one of its technology focus points in the
so-called SUSTECH program (see Appendix 3).
The intensication of chemical processes can help reduce the risks of
chemical processing and lower the energy demand and waste production. These
positive possibilities, which are evidently also linked to the business aspects, have
contributed to the growing use of process intensication. This is also expressed
in the paper of Elverding (2) at the Defacto conference on Prot, Planet, and
People in combination with process intensication, reecting the benets for
business and environment.
Many different aspects relating to business, legislation, and environment can
be dened. These are given in Table 1. In this important table one can nd many
of the benets of process intensication summed up. All of these aspects in the end
have to do with business, legislation, or the environment and show how process
intensication can have a strong positive inuence on these three main drivers and
answers the question of why one would one choose to intensify a process.
The overview in Table 1 holds, in principle, for any type of chemical industry. Additionally, different types of chemical industries may have different focuses,
depending on their starting position and on their business requirements. Knowledge of the perspectives helps in determining the main cost drivers from the list
given in Table 1 and helps therefore in nding the starting points for process
intensication studies. Table 2 presents an overview of some of the main types of
chemical industries and the specic demands they posed on process intensication when applied in these industries. A distinction can thus be made between:
Large-scale chemical industries, producingmostly in a continuous way
hundreds of kilotons of product
Fine chemical industries, which can be split into:
Multiclient chemicals, producing up to hundreds of tons of chemicals for
various customers, mostly in a batch way
TABLE 1
Positive Results of Process Intensication on Various Aspects
Aspect
Business
(costs)
Legislative
requirements
(environment
and safety)
Environment
Energy
Space
Number of
process
steps
Cost
Emissions
Waste
Less holdup
Examples
Less heat loss via integration of units (e.g., reactive

distillation)
Efcient heat transfer possible (high heat transfer
rates)
Reduction in oor space needed
Less piping
Reduced maintenance
Faster grade/product changes
Ease of dismantling and/or shipping
Fewer units
Less danger
Fewer possibilities for yield losses
Many aspects together may result in a lower cost
Theoretical goal: no limitation, other than kinetics,
gives optimal yield and least waste
Fewer possibilities for yield losses
Fewer process steps may result in lowered
emissions
Fewer possibilities for yield losses means less waste
Theoretical goal: no limitation, other than kinetics,
gives optimal yield and least waste
Intrinsically safe design: prevent large volumes, little
intermediate storage
Process
X
interruptions
and downtime
Fewer units, hence less possibility for

malfunctioning of parts
Flexible
feedstock
specications
Recyclable
Fewer stoppages due to lowered maintenance

Faster grade/product changes
Easier to adapt quickly to new process conditions
due to smaller equipment, fewer intermediate
material or grade changes
Easier to dismantle and/or ship
Easier to adapt quickly to new processes due to
smaller equipment
Many other aspects can be thought of
TABLE 2 Process Intensication for Different Types of Industries

Fine chemicals
Large-scale chemical
industries
Multiclient
chemicals
Custom
manufacturing
Pharmaceutical
industries
Characteristics
Up to hundreds of kilotons Up to hundreds of tons
Continuous
Mostly batch, some
parts continuous
Total prots are 530%
turnover
turnover
Material and energy costs Material and energy costs
are 7090%, labor costs
1030% of total costs
Up to tens of tons
Mostly batch, some
parts continuous
turnover
Material and energy costs
Up to tens of tons
Mostly batch
of turnover
Material and energy costs
are 1030%,labor costs
Why PI?
Material and energy cost
reduction
Higher efciency, higher
production capacity
Space and
waste reduction
Higher efciency, labor

cost reduction
Higher production capacity,
material cost reduction
Energy cost reduction,
optimal price
Higher efciency, labor

Labor cost reduction (also
cost reduction
in cleaning procedures)
Higher production capacity, Higher production
material cost reduction
capacity
Optimal price and time
Optimal price and time of
of delivery
delivery
How?
Focus on materials and
energy (large impact
on costs)
Focus on labor and

Focus on labor and
Focus on number of
efciency (efciency so
efciency (efciency so
steps (labor and
that all steps in the
that all steps in the
cleaning intensive)
process are well balanced)
process are well balanced)
Custom manufacturing, producing up to tens of tons of a chemical for

one specic customer, mostly in a batch way
Pharmaceutical industries, producing up to tons of a active pharmaceutical
ingredient (API), mostly in a batch way
Table 2 shows that different chemical industries have different cost focuses. It is important to know the main cost contributors of a certain process, because
this is a good way to nd step-by-step changes in the overall costs of a process.
For different types of chemical industries one can nd an idea of the corresponding main drivers in Table 2 (various examples of these main drivers can also be
found in the goals dened in Appendix 1).
Of course, apart from these general features every process is unique and
requires an individual investigation and denition of the cost drivers before one
can start a process intensication study. This will be discussed in more detail in
the next section.
Process Intensication is all about step-by-step changes. At what stage an
optimization in a process is called a step change depends not only on the type of
business but also on the maturity of a product in the lifecycle and the goals
dened by the three main aspects of process intensication (business, legislative
requirements, and environment). For example, the step change that one would
like to achieve in efciency, hence in optimizing a process without changing the
hardware drastically, depends on the lifecycle of a product. This is shown in
Figure 1. This last aspect should be taken into account when dening the reasons
for performing a process intensication study.
4. KEY FEATURES OF PROCESS INTENSIFICATION
TECHNOLOGIES
As stated earlier and in other chapters of this book (e.g., Chapter 1), process
intensication is making step-change improvements in processes. Many general
possibilities are available for reaching that goal. A large number of technologies
that have the characteristics of process intensication involve one or more of the
following three imperatives.
1. Make it small.
2. Combine.
3. Intensify the driving force.
Examples of these can be found in all chapters throughout the book. For example, belonging to imperative 1 are microreactors (Chapter 5), minireactors
(Chapter 6), and compact heat exchangers (Chapter 4). Imperative 2 represents
a large eld comprising the combining of reaction and extraction, reaction and
separation (Chapters 8, 9, and 10), reactive extrusion, reactive heat exchangers
FIGURE 1 Step changes in efciency as a function of the lifecycle of a product (ctitious curve to show the differences).
(Chapter 4), and many more. The last imperative covers technologies that use centrifugal elds for contacting (Chapters 2 and 3), separations, and crystallization or
that involve extremes of pressure and temperature, ultrasound waves, microwaves
(for e.g., drying) and electric elds (for e.g., separation or dispersion).
Basically, using these technologies one would like to move forward to the
theoretical optimum of a chemical process, which is that there are no other limitations than chemical kinetics. Normally a chemical process is inuenced by
more than just kinetics: hydrodynamics (mixing), heat transfer, and mass transfer
determine the quality of the process. Process intensication focuses on removing
these three limitations to reaching the goal of kinetically limited processes. This
is schematically depicted in Figure 2.
These three basic imperatives can be used to begin thinking about when to
try to intensify a process in a chemical plant. They are also part of another area
of chemical engineering: safety aspects of plant designs. In the 1980s, effort was
put into developing strategies for designing so-called intrinsically safe designs,
which means that the process designs are such that dangers are intrinsically
minimized so that the safety of a process does not depend on safety devices.
Examples of strategies for safe designs are: prevent large volumes, intensify contact, reduce the need for aids (like solvents), use little intermediate storage. One
can immediately see the similarities between intrinsically safe design and process
intensication. This also means that applying process intensication techniques
is benecial for process safety.
5. INTRODUCING PROCESS INTENSIFICATION
IN A CHEMICAL PROCESS
This section describes how one may intensify a process, or, said differently, how
process intensication can be introduced for a process.
When one would like to introduce process intensication for a process it is
important to consider the development phase a process is in. Roughly said, the
following phases can be discerned for a general process:
New ideas for a process Determining process chemistry Pilot plants
studies Plant design Plant startup Debottlenecking or
troubleshooting.
Every phase requires a somewhat different approach, because the boundary
conditions and possibilities for intensifying a process differ for each phase. What
follows is a short description of the phases and the approaches.
FIGURE 2 Process Intensication: Approaching the kinetic limit by using the

three imperatives: (1) Make it small; (2) combine; (3) intensify the driving force.
1. New ideas for a process: A product and a chemical route are dened.
This is the phase in which the core of the process is determined. This means that
it is already very important to think about the consequences that selecting a certain pathway has on the future nal plant and on the plant costs. Choosing a nonoptimal pathway may result in a much more expensive nal plant design than if
another pathway (or, e.g., another solvent or catalyst) were to be chosen. This is
the phase in which it is still relatively easy and cheap to make changes that produce the most intensied process. To be able to know the effect of a chemical
route on the nal plant requires a multidisciplinary team to be involved at this
phase, not just chemists, because more aspects play a role than chemistry. This
multidisciplinary team should consist of at least chemists and technologists.
2. Determining process chemistry: The specic chemical parameters of
the chosen process route are determined. In this phase, the route itself is more or
less frozen. The important parameters of the process are determined, such as the
required temperatures, pressures, and concentrations of substances in the process
steps. Making changes and optimizations in this phase is still relatively inexpensive. The effects of this phase on the efciency of the nal process can be large.
Applying intensication possibilities in this phase will reduce greatly the costs of
the nal process. In this phase the kinetic limit, as given in Figure 2, is determined, hence this is the last phase where the intrinsically optimal route may be
foundthe route with the least by-products and the least waste generation (from
auxiliaries such as solvents and from by-products). It is also the last phase in
which, apart from the optimal kinetics, the optimal process conditions can be
found that cause the fewest problems in technical implementation. Therefore, a
multidisciplinary team is required to determine the optimal process route, not just
chemists. Again, this multidisciplinary team should consist of at least chemists
and technologists.
3. Pilot plants studies: The process is scaled up to pilot-plant size to
observe scale-up effects and to determine parameters for the large-scale plant
(though one should take into account that this phase is skipped more and more in
process designs, to save time and money). In this phase, the basic technologies of
the process are checked, and the scalability of the process route developed in the
previous phases is checked. Changes in this phase are still relatively easy to make
but more costly than in the previous phases, because pilot-plant studies themselves cost money, and larger changes often mean a delay in the development
process because the previous phase will also have to be partly redone as well. In
this phase one can look for the limitations that technical equipment pose for the
process route. Heat and mass transfer limitations usually result in a poorer
process performance than the optimal lab conditions gave. In the pilot phase one
can try to optimize the equipment to overcome the limitations. For that purpose
one can make use of intensied process technologies, as described throughout this
book. These new technologies can best be tested during the pilot scale, to collect
experience with using these technologies and for the further scale-up to plant size.
Because process technology, chemistry, and future plant equipment play a role, a
multidisciplinary team is required consisting of at least chemists, technologists,
and process engineers.
4. Plant design: A commercial-scale process is developed and designed
in detail. Experience gathered in the previous phases is used for developing the
large-scale plant. In this phase, it is difcult to make large changes in the process,
because then the previous phases would have to be partly redone and the costs and
time spent in the previous phases are lost. It is important that intensied techniques are used as much as possible, since normally more limitations in the
process will arise at plant scale than in the lab or at pilot-plant scale. One wants
to approach the kinetic limit as much as possible.
5. Plant startup: The commercial plant is started. In this phase, no actions
for process intensication studies can be dened.
6. Debottlenecking or troubleshooting: While running the process, problems that may occur are solved (troubleshooting) or larger optimization projects
started (debottlenecking). In this phase, the plant is built and the process is running. One gains experience from the large-scale process. Small changes in the
process can be made, usually as troubleshooting projects or in creep projects.
These small changes, though important, are not the changes meant in process
intensication. When one would extend the plant capability with larger steps, this
is usually called debottlenecking, which mostly involves investment in the adaptations for the bottlenecks in the process. In this phase one also tries to nd possibilities to really make step changes in the cost efciency of the process, which
may be called process intensication. It again requires a multidisciplinary team,
because all aspects play a role, from chemistry to process engineering.
It can be seen that a multidisciplinary team is very important in almost
every phase when the goal is to develop an intensied process. Of course, many
of the phases just described in practice run partly in parallel, to speed up the
development process. This means that it becomes even more important to develop the most intensied process using multidisciplinary teams as early as possible.
In all phases of the process development just described one has opportunities to introduce intensication technologies to intensify the process. In phases 1
and 2, one should not forget that the choices made are crucial for the process
afterwards. Also, in these phases one should already be considering the consequences of the choices on the commercial plant and the possible scale-up difculties using specic chemical routes. The steps these teams can take to arrive at
new, intensied solutions are given schematically in Table 3.
Step 1. The rst step is to dene the goal of the study.
What is the time frame of possible implementation? When the study is a
strategic study, the time frame can be many years. The goal then is to
TABLE 3 Steps Needed to Develop New, Intensied Solution for Processes,

from Pilot Phase to Debottlenecking Phase
1. Goal denition
Determine the scope
The goal of the study

Unit and section of the plant or the
entire plant
All the people involved (also; the
internal customers)
2. Scouting of ideas
Identify the thermodynamics,
kinetics, and balances (mass,
energy) plus the cost factors
Identify the breakthroughs
For existing process: from known data

For new process from literature and
thermo databanks
Determine the theoretically optimal
process (no limitations)
In multidisciplinary teams
Make cost estimates of different options
3. Selection
Select the most feasible option
All the people involved (also, the

internal customers)
4. Detailed design
Identify the detailed
thermodynamics and kinetics
Final design of the unit or plant
Databanks and new measurements

Concluding the intensication project
have new concepts ready for the future. In that case one can also use
technologies that are still in development at the present date. When the
goal is to achieve direct implementation, the time frame is short and one
should use the available data and available technologies to optimize a
process. The budget necessary for the latter study is then also different
from that for the former type.
What part of a process should be looked at? This can be one unit, one chemical conversion step, a total process, or even a combination of processes that
are interlinked through streams of intermediate products or energy streams.
Step 2. The second step is the actual study: the scouting of the ideas. This
phase consists of two subparts. The rst part is data collection:
What are the kinetics and material properties in the process?
What are the mass and energy balances?
What are the current process steps and their limitations?

What is the theoretically optimal process (no limitations)?
What are the main cost factors?
Data should also be available to all team members of the new technologies on the
market and in development. This overview should be available before the start of
the actual idea generation:
The available technologies and technologies under development should be
known. This information should be available before starting process intensication studies. It is a one-time effort to collect these data and consequently a smaller continuous action to keep the data up to date. Overviews
can of course have various formats and sources. An example of one technology from an extensive list used within DSM is given in Figure 3. Of
course, this book is also a good reference for available technologies.
The second part of Step 2 is the identication phase. In this phase ideas are
collected to intensify the process within the boundaries as dened in Step 1. This
phase requires a well-balanced team of participants from various disciplines, e.g.,
engineers, R&D, process technologists, chemical experts. Apart from representative of various disciplines, one should ideally also have participants that know the
process well and people completely unfamiliar with the process, to get a wide
variety of ideas and suggestions. Lastly, it is benecial to mix older, experienced
members with younger members who may be less biased to company-standard
process solutions.
As a start, the existing process should be described using all the known data
gathered in the rst part. It is very important that the process also be
explained in functional units, instead of equipment. This means that the
function of a step is described instead of just the details on how a piece of
existing equipment works in the actual situation. This helps in nding the
differences between the goal of a step and the way the equipment actually
works and in nding other Intensication methods to make it work better.
Next, free discussion and brainstorming begin. One can use many different
starting points for discussions and ideas. An overview of available technologies also is important (e.g., Figure 3). Also helpful would be the list
given in Table 4.
Combine and select ideas. After brainstorming one should of course focus
on the main ideas. Often various ideas can be combined to create clusters of ideas around main themes.
Design a draft of the new process (alternatives). After having found the
main ideas, a owsheet of possible intensied processes should be
drawn. Such owcharts help in further evaluations and in gaining clear
pictures of the ideas.
FIGURE 3 Example of one technology out of an extensive of technologies

used within DSM.
Based on the selected owcharts (process ow diagrams) one can make a

rst rough estimate of the costs of the new processes. Various standard
methods for this are available, depending also on the companys systems
for cost estimation. This part of Step 2 should not be forgotten, because
it can clearly show the benets of a new process in terms of costs, which
is one of the main drivers for changes in processes. It also helps in ranking ideas.
Step 3. This step involves the selection of the most feasible route, which
should be done in a large group, including the internal customers.
Step 4. The last step is the engineering or further development of the
intensied process route. This step follows the standard engineering and development processes used for developing conventional processes, although some
new technologies may be involved. Pilot plant testing of these new technologies
is very likely to be necessary.
This method has been applied within DSM for 13 of its existing processes
from its three main business clusters (polymers and industrial chemicals, life science products, and performance materials). See Figure 4 for the scheme used
within DSM that follows this route. The results showed possibilities for reducing
the cost of the present processes to 6090% of the current costs. (This was shown
earlier, in Figure 5 of Chapter 1.) This shows that the way of performing process
intensication studies described in this chapter can result in very economical
results for various types of businesses (from life sciences to bulk chemicals). Two
concrete examples are presented in the next section to give a feeling of process
intensication.
TABLE 4 Starting Questions That Might Be Used in the Brainstorming
Phase of an Intensication Study
Keywords
Intensify
Segment
Use a different aid
Change conditions
Change in an early stage
Combine
Fix
Add or remove
Periodic action
Phase transition
Example
Make the process smaller
Divide into independent parts
A different solvent, temporary shielding agent
Change pressure or temperature
Prevent the root-cause upstream from where
the problem occurs
Combine unit operations
Fix one phase to prevent separation problems
Quickly remove or add a product or reactants
Change a continuous system into periodic
actions
Use phase transition in the process
FIGURE 4 Scheme to arrive at intensied processes as used within DSM.
6.
6.1.
EXAMPLES OF INTRODUCTIONS
S-Ibuprofen
The rst example of process intensication at DSM is the pilot-scale test of the
enzymatic production of S-ibuprofen, a nonsteroidal, anti-inammatory drug. The
molecular scheme is given in Figure 5. More details can be found in Refs. 3 and 4.
The conventional production consisted of many process steps, typical for a
ne chemical process. These process steps are given in Figure 6. The selectivity
of the enzyme is rather high. The downstream processing is rather laborious,
FIGURE 5 Production of S-ibuprofen with a racemization step and an enzymatic conversion using the carboxyl esterase enzyme.
because it requires that the product be completely enzyme free. Furthermore, the
product, S-ibuprofen, causes enzyme deactivation. Altogether, many unit operations are required to obtain the product; due to the deactivation of the enzyme, a
maximum conversion of 21% can be reached.
Removing the product as fast as possible from the reaction mixture could
possibly prevent the enzyme from deactivating. This was experimentally tried on
pilot scale using an ultraltration unit, parallel to the reactor. In this ltration unit
the product is separated and the unreacted components and the enzyme are
returned to the reactor. An even better option, using a true membrane reactor in
which the catalyst (enzyme) would remain on one side and the product would
remain on the other side, was not tested. Both options are given schematically in
Figure 7.
FIGURE 6 Processing steps for the production of S-ibuprofen.
FIGURE 7 S-Ibuprofen production options: ultraltration (left) and a membrane reactor (right).
FIGURE 8 Processing steps in the production of S-ibuprofen with the ultraltration unit.
FIGURE 9 Conversion of the S-ibuprofen process with and without the ultraltration unit.
Performing the S-ibuprofen production process with an ultraltration unit,

6 of the 11 unit production steps shown in Figure 6 could be skipped! The entire
process scheme was reduced to the one given in Figure 8.
Based on kinetic modeling of the reaction, including the enzyme deactivation, it was found that there would be an additional improvement, apart from skipping six unit operations. By removing the product quickly out of the reacting
medium, the enzyme deactivation proceeds more slowly and the conversion
increases. This has been experimentally validated in the pilot-scale system. The
results are given in Figure 9. It can be seen that the conversion is increased from
21% to 50%! This example shows that process intensication can bring a substantial cost benet to the process.
6.2.
Urea
The second example of process intensication at DSM is the urea process (5). The
history of the urea process at DSM is rather long, as shown in Table 5. Urea is produced in a two-step process. The rst step is the formation of carbamate from NH3
and CO2. This reaction is exothermic. The second step is the decomposition of carbamate into urea and water. This second reaction is slightly endothermic. Both
reactions are equilibrium reactions. The conversion to urea in equilibrium is about
60%. This means that substantial recycle ow is necessary to obtain sufcient
overall conversion. In the reaction section the main unit operations are:
The stripper, in which remaining CO2 and NH3 are being stripped with CO2
from the product ow
The scrubber, where the reactants in the reactor offgas are stripped
TABLE 5 Development of the Urea Process at DSM

1945
1956
1966
1974
1994
1995
1996
1997
1998
Start of R&D program by DSM

First commercial plant (75 mt/d)
CO2 stripping process
World-scale capacity 1750 mt/d
Implementation of rst pool condenser
200th unit contracted
Urea 2000plusTM technology
Installation of rst pool reactor, largest
single-line urea plant in operation
Startup of rst Urea 2000plusTM pool
reactor plant
The condensor, in which NH3 and CO2 are condensed into carbamate
The reactor, in which the carbamate decomposes into urea and water
In the old process, the Stamicarbon stripping process, these four units were
positioned above each other. The overall height of the plant was 76 m! After various small and larger improvements, a new concept was developed in which the
reactor and the stripper are combined in one unit, the horizontal pool reactor. A
schematic diagram and a photo of the reactor are given in Figure 10.
The layout of the new plant concept with the integrated and intensied pool
reactor now has a height of 18 m, a height reduction by a factor of 3. Also, the
number of units has been decreased. This is illustrated in Figure 11, in which the
development of the urea process is depicted. In this gure it can be seen that even
an old proven bulk chemical process can be intensied, resulting in a much
more compact and economical plant.
FIGURE 10 Urea pool reactor used in the Urea 2000plusTM process.
FIGURE 11 Development of the urea process.
7.
CONCLUSIONS
As shown in this chapter, the methodology for applying process intensication in

commercial industries requires a broad interest and cooperation within companies,
including a vision of the company management and individuals. Some boundary
conditions need to be met, such as a vision in place that offers the initial time and
money to set up the necessary infrastructure for applying these new technologies:
a basic knowledge of the possibilities and available technologies and of the
methodology. Process intensication can then bring substantial benet in terms of
business, legislation, and environment, as is demonstrated in this chapter as well
as in the entire book, therefore making PI very worthwhile to be implemented.
8.
8.1.
APPENDICES
Appendix 1: Excerpt from U.S. Vision 2020
This excerpt is taken from Ref. 6.

U.S. chemical companies must innovate and change to keep competitive
in the global environment. Chemical Industry Vision 2020 Technology
Partnership (Vision 2020) is an initiative to leverage research and development (R&D) resources through the collaborative efforts of industry,
government, and academe and focus them on priority targets identied
by the chemical industry.
New Process Chemistry Roadmap
Section: Ofce of Industrial Technologies (OIT)
This roadmap focuses on innovative new process chemistry to support
the Process Science and Engineering Technology and Chemical
Synthesis technical areas within the New Chemical Science and
Engineering Technology section of Vision 2020: The U.S. Chemical
Industry. However, the roadmap is integrally connected to other sections
of the Vision and other supporting roadmaps. Process chemistry begins
in the laboratory, but is further developed through reactor design and
process engineering. Feedstock characteristics, catalytic mechanisms,
and downstream processing (e.g., separations) all come into play in
developing new process chemistries.
Goals
Reduce feedstock losses to waste or low-value by-products by 90%.
Reduce industry-wide energy intensity (energy per unit product) by 30%.
Reduce total emissions and efuents from chemical manufacturing by
30%.
Increase usage of C1 and renewable resources to 33% of industry-wide
carbon usage.
Reduce cost of production by 25%.
Accelerate introduction of new products by 15%.
Reduce lead times and time to market for new products and technologies by 30%.
8.2.
Appendix 2: European Union Research Program

The 5th framework of the EU research program runs from 1998 to 2000.
One of the four subprograms is called the GROWTH program. In this
GROWTH program, key action 1 is called innovative products, processes,
and organization. The description is given here:
KEY ACTION 1: INNOVATIVE PRODUCTS, PROCESSES,
AND ORGANIZATION (Budget 731 MEuro)
a.
Contributing to modernization of industry and adaptation to

change, through the combined effects of improved industrial
capability and innovation capacity, while introducing more exibility and capability to respond in real time to customer needs.
Research should stimulate cross-sectoral exchanges and participation of SMEs, taking into account their specic needs and
roles in the supply chain as well as approaches able to create and
hold in Europe sufcient jobs to arrest the decline of industrial
employment while improving the overall quality of work.
b. Substantially* improving overall quality within the value
chain (quality is intimately linked to value for and timely satisfaction of customer needs at the lowest costs) and consequently reducing inefciencies and overall lifecycle product
costs by the same order of magnitude.
c. Minimizing resource consumption (e.g., materials, energy,
water) to reduce substantially the overall lifecycle impact of
product-service provision and use. These goals should be
dealt with in a synergistic way. They should not be regarded
as absolute targets for individual projects but rather as broad
indications of the direction toward which the European industrial system, supported by improved regulations, should
evolve.
8.3. Appendix 3. Excerpt from the CEFIC Technology Program
SUSTECH
The SUSTECH program was launched by a consortium of the major
chemical companies in Europe in April 1994. In doing so, they created
a framework which would enable them to collaborate effectively in areas
of research and development, which would be critical for the long term
future of the process industries in Europe. The focus for collaboration
would be those areas that while attracting public concern were nevertheless not areas in which the companies would normally compete. Such
areas as sustainable development, protection of the environment, and
technologies for making more efcient use of the earths resources were
ready targets for collaborative action.
Process Intensication.
The objective of the Process Intensication (PI) Cluster is to promote PI
and its benets to a wide industrial audience by:
Exposing technologies critically to industrial needs
Identifying priority industrial applications
* The term substantially means over 2030% in the shorter term or over 10% per year in the longer
term.
Facilitating partnerships between technology providers, equipment suppliers, and end users.
Two sessions were held at SUSTECH 7. In the morning session, process
intensication and the future direction of the cluster were discussed in
general. In the afternoon, a mini-workshop was held on gasliquid reactors. Total attendance was in excess of 60, including 23 representatives
from the chemical industry.
An industrial Steering Group has been established to determine
the priority areas for the cluster and the mechanisms required to achieve
its objectives. It was proposed to carry out analyses on representative
processes to identify the potential business benets arising from application of PI technologies.
REFERENCES
1. BHR Group. Process Intensication Conferences. http://www.bhrgroup.co.uk/confsite/
pi01home.html.
2. Elverding P. DSMs Triple Bottom Line. DEFACTO 2001; 15(5):2832.
3. Bakker RA, Stankiewicz AI, Schyns VJAJ. Process intensication within DSM, general methodology and concrete examples. In: Proceedings of the 4th International
Conference on Process Intensication for the Chemical Industry. Craneld, UK,
BHR Group, 2001.
4. Cauwenberg V, Vergossen P, Stankiewicz A, Kierkels H. Integration of reaction and
separation in manufacturing of pharmaceuticals: membrane-mediated production of
S-ibuprofen. Chem Eng Sci 1999; 54:14731477.
5. Technical information brochures on the Urea 2000plus process can be obtained
from Stamicarbon B.V., the licensing company of DSM.
6. U.S. Vision 2020, section of the Ofce of Industrial Technologies (OIT). http://www.
oit.doe.gov/chemicals/visions_new_chemistry.shtml.
7. European Union 5th Framework Research Program 19982002. Thematic program
GROWTH: http://europa.eu.int/comm/research/growth/index.html and http://
europa.eu.int/comm/research/growth/pdf/growth-workprog2000_en.pdf.
8. SUSTECH Technology program, part of the CEFIC organization. http://www.cec.be.
13
Process Intensication for Safety
Dennis C. Hendershot
Rohm and Haas Company, Bristol,
Pennsylvania, USA
1.
INTRODUCTION
Process intensication is an important strategy in the development of inherently

safer chemical processes and plants. By reducing the inventory of hazardous material or energy in the process, the potential consequence of failure to control that
hazardous material or energy is reduced. Rather than relying on add-on safety
features such as interlocks, procedures, and consequence mitigation systems, the
safety of the plant is based on reducing the magnitude of the possible damage.
While safety devices can be designed to be highly reliable, no safety device is perfect, and all will have a nite failure probability. If a chemical plant contains a
large amount of hazardous material or energy, the consequences of the failure of
the add-on safety devices may be large. A smaller plant is safer because we have
reduced its inherent capability to cause damage, rather than because we have controlled that capability through additional safety devices.
2.
INHERENT SAFETY
Inherent is dened as existing in something as a permanent and inseparable element, quality, or attribute (1). A chemical process can be described as inherently
safer if it reduces or eliminates a hazard when compared to another process alternative. To understand this denition, it is necessary to understand what is meant
by the term hazard. A hazard is a characteristic of a material or process that results

in potential harm to people, the environment, or property. A hazard is an inherent
property of a material or its conditions of use. Some examples of hazards include:
Sulfuric acid is corrosive.
Chlorine is toxic by inhalation.
Heptane is ammable.
Nitroglycerine is unstable and can detonate.
Heat transfer oil at 300C contains a large amount of energy.
A vessel full of compressed air at 40 bar contains a large amount of potential energy.
The hazard cannot be changed, but it is possible to change the material or operating conditions. The magnitude of a potential incident that could result from the
failure to control the hazard can also be reduced. An important way of accomplishing this objective is to reduce the quantity of material in the process through
process intensication.
It is generally more appropriate to describe processes as inherently safer
when compared to alternatives rather than as inherently safe. All processes have
multiple hazards, and it is not possible to eliminate all hazards. For example, it
may be possible to replace a toxic or ammable solvent for an extraction process
with supercritical carbon dioxide. While the carbon dioxide process is inherently
safer with respect to ammability and toxicity hazards, it operates at high pressure,
which introduces new hazards. Depending on the specic details of the alternative
processeswhat the ammability properties of the solvent are, how toxic the solvent is, what the size of the equipment is, what the operating pressure isthe
supercritical carbon dioxide process may be inherently safer overall. However, it
is important to consider all hazards in judging the overall inherent safety of process
alternatives and to avoid focusing on a single hazard and forgetting about others.
3.
HISTORY OF INHERENTLY SAFER DESIGN
It can be argued that engineers have always attempted to eliminate hazards in

their designs. For example, in 1828 the pioneering railway engineer Robert
Stevenson argued for simplication and minimizationtwo of the principles of
inherently safer designof the newly developed steam locomotive when he discussed an alteration which I think will considerably reduce the quantity of
machinery as well as the liability to mismanagement. . . . [I]n their present complicated state they cannot be managed by fools; therefore they must undergo
some alteration or amendment (2).
The concept of inherent safety as a specic set of design strategies to eliminate or reduce hazards in the chemical industry was rst articulated by Trevor
Kletz in the 1970s. Following the Flixborough explosion in England in 1974,
there was increased concern about safety in chemical plants, from the industry
itself, government, and the general public. This resulted in an increased focus on
controlling hazards in chemical plants. A specic worry was that the magnitude
of potential accidents was now larger because of the large size of a new generation of world-scale petrochemical facilities. In 1977, while working as a safety
advisor for the ICI Petrochemicals Division, Kletz suggested an alternative
approach in the annual Jubilee Lecture to the U.K. Society of the Chemical
Industry (3). He proposed that the industry should direct its attention to eliminating or reducing the hazards of its plants and processes rather than accepting those
hazards and working to control them. Kletz called this approach inherently safer
design. Furthermore, this hazard elimination or reduction would be accomplished
by means that were inherent in the process and, thus, permanent and inseparable
from it. Since 1977, concepts and approaches to inherently safer design in the
chemical industry have been developed and promoted (46), including a brief discussion in Perrys Chemical Engineers Handbook (7).
4. CONCEPT OF LAYER OF PROTECTION
FOR PROCESS SAFETY
The safety of a chemical process relies on multiple layers of protection to protect
people, the environment, and property from the hazards associated with the
process. A process designer recognizes that equipment can fail and that people
will make mistakes. While we can design more reliable equipment and train and
motivate people to reduce mistakes, we can never completely eliminate these failures and mistakes. Therefore, it is important to provide multiple layers of protection, a defense in depth, to reduce risk (Figure 1). Even so, there will always be
some small probability that all of the layers of protection will fail simultaneously
and an accident will occur. Also, the effectiveness of the layers of protection
depends on the ongoing maintenance of equipment, the training and performance
of people, and the management systems. If these systems deteriorate, the reliability
of the protection layers will be reduced and the risk will increase (Figure 2). The
Center for Chemical Process Safety has published a book that describes the layerof-protection concept in detail and extends it to a quantitative risk-management
technique, layer of protection analysis (LOPA) (8).
If the magnitude of the potential accident is very large, some people may
never feel completely comfortable with the residual risk that it may occur, even if
this risk is very small and management systems to maintain the protection systems continue to be good and effective. By reducing the magnitude of the potential
accident, inherently safer design acknowledges the inevitability of the failure of
equipment, people, and management systems, and it bases process safety on reducing the inherent hazard of the process. An inherently safer design reduces the
need for layers of protection for a process, and, if the magnitude of the potential
FIGURE 1 Layers of protection for a chemical process.
consequence of an accident can be reduced sufciently, it may eliminate the need

for protection layers entirely (Figure 3).
In general, the layers of protection applied to a chemical process can be
placed into four categories:
InherentEliminate or reduce the hazard by using materials and conditions
that are less hazardous or nonhazardous.
PassiveMinimize or control the hazard using design features that reduce
either the frequency or the consequence of incidents without the active
functioning of any device.
ActiveControl or mitigate incidents using controls, safety interlocks, or

emergency shutdown systems to detect hazardous conditions and take
appropriate action to place the plant in a safe condition.
ProceduralUse operating procedures, administrative checks, emergency
response, and other management systems to prevent incidents, to detect
incidents in time for operators to place the plant in a safe condition, or to
reduce the magnitude of the damage resulting from an incident.
These categories are not rigidly dened, and a design may exhibit characteristics of more than one category. Safety strategies in the inherent and passive
FIGURE 2 Higher risk resulting from degraded layers of protection.
FIGURE 3 An inherently safer process meets risk requirements with fewer or

no layers of protection.
categories are generally considered to be more robust and reliable. They depend
on the physical and chemical properties of the system rather than on the successful operation of instruments, safety devices, and procedures. Inherent and passive
strategies are often confused, but they are different. A truly inherent solution to a
safety issue will either completely eliminate the hazard or reduce the potential
magnitude of an incident associated with the hazard sufciently that it cannot
cause signicant damage. On the other hand, passive strategies do not eliminate
the hazard, but instead prevent injury and damage by eliminating or reducing the
exposure of people or property to the hazardous condition without the active
functioning of any device. A containment dike around a storage tank is an example of a passive layer of protection. It performs its function of limiting the damage in case of a leak from the storage tank simply by being present. There is no
need to detect a leak or for any device or person to perform any function for the
containment dike to do its job.
5.
INHERENT SAFETY STRATEGIES
Approaches to inherently safer process design have been categorized in a number

of ways. The Center for Chemical Process Safety (5) describes four strategies for
inherent safety, derived from Kletzs initial proposals (3,6):
11. MinimizeUse smaller quantities of hazardous substances, including
process intensication approaches. Example: Use a small, continuous
reaction system for the production of nitroglycerine in place of a large
batch reactor.
12. SubstituteReplace a material with a less hazardous substance.
Example: Aqueous latex paints reduce both ammability and toxicity
hazards when compared to solvent-based paints, both during manufacture and for the nal consumer.
13. ModerateUse less hazardous conditions or a less hazardous form of
a substance. Example: Plastic resins can be produced in pellet or
granular form, reducing dust explosion hazards when compared to a
powder form of the same material.
14. SimplifyDesign processes and facilities that eliminate unnecessary
complexity and that are tolerant of human error. Example: Design
piping to permit gravity ow of hazardous materials in a plant, eliminating the need for pumps, which can leak.
Additional discussion and more examples of these strategies can be found
in books by Kletz (6) and CCPS (4,5). The remainder of this discussion will focus
on minimization (process intensication) as an inherent safety strategy.
6. PROCESS INTENSIFICATION AS AN INHERENT
SAFETY STRATEGY
6.1.
Smaller Is Safer
Reducing the size of chemical processing equipment enhances safety in two ways.
The quantity of hazardous material that can be released in case of equipment
leakage or rupture is obviously smaller if the equipment is smaller. In addition,
the potential energy contained in the plant equipment is also smaller if the
equipment is smaller. This potential energy can be in many forms, such as high
temperature, high pressure, or heat of reaction from a reactive chemical mixture
in the equipment. If this potential energy is released in an uncontrolled manner,
an incident such as a re, explosion, or uncontrolled leak of material from the
equipment may occur.
Clearly the potential damage from the uncontrolled release of material or
energy is reduced if equipment can be made smaller. There is also another benefit to smaller equipmentit may be more feasible to provide equipment to mitigate
or control the consequences of an incident. For example, it may be feasible to
totally enclose a small reactor in a blast-proof structure. Doing this for a large reactor may not be feasible because the blast-proof enclosure would have to be much
larger. The enclosure would also have to be much stronger because it would have
to withstand a larger potential explosion from the larger reactor.
6.2.
Traditional Approaches to Minimizing Inventory
There are many opportunities to minimize inventory of hazardous material in a

chemical plant without fundamental changes in process technology. The accident
in Bhopal, India, in 1984 released methyl isocyanate, causing approximately 2000
fatalities and injuring tens of thousands of people (9). This is by far the worst accident in the history of the chemical industry. Following the Bhopal accident, most
chemical companies reviewed their operations to identify opportunities to reduce
the inventory of toxic and ammable materials. Many signicant reductions were
reported as a result of this effort, and these reductions were accomplished relatively quickly. Obviously, these companies did not rebuild plants using different
technology or make dramatic changes to the process equipment in the existing
plants in such a short time. So how did chemical plants around the world reduce
hazardous material inventories? They carefully evaluated existing equipment and
operations and identied changes in operations that would allow the existing
plants to operate with a reduced inventory of hazardous materials. The Bhopal
tragedy focused the attention of creative engineers on the problem of reducing
hazardous material inventory, and they quickly identied ways of accomplishing
this objective, even for existing plants and technologies.
6.2.1.
Storage
The single biggest reduction in hazardous material inventory of plants was in

storage facilities. This includes raw materials, in-process intermediates, and nal
products. The terrible consequences of Bhopal caused engineers and managers to
question the need for storage of large quantities of raw materials and intermediates. In many cases, a large inventory of raw materials makes it easier to operate
a plant. The company may have more exibility in ordering raw materials, to take
advantage of favorable market conditions to order large amounts of material when
prices are low. The plant is less likely to have to shut down because of transportation delays. However, if the raw material is very hazardous, and particularly
if it is very toxic and a large leak has the potential to impact population in a large
area surrounding the plant, the risks associated with storage of a large amount of
the material may be significant. A better strategy would be to devote the companys resources to ensuring a reliable and economic supply of material, effective
transportation systems, and good inventory control systems. Strategic alliances with
raw material suppliers and transportation companies, modern inventory management systems, and improved communication with supplier plants will allow a
plant to reduce the quantity of hazardous material that must be stored at the manufacturing site. There is also an economic benetworking capital is reduced
because the inventory of raw material is reduced.
Often, a plant design includes large storage tanks for hazardous in-process
intermediates. This intermediate storage decouples sections of a plant from one
another. Parts of a plant can continue to operate, either lling or emptying inprocess storage tanks, while another unit in the plant is shut down for maintenance
or because of operating problems. In fact, reliability engineers interested in increasing the on-stream efciency of a plant will encourage a plant designer to include
intermediate storage buffers in a design to improve the overall plant reliability. This
can be desirable in improving the inherent safety of a planta continuous plant is
generally safer in normal, steady-state operation than while starting up or shutting
down (10). The buffers will reduce the frequency of starting up and shutting down
sections of the plant because of unavailability of feedstock from an upstream unit
or a shutdown of a downstream unit resulting in no place to put the product.
However, if the intermediate to be stored in the buffer tank is extremely
hazardous (ammable, toxic, reactive), this benet must be balanced against the
risks inherent in the storage of a large quantity of hazardous material. There may
be other approaches to enhancing the reliability of the units within a large plant
that will eliminate or greatly reduce the need to store large quantities of hazardous
intermediates. Perhaps the intermediate buffer can be provided at another point in
the process, allowing storage of a less hazardous material or a less hazardous form
of the same material. For example, a reactive material is produced in a continuous
gas-phase reaction, then absorbed in water to form an aqueous solution, isolated
as a pure material by distillation, and stored for feeding to downstream processing
units. A buffer between this unit and the downstream units could be provided with
intermediate storage of the distilled, puried material. However, it would be inherently safer to provide this storage buffer for the aqueous solution of the material,
which is less hazardous.
There are other ways to reduce the need for in-process storage of hazardous
intermediates. Fully understanding the causes of unreliability in production units is
the key to reducing the need for in-process buffer tanks. Causes of shutdown can be
eliminated by using more robust and reliable equipment, improving the process to
make it less sensitive to variations in operating parameters, or providing redundancy for critical equipment so that the entire plant does not have to be shut down
when the critical equipment requires repair. If the reliability of individual units in
a plant can be increased, it will not be necessary to store large amounts of hazardous
in-process intermediates to maintain the desired production capacity. The design
engineer should question the need for all in-process storage. He should ask if the plant
can operate just as efciently without the intermediate storage tanks if the causes of
plant shutdowns could be understood and eliminated. In many cases, the answer
is yes, and in-process storage has been greatly reduced or eliminated. One company reported a reduction in total inventory of hazardous materials, including chlorine and hydrogen cyanide, of over 1 million pounds at a single plant site (11).
One measure of the inherent safety of a process with respect to re and
explosion risk is the Dow Fire and Explosion Index (12). Table 1 shows examples
of the impact of inventory reduction on the Fire and Explosion Index.
The benets of reduced inventory can also be quantied by estimating the
potential consequence from a potential incident. For example, one of the hazards of
storage of a liquied ammable gas such as propylene is a boiling-liquid expanding
vapor explosion (BLEVE) and the associated reball. Figure 4 shows the heat radiation intensity as a function of distance from a storage tank for a potential BLEVE
for three sizes of propylene storage vessel, ranging from 500 to 50,000 kg. The magnitude of the consequence reduction from reducing propylene inventory is clear.
6.2.2.
Piping
When designing piping for hazardous materials, the designer should attempt to
minimize inventory, by minimizing both pipe diameter and pipe length. Hazardous
material piping should be large enough to transport the quantity of material required
and no larger. Reducing pipe size from 50-mm diameter to 25-mm diameter
reduces the inventory of hazardous material in the pipe by a factor of 4. This has a
TABLE 1 Impact of Inventory on the Fire and Explosion Index
Fire and
explosion index
Ethyl acrylate storage inventory
907,000 kg (2 million pounds)
91,000 kg (200,000 pounds)
23,000 kg (50,000 pounds)
Agricultural product with
in-process intermediate storage
23 cubic m (6000 gallons)
0
Source: Ref. 13.
151
130
120
185
140
FIGURE 4 Radiation intensity from a BLEVE and resulting reball as a function of distance for propylene storage tanks in three different sizes.
major impact on the distance over which hazardous concentrations of material can
occur in the atmosphere if the pipe is broken. Figure 5 shows the footprint of a toxic
phosgene cloud for a specic set of conditions, where the only difference is the size
of the phosgene pipe. The smaller pipe results in a much smaller toxic vapor cloud.
Inventory of hazardous material in pipes can also be minimized by using
the hazardous material as a gas rather than as a liquid. The Dow Chemical Exposure
Index (14) is a tool that can be used to measure inherent safety with regard to potential toxic exposure risk. Table 2 shows the reduction in the Chemical Exposure
Index that can be realized by handling a number of hazardous materials as a gas
rather than as a liquid, assuming that the same-size pipe can deliver the required
ow rate. Figure 6 shows the decrease in the hazard zone (toxic cloud footprint)
that resulted from relocating a chlorine vaporizer from a production building to
482
Hendershot
FIGURE 5 Cloud footprint to atmospheric concentration of 1 ppm resulting

from the rupture of three sizes of phosgene pipe. Release conditions: Complete rupture of pipe while connected to a large storage tank without shutoff,
pipe elevation is 5 m above grade, wind speed is 5 m/sec, atmospheric stability class D, 1 ppm is the Emergency Response Planning Guideline-3 (ERPG-3)
concentration for phosgene, the concentration at which life-threatening
effects might result from exposure for 1 hour.
a storage area. Following the modication, the long chlorine transfer line contained
gaseous chlorine instead of liquid chlorine.
6.3.
Process intensication refers to a chemical process using signicantly smaller

equipment. Examples include novel reactors, intense mixing devices, heat and
mass transfer devices that provide high surface area per unit of volume, devices
that combine one or more unit operations in a single piece of equipment, and
devices that use alternate ways of delivering energy to processing equipment
for example, ultrasound, microwaves, laser beams or light, and radiation. Other
chapters in this book discuss these and other process intensication techniques in
more depth. These technologies can greatly increase the rate of physical and
chemical processes, allowing a very high productivity from a small volume of inprocess inventory. Clearly, this is desirable from an economic perspective
a small, highly efcient plant can be expected to be cheaper and more cost effective.
If the material contained in the plant is hazardous, because of either its physical
and toxicological properties or its conditions of use, such as high temperature or
pressure, then the risk associated with a small amount of the material will be less
than for a large quantity.
If the plant is small enough, the maximum possible accident may not pose a
signicant hazard to people, the environment, or property. This may result in an
additional reduction in the equipment needed for the plantit may not require as
much (or any) safety equipment, emergency alarms and interlocks, or other layers
of protection to manage risk. Even if the small plant still requires safety equipment,
this equipment will be smaller and cheaper. Installation and ongoing operation of
safety equipment is often a major expense; if it can be eliminated or reduced in size
and complexity, there will be cost savings. Safety need not cost moneysafer can
also be cheaper if a small, efcient, inherently safer process can be invented.
Some specic examples of process intensication resulting in safer as well
as more economical processes follow. Many more examples, described in more
detail, can be found throughout this book.
TABLE 2 Chemical Exposure Index for Failure of a 2-Inch Pipe

Material
State
Chemical
exposure index
Phosgene
Liquid
Gas
Liquid
Gas
Liquid
Gas
Liquid
Gas
1000
850
1000
490
980
310
360
110
Chlorine
Hydrogen sulde
Sulfur trioxide
Source: Ref. 14.
FIGURE 6 Cloud footprint to an atmospheric concentration of 20 ppm resulting from the rupture of a 50-mm-diameter chlorine pipe containing either
chlorine liquid or chlorine vapor. Release conditions: Complete rupture of pipe
without shutoff, pipe elevation is 5 m above grade, wind speed is 5 m/sec,
atmospheric stability class D, 20 ppm is the Emergency Response Planning
Guideline-3 (ERPG-3) concentration for chlorine, the concentration at which
life-threatening effects might result from exposure for 1 hour.
6.3.1.
Nitration
Nitration reactions are highly exothermic, can generate high pressure in a closed
system from noncondensible by-products from undesired side reactions, and
often produce unstable reaction products, such as explosives. Many years ago,
products such as nitroglycerine were manufactured in large batch reactors. As
engineers began to understand the physical and chemical processes involved in
nitration chemistry, they recognized that the chemical reaction actually occurs
very rapidly once the reactants come into contact with each other. The large reactor
size and long reaction times were actually the result of poor mixing, poor removal
of the heat of reaction, and poor mass transfer in two-phase reaction mixtures. This
knowledge of the physical and chemical processes involved in an industrial-scale
nitration process was used to design new types of reactors to efciently contact
the reactants and liquid phases and remove the heat of reaction. Modern nitration
plants use very small continuous stirred-tank reactors with intense mixing and
large heat transfer area or jet reactors of various designs to provide intense mixing and rapid contacting of reactants (6).
6.3.2.
Polymerization
A number of innovative polymerization reactors using loop reactors, plug-ow

and static mixer reactors, and continuous stirred-tank reactors have been reported.
For example, Wilkinson and Geddes (15) describe a 50-liter reactor that has the
same capacity as a 5000-gallon batch reactor. Extruders, thin-lm evaporators,
and other devices designed to provide intense mixing for viscous or unstable
materials have also been used as reactors.
6.3.3.
Tubular or Jet Reactors
Continuous reactors, including simple plug-ow pipe reactors, tubular reactors containing static or other mixing devices, and jet reactors of various types, have been
used to efciently produce toxic materials for immediate consumption in downstream processing operations with little or no inventory. Some examples follow.
Methyl isocyanate (MIC), the material that was released at Bhopal, can be
produced and immediately converted to nal product in a process that
contains a total inventory of less than 10 kg of MIC (6).
Caros acid, an equilibrium mixture of sulfuric acid, water, and peroxymonosulfuric acid, is used in the metal-extraction industry. It is manufactured
by reacting concentrated sulfuric acid with hydrogen peroxide. Caros
acid is a powerful oxidizing agent and decomposes readily. A process
was developed to manufacture 1000 kg/day of Caros acid in a tubular
reactor with a volume of 20 ml and a residence time of less than one
second, with the product immediately mixed with the solution to be
treated (16).
A continuous tubular reactor was developed to manufacture phosgene for
immediate consumption by a group of batch-processing buildings (17). One
plant using the new design contains 70 kg of phosgene gas, compared to
a total inventory of 25,000 kg of liquid phosgene in the old plant.
Because the new plant is small, it is also feasible to provide a secondary
containment building for the equipment containing phosgene, providing
an additional barrier between a highly toxic material and people and the
surrounding environment (18).
6.3.4.
Heat Exchangers
Heat exchange equipment varies widely in efciency in terms of available heat

transfer area per volume of inventory contained in the exchanger. Innovative heat
exchanger design can reduce the volume of hazardous material in a heat exchanger
by a factor of 10 or more when compared to a standard shell-and-tube exchanger.
Some more efcient alternatives include plate, shell-and-nned tube, plate-n, and
rotary exchangers. With some of these devices, it is important to consider the potential for additional leak scenarios, such as gasket leaks in plate exchangers or hazards associated with seals and moving parts in rotary exchangers. The designer
must balance the benets of reduced inventory against the possibility that leaks
may be more likely. Kletz (6) discusses alternative heat exchanger designs.
6.3.5.
Distillation
Innovative design of distillation devices can greatly reduce inventory and can also
reduce the residence time in the distillation system, which may be important for
safely processing thermally sensitive materials. Wiped lm evaporators have been
in use for many years, particularly for distillation of reactive materials, such as
monomers, and for other heat-sensitive compounds. In more traditional distillation equipment, columns and trays can be designed to minimize the inventory of
liquid in the column. Often the largest inventory of hazardous liquid is contained
in the bottom of the column and in the reboiler. This is particularly undesirable
for a reactive or thermally sensitive material because this is part of the distillation
column that is at the highest temperature. It is possible to design the bottom of a
column to minimize this inventory. For example, use a conical column bottom or
a small-diameter column bottom that still provides sufcient liquid head for bottoms or reboiler recirculation pumps but reduces the total quantity of hot liquid.
Centrifugal distillation equipment such as Higee (19) can be much smaller than
conventional distillation equipment.
6.3.6.
Extraction
Extraction columns are often very large devices, and they may contain a large
quantity of ammable or toxic solvent. The inventory of hazardous material in an
extraction system can be greatly reduced by using a centrifugal extractor. In this
case, the inherent safety benets of reduced inventory must be balanced against
the new hazards introduced by the centrifugal extractor, including operation at
high speed and potential for leakage from seals, to determine the best choice for
a particular application.
6.3.7.
Combined Unit Operations
Equipment that combines more than one unit operation in a single piece of equipment is another approach to process intensication. Reactive distillation is a good
example. In one case, a traditional process for the manufacture of methyl acetate uses
a stirred-tank reactor, eight distillation columns, and an extraction column. A new,
reactive distillation process uses one reactive distillation column and two additional
columns (5). The total inventory of combustible material in the process is reduced.
In this example, the reactive distillation system also results in a simpler plantone
with fewer major vessels. The process is also simpler because there is much less supporting equipmentcondensers, reboilers, pipes, valves, pumps, instruments. Safety
is enhanced because every valve seal, ange, pump seal, and instrument connection
that is eliminated from the plant is one less place that the process can leak. This
reduces fugitive emissions from this equipment, which contribute to plant emissions
and pollution, and also the likelihood of bigger leaks that can cause a re, personnel
exposure or injury, or a signicant environmental incident.
6.3.8.
Innovative Energy Sources
Energy sources such as laser light, ultraviolet light, microwaves, and ultrasonic
energy can be used to apply energy in a controlled fashion to a chemical reaction
or physical unit operation to increase efciency. For example, technology for the
distributed, small-scale manufacture of hydrogen cyanide using microwave energy
to direct heat to the reactor catalyst is under development (20). This would allow
hydrogen cyanide to be manufactured in small quantities where it is needed,
rather than manufacturing it in a large central facility, storing it, and transporting
it to the sites where it is needed.
7.
METRICS FOR INHERENT SAFETY
How do you measure inherent safety? This is an important question that must be
answered to effectively promote the development of inherently safer process technologies, including process intensication. Development of new technology
requires resources, and these resources can be more easily obtained if the costs
and potential benets of the new technology, including economics, safety, and
environment, can be measured. Also, chemical processes always involve multiple
hazards. A process that is inherently safer with respect to one hazard may be less
safe with respect to a different hazard, or it may introduce new hazards. For
example, our earlier discussion about extraction points out the benets of reduced
inventory that can be obtained with a centrifugal extractor but acknowledges the
new hazards introduced by the use of high-speed rotating equipment and the
potential for leakage from seals. Some method of quantifying these risks is essential to making the best technology decisions.
The chemical industry is just beginning to develop tools for measuring
inherent safety. Some of these tools have been used for risk management and loss
prevention for some time, but we are just beginning to recognize their value in
understanding the inherent safety of processes.
7.1.
Accident Consequence Analysis
The analysis of the potential consequences of an accident is a useful way of

understanding the relative inherent safety of process alternatives. These consequences might consider, for example, the distance to a benchmark level of damage
resulting from a re, explosion, or toxic material release. Accident consequence
analysis is of particular value in understanding the benets of minimization, moderation, and limitation of effects. This discussion includes several examples of the
use of potential accident consequence analysis as a way of measuring inherent
safety, such as the BLEVE and toxic gas plume model results shown in Figures 4,
5, and 6.
There are many commercial and public domain tools available for accident
consequence modeling. Guidelines for Use of Vapor Cloud Dispersion Models (21)
reviews many of the available models for ammable and toxic gas clouds in
the atmosphere. Guidelines for Consequence Analysis of Chemical Releases (22)
describes modeling techniques for res and explosions, some of the simpler
atmospheric dispersion models, and models for estimating the impact of different
types of incidents on people and property. This book also includes a set of spreadsheets for the models discussed. The TNO Yellow Book (23) describes a wide
range of models for many types of potential accidents in a chemical plant. The
TNO Green Book (24) reviews models for estimating the potential impact of
accidents on people and property.
7.2.
Risk Indices
A number of risk indices have been developed over the years as chemical process
loss prevention and risk management tools. Many of these are based on the inherent characteristics of the processes, and they can be used as measures of process
inherent safety. In general, these indices measure a single aspect of inherent safety,
and it is necessary to use several indices to obtain a full understanding of the overall process characteristics.
The Dow Fire and Explosion Index (FEI) (12) and the Dow Chemical
Exposure Index (CEI) (14) are two commonly used tools that measure inherent
safety characteristics. Gowland (25) reports on the use of the FEI and CEI in the
development of safety improvements for a urethane plant. Tables 1 and 2 illustrate
the application of the FEI and CEI in measuring inherent safety characteristics of
process design options. These indices measure the inherent safety characteristics
of processes in only two specic areasre and explosion hazards and acute
chemical inhalation toxicity hazards. Other indices would be required to evaluate
other types of hazards.
Because the material inventory is considered in these indices, process intensication will result in a lower value (greater safety) for either index. However,
the indices do also consider other factors, such as temperature and pressure, that
might be higher for an alternative process. The index is therefore valuable in helping to understand the relative value of a reduced inventory of hazardous material
compared to other hazard factors that might increase.
7.3.
Overall Inherent Safety Index
Some initial work on the development of an overall inherent safety index has been
done at Loughborough University in the United Kingdom (26). Other, similar
work has been done at VTT in Finland (27). Both indices are considered prototypes by the developers, and more work is needed. These proposed inherent safety indices evaluate a number of factors related to inherent safety, including:
Inventory
Flammability
Explosiveness
Toxicity
Temperature
Pressure
A single-number overall index characterizing the inherent safety of the overall
process is generated by both proposed inherent safety indices. Process intensication will lower the value of the index (indicating an inherently safer process)
because it will reduce the penalty for inventory. If the alternative process results
in an increase in the inherent hazard due to other factors, the index will be useful
in understanding the inherent safety characteristics of the different alternatives.
The relative contributions of the various components of the index to the total
value may also be useful in understanding process safety characteristics. Table 3
summarizes the application of this proposed inherent safety index to a number of
alternative routes for the manufacture of methyl methacrylate.
TABLE 3 Evaluation of Alternate Methyl Methacrylate Processes

Using the Edwards et al. Proposed Inherent Safety Index
Process route
Acetone cyanohydrin
Ethylene based/propionaldehyde
Propylene based
Ethylene based/methyl propionate
Isobutylene based
Tertiary butyl alcohol based
Inherent
safety index
120
75
70
50
50
50
8. PROCESS INTENSIFICATION BENEFITS FOR PASSIVE

AND ACTIVE LAYERS OF PROTECTION
While a smaller process may not totally eliminate a hazard, it often can have the
benet of making effective passive layers of protection for the process more
feasible and cost effective. Passive protection devices such as containment dikes,
blast-resistant enclosures, and containment buildings to prevent the escape of
toxic gas can be smaller. Active safety devices such as rupture disks, ares, and
scrubbers will be reduced in size. Smaller processing equipment will also respond
more quickly to other common safety interlock actions, such as shutting off reactant
feeds, increasing cooling to a vessel, adding reaction shortstop agents, and emptying a reactor to a reaction quench tank. Some examples of the potential benets of process intensication in the application of other safety features follow.
Unstable materials such as explosives are sometimes manufactured in
remotely controlled facilities protected by blast-resistant enclosures or bunkers.
In this situation, if an explosion occurs the process equipment may be severely
damaged or destroyed, but nobody will be injured and the environment and other
property will be protected. This would be considered to be a passive safety feature
the blast-resistant enclosure does not require the action of any equipment or people
to perform its function. While this type of blast-resistant enclosure may be practical
for small equipment, it may become prohibitively expensive for large equipment.
Clearly a larger structure would be required for larger equipment. However, the
enclosure would also have to be much stronger because the potential explosion in
the large vessel would be of greater magnitude.
Process vessels are often protected from overpressurization by active devices
such as relief valves and rupture disks. These devices open at a set pressure and
allow gas and liquid to escape from the protected vessel to limit the pressure. Many
years ago, the rupture disk or relief valve would simply discharge to the atmosphere.
However, this is often unacceptable today because we cannot allow hazardous material to escape to the environment, even in an emergency situation. Emergency
relief devices often must discharge to a collection-and-treatment system to ensure
that no hazardous material is released to the atmosphere. This treatment system
might include equipment such as vapor liquid separation devices, scrubbers,
absorbers, ares, or thermal oxidizers. If the process vessels can be made smaller,
the size of the required treatment system for the emergency relief discharge is correspondingly reduced. Total containment of the emergency relief device efuent in
a large pressure vessel may even be possible, eliminating all discharge to the environment during the event (but the contents of the containment vessel will have to
be treated and disposed of later on).
For extremely exothermic reactions, emergency quench systems are sometimes used to protect against a runaway reaction. If the reactor temperature exceeds
a predetermined maximum safe temperature, the reactor contents are rapidly
discharged to another vessel containing a material that will stop the reaction.
These systems are more feasible for a small reactor. A reactor of a couple of cubic
meters volume can be emptied to a quench tank in a few seconds through a largediameter dump valve, but it might take many minutes to discharge the contents of
a large reactor. It may not be possible to empty the large reactor quickly enough
to prevent the runaway reaction.
9.
SUMMARY
Safety considerations are an inseparable part of the development of a chemical

process and the design and operation of a chemical plant. While risk management and safety features can be added on to a plant design or to an operating
plant, safety is most reliably and robustly ensured by developing inherently safer
processes.
Safety strategies can be categorized as inherent, passive, active, and procedural. Inherent and passive strategies generally relate to the basic process technology and plant design and are nearly always implemented early in the design
life cycle. They focus on elimination of hazards or minimizing the degree of hazard rather than on management of hazards. Process intensication is an important
approach to the development of inherently safer chemical processes because it
reduces the quantity of hazardous material in the process, thereby reducing the
inherent risk.
Active and procedural strategies are usually also a part of a chemical process
risk management programit is not often possible to eliminate all hazards.
Process intensication can also make active and procedural safety features more
effective and economical. Safety equipment can be made smaller and less costly.
It may be feasible to use safety devices to protect against the hazards from small
processing equipment that are impractical for use in a large plant. The faster
response time of small equipment may allow effective automatic or manual intervention to detect an incipient problem and take action to prevent it from developing into a serious accident. Chemical process safety cannot be viewed in isolation
from other process and plant design criteria. The chemical plant must meet many
requirements for workers (safety, long-term health, employment and wages), owners (operating costs, capital investment, protability), customers (product quality,
reliability of supply, cost), neighbors (safety, health, environmental impact, economic impact), and government (compliance with laws and regulations). All of
these are important, and they may be in conict. The chemical process designer
must work to select the optimum design that considers all stakeholders. Process
intensication is an important approach to minimizing the hazards associated
with chemical handling and manufacture and will be an important factor in the
future for designing safe, environmentally friendly, and economically competitive
chemical plants.
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14
Process Intensication Contributions
to Sustainable Development
G. Jan Harmsen, Gijsbert Korevaar, and
Saul M. Lemkowitz
Delft University of Technology, Delft, The Netherlands
This chapter is meant for developers and designers of processes, in particular of

intensied processes, who want to ensure that their processes contribute to sustainable development. To this end problems with the present technological solutions in relation to the world-scale environment and society are explained in the
rst section. Then in the second section sustainable development is explained and
the role and criteria for sustainable technology are derived. Finally process intensication is assessed on its contribution to sustainable development.
The information presented should be sufcient for a developer or designer
of a process to raise awareness of design aspects related to sustainable development, to yield hints to modify the design in the direction of sustainable development, and to nd references for further detailed information.
1.
1.1.
PROBLEMS LEADING TO SUSTAINABLE DEVELOPMENT

Environmental Problems
The disturbance of several natural ecological cycles became a problem with the
start of the Industrial Revolution in the 19th century. The emissions to air, water,
and soil increased exponentionally. In the 20th century these changes in the environment reached global proportions:
Increases of concentrations of greenhouse gases in the global atmosphere
occurring at rates and to levels higher than those ever reached during the
previous thousands of years (1).
Massive deforestation occurring faster than at any time in human history (2).
Species extinction and loss of biodiversity at rates higher than 10,000 per
year (3).
The publication of the report Limits to Growth (4) by the Club of Rome
had a major impact on thinking about the environmental impact of our cultural
development. Under the assumption that the ve basis elements of this study
population, the production of food, industrialization, pollution, and the use of nonrenewable resourceswill keep increasing exponentially, they showed that, if
unchanged, this would lead to enormous problems, as soon as the 21st century. The
social consciousness of the problems caused by unlimited growth of these elements was greatly increased by this report by the Club of Rome.
In the present situation, one can say that natural resources and the environment can no longer be regarded as inexhaustible reservoirs of products and services. On the contrary, in general it is now recognized that natural resources are
limited, that the natural environment has a limited capacity, and that this must
have consequences for the way we act.
1.2.
Socioeconomic Problems
In addition to adverse changes to the world environment, economic differences

between rich and poor are increasing (decreasing equity), both within nations
and between nations. The richest fth receives 83% of the total world income (5).
Moreover, the gross domestic product (GDP) per capita stays more or less the
same for poor countries. This unfairness is also a part of unsustainability, because
it blocks possibilities toward worldwide cooperation. It limits the real growth of
the intrinsic quality of life, which is wanted by every human being thinking about
his or her childrens future. It also leads to extensive illegal immigration of the
poor to the richer parts of the world.
Also, all parts of society contribute to the problem. For instance, carbon
dioxide emissions to the atmosphere due to fossil fuel combustion is caused 50%
by industry; the other parts are domestics and transport (the electric power contribution is divided between industry and domestics) (6,7).
1.3.
Present Technology Is Part of the Problem
Since awareness arose of the large-scale environmental, resource, and socioeconomic problems, several technological solutions have been implemented. However,
they did not solve the problems and in some cases caused even bigger problems,
as is shown in the cases described later.
1.3.1.
High Chimneys for Acidic Flue Gases
In the 1960s a large number of cities in western Europe suffered from smog formation. One of the major causes was the local emission of acidic ue gases from
large industrial areas. Under still weather conditions, these acid components would
remain in the atmosphere near the earths surface and form smog. The technological solution was to build very high chimneysover 200 meters highcutting
through the atmospheric inversion layer. The ue gases where dispersed in this way
over a larger area. In the decade that followed, it appeared that in more rural areas,
notably Sweden, these acid gases caused acidication of forests and lakes, with
negative effects on their biological quality. Trees and sh died on a large scale.
1.3.2.
CFC Use
In the 1960s and 70s, CFCs were used on a large scale as propellant gases in spray
cans and as a refrigerant in refrigerators. These gases were considered inert to
humans and the environment. Hence, release into the atmosphere was considered
acceptable. In 1973, however, Molina discovered that these CFCs broke down the
ozone layer high up in the atmosphere (8). This ozone layer itself absorbs the ultraviolet radiation of sunlight and in this way prevents ultraviolet radiation from
reaching the earths surface and thereby harming humans (skin cancer formation)
and other living species (algae in oceans). Due to the slow breakdown of CFCs the
effect on the ozone layer is expected to last for centuries (9).
1.3.3.
HFC Replacement of CFC for Refrigeration
Due to the negative effect of CFCs on the ozone layer, a replacement was developed: HFC. This component hardly breaks down the ozone layer. It is now replacing CFCs in domestic refrigerators and air conditioners in cars on a very large scale.
However, HFC has a global warming gas potential that is a factor of 1000 higher
than carbon dioxide. The present amount of HFC in the atmosphere is estimated
to account for a global warming effect of 0.6C (10).
1.3.4. MTBE in Gasoline as a Replacement
for Lead Components
In gasoline, lead components are used to enhance the octane number. It became
clear that these lead components, once emitted from car exhaust pipes, cause
brain damage. California was the rst to ban these lead components and to stimulate the use of MTBE as a replacement. MTBE both acts as an octane booster
and enhances the gasolines combustion, by which less volatile organic carbon
components are emitted from the car exhaust pipes. However, it appeared that
MTBE entered underground water reservoirs by occasional spillage of gasoline.
This made the water unt for drinking due to its bad smell. In California billions
of gallons of drinking water are already contaminated in this way, and legislation
is under way to ban the use of MTBE in gasoline.
1.3.5.
Brent Spar Oil Platform in the North Sea
In the 1970s, the awareness of the limited oil resources resulted in a sudden oil
price increase by a factor of 4. It became economical to produce crude oil from
sea bottoms. One of the rst oil platforms in the North Sea was the Brent Spar. In
the 1990s, oil production ceased and the platform had to be demolished. In the
Brent Spar design, demolition had not been taken into account, and so the demolition appeared to be very difcult. In consultation with the British government it
was decided that dumping in a deep trough in the ocean would be the best economical and environmental solution.
The environmental activist organization Greenpeace disagreed with this
solution, arguing that the problem was not the dumping of the Brent Spar; the real
issue, they held, was the principle of dumping in the ocean in general and that the
Brent Spar dumping would be used by other companies (nuclear energy companies and others) to claim the same right of dumping.
Greenpeace started a campaign to prevent this dumping by asking the general public to boycott Shell gasoline purchases. Especially in Germany this boycott had a noticeable effect, and Shell decided to reverse it decision and to invite
any company or organization to propose alternative solutions. In the end, it was
decided to bring the platform to a fjord and dismantle it there in such a way that
parts could be reused in other applications.
1.3.6.
Preliminary Conclusions on Technology Cases
All the technological solutions mentioned already have in common that the problem to be solved was dened too narrowly in space, time, and lifecycle phases.
Wider-ranging and longer-term effects on the local and global scales on humans,
nature, and ecology were not taken into account.
2. SUSTAINABLE DEVELOPMENT AND REQUIRED
TECHNOLOGY
2.1.
General Concept of Sustainable Development
The general opinion about the aforementioned problems and the ad hoc technical
solutions is that they are by no means sufcient. The essential concept when thinking about these subjects nowadays is sustainability. It was greatly helped by the
description and denition by the Brundtland report of the World Commission on
Environment and Development (WCED), Our Common Future (11):
Sustainable development is not a xed state of harmony, but a process of
change in which the exploitation of resources, the direction of investments,
the orientation of technological development and institutional change are

made consistent with future as well as present needs. Sustainable development is development that meets the needs of the present generation without compromising the ability of future generations to meet their own needs.
This denition contains two key concepts:
The concept of needs, in particular the essential needs of the worlds poor,
to which overriding priority should be given
The idea of limitations imposed by the state of technology and social
organization on the environments ability to meet present and future
needs (12).
The most admirable aspect of this report is the attempt to bring the two
largest world problemsunlimited exploitation of nature and growing inequity
within and among nationstogether in one concept that everyone from government to citizen can work on.
Two very important remarks have to be made about the denition of the
Brundtland Commission.
1. The denition makes clear that development of new technologies, social
structures, or whatever has to take into account economic and social
issues ( present generations) and long-term and large-scale environmental issues ( future generations). Thus developments that have to lead to
sustainability are limited and have to consider the idea that every human
being must be able to fulll his or her needs in a more or less equal way.
2. We have to distinguish between two different kinds of development: one
that leads to technological innovation, as used in the term research and
development, and one that is about improving the welfare of a society,
as used in the term developing countries. This distinction is very important, because it makes clear that sustainable development has different
meanings in different countries. In a rich country, sustainable development sets limits to the growth of afuence or the possibilities of new and
innovative technologies. In poor countries, sustainable development has
to do with helping the population to survive and if possible to thrive.
To further understand what the commission meant by this denition it is necessary to read the whole book, because a lot of discussion occurred within the commission about poverty and afuence, distribution of knowledge and information,
the rights of the northern part of the world to live more afuently than the southern
part, the right to develop, etc. Here we use the summary by Install (13):
Set priorities among the needs.
Ever-lasting growth is unsustainable, because large parts of earths natural
capital are not substitutable by human-made capital.
The actual world economy rules are unsustainable.

The existence of various cultures should be encouraged.
Intergenerational equity results in a maximum well-being for ourselves under the
constraints that the well-being of future generations must be at least equal to
ours.
2.1.1.
Ideas Complementary to Brundtland
The denition and vision of the Brundtland Report are described more practically
by three other United Nations Commissions, the International Union for Conservation of Nature and Natural Resources (IUCN), the United Nations Environment
Program (UNEP), and the World Wide Fund For Nature (WWF), called Caring
for Earth: A Strategy for Sustainable Living (14). This report denes sustainable
development as: Improving the quality of human life while living within the
carrying capacity of supporting ecosystems. This report contains nine chapters,
with the following titles, that also can be seen as nine issues of sustainable
development.
1.
2.
3.
4.
5.
6.
7.
8.
Respecting and caring for the community of life

Improving the quality of human life
Conserving the earths vitality and diversity
Minimizing the depletion of nonrenewable resources
Keeping within the earths carrying capacity
Changing personal attitudes and practices
Enabling communities to care for their own environments
Providing a national framework for integrating development and conservation
9. Creating a global alliance
2.1.2.
The Three Parts of Sustainable Development
So far the ideas of sustainable development have been described mainly in global political terms. The nancial and business world also took hold of the concept
and reformulated it into three parts: social, ecological, and economic (15,16).
This in turn was translated into a catch phrase: People, planet, and prot (17). We
will summarize these parts.
2.1.2.1 Ecological Part (Planet). The ecological part has to do with the
impact of human action on nature. Mainly this means all the known environmental problems and processes that disrupt the ecosystems (ozone depletion, acidication, greenhouse effect, destruction of species, wastes, etc.). In a sustainable
world all those known problems must be minimized or avoided. In addition, for
as far as possible, sustainable development must have the power to avoid new
problems. The precautionary principle is therefore adopted.
Precaution principle: At the United Nations Conference on Environment

and Development (UNCED) in Rio de Janeiro the (nonbinding) Rio Declaration
of 1992 was agreed on, with the following text:
Principle 15.
In order to protect the environment, the precautionary approach shall be
widely applied by States according to their capabilities. Where there are
threats of serious or irreversible damage, lack of full scientic certainty
shall not be used as a reason for postponing cost-effective measures to
prevent environmental degradation.
This is a better-safe-than-sorry principle that advocates the reduction of inputs
into the environment of substances especially where there is reason to believe that
harmful effects are likely to occur (18). Therefore, the precautionary principle has
to play an important role in decisions about new technology.
2.1.2.2 Social Issues (People). The sustainable development of society
concerns needs. This means that consumer participation is very important and
that the creation of new markets has to be done with caution. Further, concerning
the lasting factor of societies, it is essential that sustainable development be in
agreement with local culture.
2.2.2.3 Economic Issues (Prot). It is obvious that if scarce nonrenewable resources such as fossil fuels and rich metal ores are going to be depleted,
prices will become extremely high. Therefore, economics is very important in
sustainable development. This is also true for the feasibility of sustainability concepts: If they are not protable, then they will not be accepted. However, it is very
important to think over the meaning of the term protability. Indeed, if external
costs are taken into account, sustainable technology will be more protable in the
long term than conventional technology.
External costs is an economic concept, which gives the possibility of setting
the prices right. External costs are the cost involved by the rest of the lifecycle of
products and by-products and not accounted for in present cost calculations. For
example, the price of fossil fuels depends not only on exploration costs but also on
the costs involved by the production of CO2 and resultant adverse climatic effects,
which will be many trillions of dollars. In an article in Nature the value of the
world ecosystem services is estimated to be worth 33 1012 $ per year (19). This
means that for economic activities that destroy part of the ecosystem, the ecovalue (service) reduction should be accounted for.
These external cost can be considerable compared to the present calculated
cost. The present global economic production expressed as GNP is estimated at
18 1012 $ per year; so the world ecosystems produce a factor 1.8 higher annual
value (19). This means that the external cost can even exceed the present cost
when the ecosystem is seriously affected by human activity.
2.1.3.
Other Views on Sustainable Development
So far the mainstream thoughts about sustainable development have been

described. However, there are other voices, which have a different view on sustainable development and critisize (part of) the Brundtland description. Their
general comment is that the Brundtland description stems from an anthropocentric worldview that places man too much at the center. Two other views are the
ecocentric and the theocentric Judeo-Christian worldviews. A brief description of
each follows, together with their main criticism on the Brundtland view.
2.1.3.1. Ecocentric Worldview. In this view nature has a value of its
own. It places nature at the center and man as a part of nature. Man should not
have a large impact on nature. All biological species should be maintained.
Technology should t into and depend on nature. Nature should be kept in a
steady state. If this means that human needs are to be restricted, then that is
accepted. To quote Gandhi: The world provides sufcient for everybodys need
but not for everybodys greed.
People who have this worldview often criticize the Brundtland description because it sees nature mainly as a source for goods and services for mankind (20).
2.1.3.2. Theocentric Judeo-Christian Worldview. In this view, nature is
seen as Gods creation. Man is mandated to be Gods steward for this creation. A
typical Bible text in this respect is: to work it and to take care of it (Bible,
Genesis 2:15). Also, in this worldview people should take care of their neighbors
and in particular take care of the weak and the poor. Furthermore, in this view
man should restrain himself in his needs. He should not be greedy. A comprehensive description is given by Elsdon (21).
Some criticism of people with this worldview on the Brundtland description is that it sees nature as mans possession and that it does not mention a
restriction on mans greed.
2.2.
Sustainable Technology Positioning
In the last 30 years, environmental impact has been mainly reduced by end-ofpipe solutions. These solutions always mean that more construction material and
energy is required; hence they reduce the environmental impact for a certain component but often increase the impact for another component and are always more
expensive.
Then the next concept arrived: clean production technology. Jackson (1993)
denes clean production as a conceptual and procedural approach to production
that demands that all phases of the lifecycle of a product or a process should be
addressed with the objective of prevention or minimization of short- and longterm risks to human health and to the environment (18).
With this type of technology, products and processes are reformulated to

manage emissions and waste upstream. These solutions can mean both less
emission and less cost and energy.
In these views of technology, the social part and the economic parts of sustainable development are not taken into account. In the next section we will derive
a general view on sustainable technology, rst by showing all interactions with
the sustainable development aspects and then some specics for each sustainable
development part.
2.2.1. Social, Economic, and Ecological Interactions
with Sustainable Technology
Providing for the needs of society while staying within ecological constraints is not
only a task for technology, but also the result of the interaction of culture, political
structure, and technology; (22). Culture determines the size and the nature of the
needs for which fulllment is justied and the conditions that technology and structure have to satisfy. Structure is the way in which fullling the needs is organized
by means of production and consumption. It has to do with organization, economy,
and policy. Technology is not only the total of means available for fullling the
needs; technology itself also has an inuence on the culture. The latter inuence is
difcult to predict but can be discovered from the past.
For instance, the development of lightweight, low-cost plastics led to packaging of small-portion consumer items. This in turn enhanced the development of
self-service supermarkets, which led to shopping by car rather then walking to
nearby small shops (23). This contributed to a more individual culture. Presently
the whole infrastructure of a developed country is based on auto transport. The
road is no longer a meeting place of persons but a depersonalized area, again
leading to a more individualistic society.
Stainer et al. give some guidelines for the different actors in a technologybased culture (24):
Engineers: Be aware of the implications for society and environment.
Nonscientists: Understand applied science.
Companies: Sustainable growth is allied to risk management.
Politicians: Develop the skills for sustainable policy.
All groups: Recognize the need for communication.
A very interesting concept developed by Moser is the principle of invasiveness in relation to embeddedness of technology (25). This concept makes it clear
that current technologies have a high impact on the environment (invasiveness) but
that their rapid development and the high public concern about their impact are not
very well anchored in society; this means a low embeddedness. New, cleaner technology, and especially sustainable technology, has to be developed so that they will
not need to change very fast and be more strongly embedded in society.
All this is said to make clear that something has to change drastically in the
focus about using technology if we want to speak about sustainable technology.
In sustainable technology, technology is still serving humans and their society
(otherwise, we need not speak about technology at all!). However, the technology
should also be the servant of nature, both in an active and a passive way.
2.2.2. Ecological Impacts as a Function of Cultural,
Economic, and Technological Activities
The ecological impacts caused by human activities are large. To give more insight
into the effects of economy, culture, and technology on ecological impacts, the
following semiquantitative expression is often used. It is the so-called master
equation. This expresses the environmental impact as a product of population size
(P), gross domestic product per person {GDP/P} and environmental impact per
unit GDP {EI/GDP}
EI P * {GDP/P} * {EI/GDP}
Often the following substitution is made:
GDP/P W (W meaning wealth)
EI/GDP T (T meaning technology)
resulting in
EI P * W * T
This master equation can then be used to calculate the increase in environmental
impact for the population, or the increase in wealth with the same technology, or to
calculate the required emission reduction per unit GDP by new technology. If, for
instance, wealth worldwide reaches the same level as now in the industrialized world,
then W increases by a factor of 4. If the population (P) does not increase and technology (T) stays the same, then EI (e.g., carbon dioxide emissions to the atmosphere)
would increase by a factor of 4. To keep EI at the same level, the technology should
be improved to give an emission reduction of a factor 4 per unit product or service.
In reality this use of the expression is too simplistic:
Population growth is a function of the level of wealth. In Western society
the natural population growth is less than zero (the birth rate is less than
2 per woman). The same could happen in developing countries once a
certain level of wealth has been reached.
Replacing GDP/P by wealth is also under debate. All kinds of occurrences,
such as car accidents leading to medical care consumption, are adding to
GDP, while these things do not add to wealth at all. Corrections to the GDP
for these aspects have already been proposed by (26).
There is a trend that beyond a certain wealth, the environmental impact
emission per unit capita is reduced. Jackson shows that on average above
5000 GDP per capita, the hazardous waste per unit GDP is reduced (18).
Hence the level of W also has an effect on EI/GDP.
The environmental impact per unit GDP (T) is not only a function of technology but also a function of human behavior and societal culture.
Jackson shows that countries with the same GDP per capita show large
differences in hazardous waste per unit GDP. For instance, Scandinavian
countries, compared to Canada and the United States show, a similar
GDP per capita but up to a factor 4 difference in hazardous waste per unit
capita (18, p. 115). This difference is due to differences in culture.
Scandinavian countries value nature more than does the United States. A
good source for further reading on this aspect of wealth increase and
impact reduction is von Weizscker et al. (27).
2.2.3.
Transition to Sustainable Technology System Levels
Now when we talk about the transition to sustainable technology it is helpful to

understand that technology has to deal with different system levels, as shown in
Table 1. It is obvious that changes in societal infrastructure are more complex and
require more disciplines and more stakeholders involvement. These changes are
on a very long time scale (decades to centuries). Scenario building is an important part of the methods to robust long-term developments (28). This eld is too
big to elaborate further in this chapter.
Changes to new, sustainable products or new processes, tting into existing
infrastructures, are less complex and can be achieved on a shorter time scale. The
system levels, from process downward, will be further discussed later.
TABLE 1 System Scale Levels and Technology Disciplines

System scale levels
World biotic and abiotic
Societal infrastructure
Industrial complex
Process
Unit operation
Equipment
Catalyst/dispersed entity
Nano
Molecules
Major disciplines involved

Ecology, politics, physics, chemistry
Politics, social science, economics, laws,
ecology, civil engineering, city and
landscape architecture
Civil engineering, economics, law
Chemical engineering
Chemical engineering
Chemical engineering, mechanical
engineering
Chemistry, physics, chemical
engineering
Chemistry, physics, engineering
Chemistry, physics
2.3.
Sustainable Technology Scorecard
To aid the developer or designer of a new technology the author has derived a
scorecard to assess the technology on its contribution to sustainable development.
It is based on the sustainable development aspects: social, ecology, and economy.
The scorecard is shown in Table 2. The basis and use of the scorecard will now
be explained.
TABLE 2 Sustainable Technology Scorecard

Sustainable development item
Social/people
Provide for the needs of the poor:
water, food, clothing, local
energy, etc
Fair distribution of wealth, power,
and knowledge
Social acceptance
Safe
Noise
Smell
Occupational health
Plot area impact

Skyline impact
Ecological/planet
Sensitivity to world-scale nature
and ecology
Depletion of abiotic resources
Depletion of biotic resources;
biodiversity
Dehydration
Ozone depletion potential (ODP)
Global warming potential
Photochemical ozone pollutants
Comment
Prime goal
Adaptable, nondisruptive to society

By stakeholder engagement
Loss prevention at all conditions
Below legal limits
No obnoxious emissions
Long-term effects of exposure to
chemicals should be known and
acceptable
Low; important in densely
populated areas
Low aesthetic and bird friendly
No emission of components whose
ultimate environmental fate is
unknown
Keep air, surface water, and soil
healthy
Maintain biodiversity
Maintain water reservoirs
No ODP gas emissions
Green house gas emissions reduced
by factor 4
Volatile organic component
emissions below expected future
legal limits
TABLE 2 (cont.)
Acidication
Human toxicity
Ecotoxicity (terrestrial and aquatic)
Nutrication (eutrophication)
Radiation
Thermal pollution
Waste
Economy/prot
Scarce resource depletion
Drinking water resource depletion
Fossile fuel depletion
External (future) cost
Capital expenditure and
decommisioning cost
Operational cost long term
Protable over total lifecycle
2.3.1.
Comment
emissions below expected
legal limits
legal limits
legal limits
legal limits
legal limits
legal limits
legal limits
future
future
future
future
future
future
future
No full depletion; replacement by

renewables
No depletion
No full depletion; replacement by
renewables
Include in present accounting
Social/People
A prime goal of sustainable development on a world scale is to provide for the

needs of the poor. Throughout one should keep in mind that developed
economies have different challenges than survival economies. For survival countries the main goal is to provide for the needs of the people in an affordable way
while not consuming natural capital (29). Hence this is an important item on the
scorecard. One can think of technology providing water, food, clothing, and clean
energy for cooking and housing while adapting to the local social, economic
(resources), and ecological situation (30).
Another item on the scorecard requiring some explanation is social acceptance. In the previous sections it is shown that sustainable technology is to be
embedded in society. This means, in our view, that society should be considered
in the design stage. A discussion with representatives of stakeholders should be
held to clarify the effects of the new technology on the ecology, society, and
economy and to seek acceptance. Stakeholders can be environmental activists,
civilians, government representatives, manufacturing companies, and consumers.
These stakeholders often have different worldviews. In stakeholder discussions this is often not recognized. The previous section on worldviews in relation
to sustainable development should help to understand the background of certain
arguments used in stakeholder discussions.
Scholes reveals that such a stakeholder discussion was carried out by Shell
in the design phase and led to changes in the design and to greater acceptance of
the new process (31).
2.3.2.
Ecological Assessment
The precautionary principle should be applied. This means that for all emissions
over the whole lifecycle, the nal environmental fate needs to be known. If this
knowledge is not available, the emission of that component should be kept at
zero.
All other scorecard items stem directly from lifecycle analysis assessment
theory (32). For some impact types, quantitative norms can be stated. For stratospheric ozone layer depletion components, the emission norm is zero. This means
in practice that components such as CFCs and SF6 should not be used at all, not
even in contained technical applications, because containment over the lifecycle
cannot be ensured.
For other emissions, such as potential global-warming gases, the norm will
depend on the time horizon of the application. If the application is foreseen for a
long time horizon, say, 50 years, then the global-warming gas emissions should
be reduced by a factor of 410 compared to the present (27).
To be able to assess the environmental impact of a technology over the
whole lifecycle, a lifecycle assessment (LCA) should be performed. A brief
description of LCA follows.
Life cycle assessment is a method for calculating the environmental impact
of a product or service over its whole lifecycle. Steps in a lifecycle include:
Exploration
Rening
Manufacturing
Use
End of product life (i.e., combustion, reuse, or recycle)
Process decommission
A process (manufacturing) is therefore part of a product recycle. Often the decommissioning phase of the process plant is not taken into account in the LCA. As, for
instance, happened in the Brent Spar case and for most nuclear power plants.
An LCA consists of the following stages:
1.
2.
3.
4.
5.
Goal denition and scoping

Inventory analysis
Impact assessment (classication)
Valuation
Improvement
1. Goal denition and scoping denes the purpose of the LCA and its
scope, the latter meaning depth and broadness. This is important because LCA
can be carried out in great detail, requiring great input of time and money. When
the goal is comparing alternatives it is sufcient to gather knowledge that is not
absolutely correct but good enough to make relative comparisons. Scope involves
selecting system boundarieswhat and what not to include. For example, infrastructure may include the plant that makes a product but also the whole transportation system (e.g., roads, their construction and maintenance) to distribute it.
Limiting scope is essential for practical execution of LCA studies.
2. The inventory analysis determines the material and energy inputs and
outputs relating to one functional unit of product or service and links these to
environmental impacts. This stage is simply a material and energy balance, albeit
a complete one, that is, covering all lifecycles of the product or service being considered and relating to all inputs and outputs of all of these lifecycles, including
even micro-outputs, such as (when relevant) micro-emissions of dioxins down to
milligrams per year for plants, with total emissions in megatons per year (e.g.,
power plant).
3. Impact assessment translates the inventories into recognized environmental impacts and calculates a value for each of these impacts. Generally recognized environmental impacts are given in Table 3. Assigning an emission of a
given substance a given environmental impact depends on the properties of the
given substance. Emitted sulphur dioxide, for example, is converted into sulphuric
acid and is therefore classied as an acidication impact. Emitted carbon dioxide
and nitrous oxide are greenhouse gases and are therefore classied as global
warming substances.
Once emissions have been classied into a given environmental impact,
they must be assessed. This means calculating the quantitative value of this
impact. Environmental impacts are calculated by means of conversion factors, or
TABLE 3 Generally Recognized Environmental Impacts

Depletion
Abiotic
resources
Biotic resources
Pollution
Depletion of stratospheric
ozone layer
Global warming
Formation of
photochemical
oxidants and
pollutants
Acidication
Human toxicity
Ecotoxicity (terrestrial and
aquatic)
Radiation
Thermal pollution (dispersion
of heat)
Noise
Smell
Occupational health
Disturbances
Desiccation
(dehydration)
Physical ecosystem
degradation and
landscape
degradation
Human victims
so-called equivalency factors. We illustrate this by using the impact category

global warming.
Conversion factors for global warming potential (GWP) are expressed in
terms of CO2 equivalency (kg CO2 equivalent), as given in Table 4. Using GWP
values, emissions to the air of various substances can be converted to an equivalent CO2 global-warming effect by means of the following formula:
n
Global - warming effect (kg) (Emissions to air)i (GWP)i

i1
Example: The GWP of a factory that per year emits 1 megaton of CO2, 10 kilotons of CH4, and 1 kiloton of N2O is
3(1 1 megaton 0.01 62 0.001 290)
1.352 megatons CO2 equivalent per year
Other environmental impacts can be calculated similarly by using the
appropriate equivalency factor. Impacts of human toxicity and ecotoxicity are, for
example, determined by factors such as toxicity data (for humans, resp. various
nonhuman life forms), persistence, and bioaccumulation. Equivalency factors for
TABLE 4 Global Warming Potential (GWP) for a Number of Substances (32)

Substance
Substance formula
Carbon dioxide
Methane
Nitrous oxide
CFC11
CO2
CH4
N2O
CFCl3
GWP
(kg CO2/kg substance)
1
62
290
5,000
Source: Hauschild, 1998, vol. 1.
a wide range of substances can be found in the literature (32) and for industrial
chemicals (33).
4. Valuation. In the valuation step, all impacts are multiplied by norm factors. The resulting gures are added up to yield a single total gure. The norm
factors are subjective, for they express the relative importance one gives to totally
different environment effects. This subjectivity can be made more acceptable by
having the norm factors set by a panel with representatives of various worldviews
or political parties.
5. Improvement. One of the great uses of LCA is to pinpoint places in the
lifecycle that cause major environmental impacts and thus lead to highly efcient
improvement of the impact spectrum for a given product.
The LCA results can be used for a sustainability assessment of a new technology by comparing the outcome with the existing technology results. In the
conceptual phase of the new technology, a relative assessment can be used to
highlight where improvements should be made and where the problem areas are.
This is shown in Section 3 on process intensication assessment.
Detailed Information on the LCA method is provided by Hauschild (32).
2.3.3.
Economy/Prot
It is obvious that if scarce nonrenewable resources such as fossil fuels and rich
metal ores are going to be depleted, prices will become extremely high. Which
means that the next generation will experience higher costs for the same goods,
which is not fair. If scarce resources are depleted, then developments should also
start to provide alternatives at a similar price, so-called strong sustainability
economic development (2). Obvious scarce resourceswater and fossil fuels
are explicitly put on the scorecard.
The future high resource cost and the external cost related to emissions
should also be taken into account in the total lifecycle cost.
Long-term prot is also placed on the scorecard. If a technology is not profitable it will not be accepted by business. However, it is very important to think
over the meaning of the term long-term protability. It is recommended that the
external costs, as far as they are known, be included in the cost calculations, for
in the long term these external costs will likely become internalized via taxation
or otherwise. Some external cost gures can be obtained from the literature. Table 5
gives the values for carbon dioxide and volatile organic components.
The estimation of external cost is a scientic eld in development. To nd
more data, the reader could search the literature on external cost or future cost.
2.3.4.
Use of the Scorecard in the Conceptual Design Phase
In the conceptual design phase a quantitative assessment requiring lots of information is not desirable. A qualitative assessment highlighting the main improvements
and areas of major concern requiring alternative designs is more suitable. The scorecard can be used qualitatively, for instance, by estimating whether the new technology improves individual scorecard items as compared to existing technologies.
Note: There is a tendency to arrive at a single sustainability score. In the
authors opinion little is gained and a lot is lost by the use of a single gure.
What is lost is the information about where the problems with the new technology are located. This in turn means that suggestions for improvements cannot be
found. Also, the danger of balancing poor-scoring areas with very positive areas
becomes real. A sustainable technology should score positive on all three legs
(social, ecology, economy) and should have no signicant negative score in any
impact area.
3. THE POTENTIAL FOR PROCESS INTENSIFICATION
TO CONTRIBUTE TO SUSTAINABLE DEVELOPMENT
Elaborate descriptions of process intensication will be found elsewhere in this
book. Here a short description sufces, followed by an assessment on its potential to contribute to sustainable development, based on present industrial cases
and general features.
TABLE 5 Estimates of External Cost for Two Components Relevant to

Chemical Processes
Emission type
External cost
Carbon dioxide net emission to atmosphere

Volatile organic carbon emission to atmosphere
$46/ton (34)
$8000/ton (34)
Source: SIKA, 1995.
3.1.
Denition of Process Intensication
Process intensification consists of the development of novel apparatuses and

techniques that, compared to those commonly used today, are expected to bring
dramatic improvements in manufacturing and processing, substantially decreasing the ratio of equipment size to production capacity, energy consumption,
or waste production and ultimately resulting in cheaper and more sustainable
technologies (35).
Stankiewicz and Moulijn further divide PI into two areas: equipment and
methods. They give an extensive list of equipment examples. The methods are
subdivided into multifunctional reactors, hybrid separations, alternative energy
sources, and other methods.
For multifunctional equipment, Siirola provides a general description of
functions and how to combine them into a piece of equipment (36). Functions
operating in the same temperature and pressure range can be combined in one
piece of equipment. Multifunctional reactors represent one subclass of solutions
with promising features in cost and energy requirements (37).
3.2. Present Status of Process Intensication
from Industrial Cases
We now apply the criteria for sustainable technologies derived in Section 2, Table 2,
to industrial PI cases. Table 6 shows the results. A short description of the cases
follows. Italic numbers in the table are derived from the references, as is explained
in the following text.
3.2.1. Industrial Cases of Process Intensication:
Background for Table 6
3.2.1.1. Case E: Eastman Chemical Methyl Acetate Process (Siirola,
1995, 1998). In the commercial operation of the Eastman methyl acetate
process, many reaction and separation functions are combined in one single large
column (a few meters in diameter and 80 meters high (38). The number of pieces
of major equipment compared to a conventional design is reduced by a factor of
10 (36). The primary energy consumption and capital expenditure is reduced by
a factor of 5 (38).
The plot area of this process is probably a factor of 10 smaller than the conventional process, because the number of major units has been reduced by a factor of 10.
The major contributions to global warming, acidication, thermal pollution, and fossil fuel depletion are probably all directly related to the energy
required. Because this is reduced by a factor of 5, it is assumed that these contributions reduce by the same factor, 5.
TABLE 6 Sustainable Technology Scorecard Results for Industrial PI Cases

Improvement potential
(reduction factor)
SG
SP
Range
Social/people
Provide for the needs of the poor:
water, food, clothing
Fair distribution of wealth, power,
and knowledge
Social acceptance
Safe: lower reactive, dangerous content
Noise
Smell
Occupational health
Size (equipment volume reduction)
Smaller plot area impact
10
Smaller skyline impact
Yes
Ecological/planet
and ecology
(clean air, etc.)
Depletion of biotic resources;
biodiversity
Dehydration
Depletion of stratospheric ozone layer
Global warming
Formation of photochemical
pollutants
Acidication
Human toxicity
Radiation
Thermal pollution
Waste
5
10
>1.4
1.4
1.2
1.2
1.25
1210
>1.4
1.4
1.2
1.25
16
1.4
3.5
1.2
1.216
3.5
>1.4
1.2
1.25
1.6
1.6
0.85
1.45
Economy/prot
Fossil fuel depletion
External (future) cost low
Capital expenditure
Operational cost
Yes
3
410
3
4
5
5
0.81.6
1.4
Derived from process data, assuming other lifecycle steps are hardly affected.
It is likely that the number of anges and valves has been reduced at least
by the same number as the pieces of equipment. The VOC reduction in the
Eastman case can therefore be a factor of 10 lower than for the conventional
design.
3.2.1.2. Case S: Sulzer Hydrogen Peroxide Distillation System (39).
The safety in this new process is drastically improved because of low operating
temperature, minimal product holdup in the system, reliable safety devices, and
proper selection and treatment of the construction materials (39).
The number of units has been reduced by a factor of 4; therefore it is
assumed that the plot area is reduced by the same factor, 4.
The energy consumption has been reduced by 30% (reduction factor is 1.4).
We have used this factor for global warming, acidication, and fossil fuel depletion. The thermal pollution from cooling water is reduced by a factor of 16 and
the operational cost by a factor of 5 (39).
3.2.1.3. Case SG: Shell Global Solutions Natural Gas Dehydration (40).
This case involves membrane separation for natural gas conditioning (dehydration). The mass of equipment is reduced by 70% (factor of 3 reduction) compared
to the conventional process. From this we derived that the construction volume is
reduced by the same factor, 3. The capital expenditure and operation cost reduction gures are given by Rijkens (40).
3.2.1.4. Case G: GlaxoSmithKline Fine Chemical from Carbonyl Process
(41). The ne chemical is produced in a high-heat exchange reactor. The residence time is thereby reduced by a factor of 1800(!) compared to a conventional
batch reactor. The reactive content is thereby considerably reduced; hence the
process is safer.
The CO2 emission related to this process is reduced by a factor of 1.4 (from
18 to 13 g CO2/mol product). The global warming, acidication, and thermal pollution are assumed to be reduced by the same factor.
The waste is reduced by a factor of 3.5.
3.2.1.5. Case SP: Shell International ChemicalsPDC Bulk Chemical
Process Design (37). This new process design consists of a multifunctional
reactor, which largely combines reaction, heat exchange, and component separation in one piece of equipment. Data on energy and cost element reductions are
provided.
3.2.2.
Conclusion on the Industrial PI Cases
It is clear that for all cases, considerable improvements are made compared to
conventional processes in some criteria in the social, ecological, and economic
areas. It is also clear that for most criteria, no assessment can be made because
data are not reported.
3.3. Potential Contribution of Process Intensication

to Sustainable Development
From the denition and the examples given it is clear that process intensication
does not belong to end-of-pipe technology. Most example cases belong to the category of clean technology. In the following section we will concentrate on its
potential for contributing to sustainable development.
Table 7 contains a summary of the potential of process intensication for sustainable development. Some aspects will be explained in the sections that follow.
3.3.1.
Social/People
3.3.1.1. Providing for Needs, Especially of the Poor. Process intensication is mainly concerned with processes and less with consumer products.
Moreover it is only located on the system-level process. So a big overall contribution to sustainable development is not expected. However, by miniaturization
of certain processes those processes may become part of a higher system level
and have a larger impact then initially imagined. Take, for instance, the development of small fuel cells for electricity production in remote villages in developing
countries, fed with hydrogen from biomass waste. These fuel cells may be massproduced at low cost, by which they enhance the quality of life in developing countries.
3.3.1.2. Social Acceptance. Social acceptance of chemical plants is still
an issue. This is due to the fact that big disasters have occasionally occurred
(Bhopal, Seveso) and also because chemical plants smell, due to diffusive emissions of volatile components. Via process intensication the amount of chemically hazardous, reactive material can be reduced considerably, by which the size of
an emission in the case of an explosion will be far less and the chance of an explosion itself reduced by the lowered hazardous, reactive content.
Often this low reactive content can lead to designing for total containment;
i.e., no relief system is required by which further emission reductions are achieved.
Moreover, the diffusive emissions (smell) can be reduced by reducing the number of anges and valves. Because the size of the plant will also be reduced, it is
likely that the social status of a chemical plant can be raised by the introduction
of process intensication.
3.3.2.
Ecology/Planet
3.3.2.1. Dematerialization. By scale, the reduction of material and

energy intensity by process intensication should reduce environmental impact.
3.3.2.2. Global-Warming Impact Reduction. There is a general reason
why PI, via by function integration, can result in lower energy requirements and
thereby in lower carbon dioxide emissions (given the present way of providing
TABLE 7 Sustainable Technology Scorecard for the Potential Contribution

of PI to Sustainable Development
Social/people
Provide for the needs of the poor: water,
food, clothing
Fair distribution of wealth, power, and
knowledge
Social acceptance
Safe: lower reactive, dangerous content
Noise
Smell
Occupational health
Construction volume reduction
Plot area impact
Skyline impact
Ecological/planet
and ecology
(clean air, etc.)
Depletion of biotic resources; biodiversity
Dehydration
Depletion of stratospheric ozone layer
Global warming
Formation of photochemical pollutants
Acidication
Human toxicity
Radiation
Thermal pollution
Waste
Economy/prot
Fossil fuel depletion
External (future) cost low
Lower capital expenditure
Lower operational cost
Process intensication
improvement potential
Not identied yet

Not identied yet
Probably yes
Yes; factor > 10 possible
Yes; fewer pumps and
pieces of equipment
Yes; fewer anges, less
diffusive emissions
Yes; by less diffusive
emissions
To be assessed for each case
Yes; lower emissions
Not identied
Not identied
Yes; far less energy required
Yes; less diffusive emissions
VOC
Yes; less energy required
Yes; less energy required

Yes
To be assessed for each case
Not identied yet
Yes; improvement factor > 4
Yes
Yes; factor > 4
Yes; factor > 4
Likely
power via fossil fuel combustion) and thereby reducing the impact of the chemical process industry (from CO2 emissions) on global warming.
The basic principle behind high-quality energy carriers (fossil fuels, solar
energy) follows from thermodynamics. All process steps are carried out in a nite
time and are therefore irreversible, by which high-quality energy is converted to
lower-quality energy. This is called exergy loss. By reducing the number of highly
irreversible process steps, exergy losses are reduced (42).
This can be achieved by combining process functions into one process step. It
can also be obtained by reducing the number of units just by selecting the best units
and their sequence. It can also be achieved by reducing the biggest driving forces by
evenly spreading them over the process steps. This will result in general in energy
savings and in reductions of carbon dioxide emission (43). For distillations the savings are of the order of 30% (reduction by a factor of 1.4) (43).
Individual pieces of PI equipment, as listed by Stankiewicz and Moulijn
(5), requiring alternative energy sources such as microwaves and centrifugal
elds will often result in higher energy requirements. Once again, the process
step is made more irreversible (faster by higher driving forces). By assessing the
energy requirements of the whole lifecycle, energy requirement reductions may
be achieved, via, for instance, a higher selectivity, i.e., a reduction in feedstock consumption. And feedstock preparation is also associated with energy requirements.
3.3.2.3. Photochemical Pollutant Reduction. Smog is caused by photochemical oxidants. The formation of photochemical oxidants is mainly due to
volatile organic compound (VOC) emissions. Seventy to ninety percent of VOC
emissions from chemical plants are from leaking anges, seals, etc. (44). Process
intensication can reduce considerably the number of pieces of equipment and
thereby the number of anges and seals. Moreover, the few remaining anges
could be designed such that fugitive emissions are below the limits for smog formation, and the additional cost can be limited. This means fewer leaks and lower
fugitive emissions to air, water, and soil. The introduction of process intensication could therefore make a major contribution to VOC emission reduction.
3.3.2.4. Acidication. The acidication and thermal pollution impacts
of a chemical plant in general do not come from the plant itself but are related to
the conversion of fossil fuel to energy (steam, electricity); hence the same emission reduction factor as for carbon dioxide is assumed for the process intensication potential.
3.3.3.
Economy/Prot
3.3.3.1. Scarce Resource Depletion. For any new technology, the longterm and worldwide effects on scarce-resource consumption should be assessed
over its entire lifecycle. For instance, even minute amounts of rare earth metals per
application can, in the long run (and when the technology is applied worldwide),
deplete that scarce resource. (This is of course not only an economic issue but
also an ethical and ecological one).
The present resources of drinking water and fossil carbon components are
already seen as limited. Careful use and development of alternatives is now being
pursued. Process intensication has the potential of requiring less energy and
thereby requiring less fossil carbon as fuel.
3.3.3.2. Economic Cost Reduction Potential. The major part of the cost
of manufacturing chemical products is the feedstocks. The capital expenditure per
unit product is in general between 10% and 30%. The energy cost is in general
between 5% and 10%.
With bulk chemicals the feedstock costs are in general close to the theoretical minimum, due to the high selectivity achieved (90% and higher). The introduction of PI in this eld can lead to a reduction in capital expenditure and of energy
utilities by a factor 5 (38); a variable cost reduction factor of 1.4 is achievable.
In the ne chemicals industry the selectivity gures are in general far lower.
Here big feedstock cost savings is achievable by more selective processes. This is
mainly achieved by changing from stoichiometric acid and alkaline feed-driven
processes to truly catalytic processes (45).
But via, for instance, high-heat exchange reactors (HEX reactors) that
allow a much shorter reaction time and at the optimal temperature, process intensication can also reduce the formation of by-products considerably. A by-product
reduction by a factor of 4 is achieved via a HEX reactor (46). This means a considerable reduction in feedstock cost and waste handling.
3.4. Traps for Process Intensication Leading to
Unsustainable Technologies
Larger emissions or consumption of scarce resource could occur elsewhere in the
lifecycle via the large-scale introduction of process intensication. For example,
the proposed printed circuit board reactors could in the manufacturing step cause
large emissions of VOCs from cleaning chemicals. And the demolition phase could
also cause a large waste stream.
4.
EPILOGUE
It is clear from the foregoing that presently known PI methods can contribute considerably to the process industry in meeting the social, ecological, and economic
constraints of sustainable development. For each new application it remains a
challenge to the engineers to identify ways to provide for the needs of people,
especially the poor, while meeting all SD constraints.
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RE-ENGINEERING

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1. Fluid Catalytic Cracking with Zeolite Catalysts, Paul B. Veriuto and E.

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23. Modern Control Techniques for the Processing Industries, T. H. Tsai, J.

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51. Computer-Aided Design of Catalysts, edited by E. Robert Becker and

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78. The Desulfurization of Heavy Oils and Residua, Second Edition,

Handbook of Methyl Tertiary Butyl Ether, edited by S. Halim Harriid and

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educated and environment-conscious society, there will be no room (literally and

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7. Inline and High-Intensity Mixers

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David W. Agar Lehrstuhl fr Technische Chemie B, University of Dortmund,

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Freek Kapteijn Delft University of Technology, Delft, The Netherlands

Greth, CEAGrenoble, Grenoble, France

The Dow Chemical Company, Freeport, Texas, U.S.A.

Henk van den Berg Faculty of Chemical Technology, University of Twente,

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metallurgical processing (4 7) (an interesting coincidence, considering that

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FIGURE 3 DSMs vision of process intensication.

Source: Ref. 32.

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FIGURE 4 Main benets from process intensication.

Process intensication leads to substantially cheaper processes, particularly in

Process intensication drastically increases the safety of chemical processes. It

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Process intensication also offers substantial improvements to those sectors of

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TABLE 2 Some 20th Century Disasters in the Chemical Industry

4,500 tons exploded

ca. 600 dead, 1500 injured

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14 dead, 107 injured

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PROCESS INTENSIFICATION TOOLBOX

The toolbox for process intensication is schematically shown in Figure 7. It

As already mentioned, one classic example of technological breakthroughs in

FIGURE 7 Process intensication toolbox.

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FIGURE 8 Various types of static mixers. (Courtesy: Koch-Glitsch.)

FIGURE 9 Static mixer reactor developed by Sulzer. (Courtesy: Sulzer

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FIGURE 10 Sulzers KATAPAK-M. (Courtesy: Sulzer Chemtech.)

KATAPAKs are applied in catalytic distillation and in some gas-phase exothermic

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FIGURE 11 Super X-Pack, developed by Nagaoka International Corp.

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FIGURE 13 Monolithic catalysts.