CHAPTER I

INTRODUCTION

TO PERVAPORATION
 CHAPTER-1

INTRODUCTION TO PERVAPORATION

This chapter deals with the general introduction on membrane science and
technology. It describes the history, definition of terms pervaporation, classification
of membranes, different membrane processes, pervaporation mechanism,
applications of membranes, advantages of membrane technology etc. The literature
survey pertaining to the present investigation and aim and the scope of the present
investigation also included in this chapter.

Chapter-1 1
1.1 General Introduction:

The separation and purification' of liquid mixtures is major problem in the

chemical industries. Efficient separation processes are needed to obtain high-grade
pure products in the food and pharmaceutical industries to supply communities and
industry with high-quality water, and to remove or recover toxic or valuable
components from industrial effluents. For this task member different methods of
separation techniques such as distillation, precipitation, crystallization, extraction,
adsoiption, and ion-exchange are used today. More recently, these conventional
separation methods have been supplemented by a family of processes that utilize
semipermeable membranes as separation barriers.

Membranes and membrane processes were first introduced as an

analytical tool in chemical and biomedical laboratories; they developed very
rapidly into industrial products and methods with significant technical and
commercial impact [1-5]. Today, membranes are used on a large scale to
produce potable water from sea and brackish water, to clean industrial effluents
and recover valuable constituents, to concentrate, purify, or fractionate
macromolecular mixtures in the food and drug industries, and to separate gases
and vapors in petrochemical processes. They are also key components in energy
conversion and storage systems, in chemical reactors, in artificial organs, and in
drug delivery devices.

The membranes used in the various applications differ widely in their

structure, in their function and the way they are operated. However, all
membranes have several features in common that make them particularly
attractive tools for the separation of molecular mixtures. Most important is that
the separation is performed by physical means at ambient temperature without
chemically altering the constituents of a mixture. This is mandatory for
applications in artificial organs and in many drug delivery systems as well as in
the food and drug industry or in downstream processing of bioproducts where
temperature-sensitive substances must often be handled. Furthermore, membrane

Chapter-1 2
properties can be tailored and adjusted to specific separation tasks, and
membrane processes are often technically simpler and more energy efficient than
conventional separation techniques and are equally well suited for large-scale
continuous operations as for batch-wise treatment of very small quantities.

A membrane can be much more complex in both structure and function. A

membrane may be solid or liquid, homogeneous, isotropic or anisotropic in its
structure. A membrane can be a fraction of a micrometer or several millimeters
thick. Its electrical resistance can vary from millions of Ohm to a fraction of an
Ohm.

Another characteristic property of a membrane is its permselectivity,

which is determined by differences in the transport rates of various components
in the membrane matrix. The permeability of a membrane is a measure of the
rate at which a given component is transported through the membrane under
specific conditions of concentration, temperature, pressure, and/or electric field.
The transport rate of a component through a membrane is determined by the
structure of the membrane, by the size of the permeating component, by the
chemical nature and the electrical charge of the membrane material and
permeating components, and by the driving force, i.e. concentration, pressure or
electrical potential gradient across the membrane. The transport of certain
components through a membrane may be facilitated by certain chemical
compounds, coupled to the transport of other components, or activated by a
chemical reaction occurring in the membrane.

These phenomena are referred to as facilitated, coupled, or active

transport. We can distinguish between biological membranes, which are part of

the living organism, and synthetic membranes that are man-made. Biological
membranes carry out very complex and specific transport tasks in living
organisms. They accomplish them quickly, efficiently, and with minimal energy
expenditure, frequently using active transport.

Chapter-1 3
 Synthetic membranes are not nearly as complicated in their structure or
function as biological membranes. They have only passive transport properties and
are usually less selective and energy efficient. In general, however, they have
significantly higher chemical and mechanical stability, especially at elevated
temperatures. The selectivity of synthetic membranes is determined by a porous
structure according to their size or through a homogeneous structure according to
the solute solubility and diffusivity. The permeability of the membrane for different
components, however, is only one parameter determining the flux through the
membrane, just as important as the permeability is the driving force acting on the
permeating components. Some driving forces such as concentration, pressure, or
temperature gradients act equally on all components, in contrast to an electrical
potential driving force, which is only effective with charged components. The use
of different membrane structures and driving forces have resulted in a number of
rather different membrane processes such as reverse osmosis, micro-, ultra- and
nanofiltration, dialysis, electrodialysis, Donnan dialysis, pervaporation, gas
separation, membrane contactors, membrane distillation, membrane-based solvent
extraction, membrane reactors, etc.

Even more heterogeneous than membrane structures and membrane

processes are their practical applications. The large-scale industrial utilization of
membranes began about 1970 with water desalination and purification to produce
potable and high quality industrial water. Since then membranes have become a
widely used tool in process engineering with significant technical and commercial
impact.

Today membrane processes are used in three main areas. The first area
includes applications such as seawater desalination or wastewater purification.
Here, the use of membranes is technically feasible, but there are other processes
such as distillation and biological treatment with which membranes must compete
on the basis of overall economy. The second area includes applications such as the
production of ultra pure water or the separation of molecular mixtures in the food

Chapter-1 4
and drug industry. Here, alternative techniques are available, but membranes offer
a clear technical and commercial advantage. The third area includes membrane
applications in artificial organs and therapeutic systems. There is no reasonable
alternative to membrane operations in this area.

With the development of new membranes having better separation

efficiency, new membrane processes such as membrane contactors and membrane
reactors are becoming common unit operations in process engineering [2,6-8], The
large-scale use of membranes is rapidly extending far beyond its present level.

1.2. History of membranes

Synthetic membranes are a rather recent development and the technical

utilization of membrane processes on a large scale began just 40 years ago. The
first recorded study of membrane phenomena and the discovery of osmosis dates
back to the middle of the 18th century when Nollet [9] discovered that a pig's
bladder passes preferentially ethanol when it was brought in contact on one side
with a water-ethanol mixture and on the other side with pure water. Nollet was
probably the first to recognize the relation between a semipermeable membrane
and the osmotic pressure. More systematic studies on mass transport in
semipermeable membranes were carried out by Graham who studied the diffusion
of gases through different media and discovered that rubber exhibits different
permeabilities to different gases [9].

Most of the early studies on membrane permeation were carried out with
natural materials such as animal bladders or gum elastics. Traube was the first to
introduce an artificially prepared semipermeable membrane by precipitating
cupric ferrocyanide in a thin layer of porous porcelain. This type of membrane was
used by Pfeffer in his fundamental studies on osmosis. The theoretical treatment
and much of the interpretation of osmotic phenomena and mass transport through
membranes is based on the studies of Fick who interpreted diffusion in liquids as a
function of concentration gradients, and van t'Hoff who gave a thermodynamic
explanation for the osmotic pressure of dilute solutions [10].

Chapter-1 5
 Little later Nemst and Planck introduced the flux equation for electrolytes
under the driving force of a concentration or electrical potential gradient. With the
classical publications of Dorman describing the theory of membrane equilibria and
membrane potentials in the presence of electrolytes, the early history of membrane
science ends with the most of the basic phenomena satisfactorily described and
theoretically interpreted [11].

In the early days of membrane science and technology membranes had been
mainly a subject of scientific interest with only a very few practical applications.
This changed drastically from 1950'on when the practical use of membranes in
technically relevant applications became the main focus of interest and a significant
membrane-based industry developed rapidly. Progress in polymer chemistry
resulted in a large number of synthetic polymers which ultimately became
available for the preparation of new membranes with specific transport properties
plus excellent mechanical and thermal stability. Membrane transport properties
were described by a comprehensive theory based on the thermodynamics of
irreversible processes [12]. A second route for describing membrane processes was
based on postulating certain membrane transport models such as the model of a
solution- diffusion membrane. The properties of ion-exchange membranes and
their practical use were also subject of extensive studies [13].

Soon after the development of efficient membranes, appropriate membrane

housing assemblies, called modules, were devised. The criteria for the design of
such modules included high membrane packing density, reliability, ease of
membrane or module replacement, control of concentration polarization, and low
cost. Membranes were produced in three different configurations, i.e. as flat
sheets, as hollow fibers or capillaries, and as tubes. In today's reverse osmosis
desalination plants mainly spiral wound modules are used while hollow fiber
membrane modules are utilized in gas separation and pervaporation. In medical
applications such as artificial kidney and blood oxygenator capillary membranes
play a dominant role today. Tubular membranes are mainly used in micro- and
ultrafiltration.

Chapter-1 6
 Even earlier than the large scale use of reverse osmosis for sea and brackish
water desalination was the industrial scale application of electrodialysis. The
history of electrodialysis goes back to the development of the first multi-cell stack
[14]. However, modern electrodialysis became a practical reality with the
development of the first reliable ion- exchange membranes having both good
electrolyte conductivity and ion-permselectivity [15]. Electrodialysis was first
commercially exploited for the desalination of brackish water by Ionics Inc. The
commercial success of Ionics was due to their membranes, their compact stacking,
and the mode of operation referred to as electrodialysis reversal, which provided a
periodic self-cleaning mechanism for the membrane stack and thus allowed long­
term continuous operation at high concentrations of scaling materials without
mechanical cleaning of the stack [16].

In the early 1980's a completely new area for the application of

electrodialysis was opened up with the introduction of bipolar membranes for the
recovery of acids and bases from the corresponding salt solutions [17]. The large-
scale separation of gases and vapors is also a relevant industrial area for
membrane applications. Gas separation was pioneered by Monsanto Inc. [18].
Originally, the aim was to recover hydrogen from off-gases and to produce oxygen-
or nitrogen-enriched air. Today, however, a large number of other applications
such as the removal of CO2 from natural gas or the recovery of organic vapors
from off-gases are typical applications for gas and vapor separation. Pervaporation
which is closely related to vapor separation was studied extensively, and a large
number of interesting potential applications were pointed out [19].

But so far very few large commercial plants have been built. Other
applications of membranes which were developed in recent years that have
reached large technical and commercial significance include the controlled release
of drugs in therapeutic devices and the storage and conversion of energy in fuel
cells and batteries. However, the commercially most important application of
membranes today is in reverse osmosis water desalination and in hemodialysis
and hemofiltration.

Chapter-1 7
1.3. Definition of membrane

Membrane is defined essentially as a barrier, which separates two phases

and restricts transport of various chemicals in a selective manner. A membrane can
be homogenous or heterogeneous, symmetric or asymmetric in structure, solid or
liquid; can carry a positive or negative charge or be neutral or bipolar.

1.4. Classification of membranes

Membranes are being developed from a wide range of materials including

metals, polymers, ceramics and biological materials. Membrane morphology and
structure can be manipulated by physical and chemical methods to bring the desired
separation, However, the choice of method and material for separation is often
dictated by the economics of the technology involved. Membranes can be classified
based on the origin (Synthetic or Natural), Nature (organic and inorganic), structure,
applications and the mechanism by which the separation is affected. Classification
of membranes based on applications is presented in Fig 1.2.

Symmetrical membranes

Isotropic micro porous Nonporous dense Electn tally charged

membrane membrane membrane

Anisotropic membranes Supported liquid

membrane

Liquid-
filled
pores

Loeb-Sourirajan
anisotropic membrane
Thin-film composite
anisotropic membrane t Polymer
matrix

Fig 1.1: Classification of Membranes

Chapter-1 8
1.5. Separation processes

Separation processes have importance in the manufacturing of the chemical

process industries. They are used for important tasks as removal of contaminants
from raw materials, recovery and purification of primary products and elimination of
contaminants from effluent water and air streams. There are many types of
separation processes viz., fractional distillation, solvent extraction, adsorption and
membrane separations. The heart of the separating process is the mass-separating
agent. In fractional distillation, it is heat; in solvent extraction, the solvent; in
adsorption, the adsorbent; and in the membrane separation processes, the membrane
material. Separation of solvents or gas mixture is of extreme importance in a variety
of industries like from chemical, food and pharmaceuticals.

Distillation and liquid-liquid extraction are two of the most common and
traditional technologies used for solvent separations. Both of these technologies are
mature and have been extensively used for commercial large-scale separations.
However, these technologies have certain disadvantages associated with them.
Distillation generally is an energy intensive process and since the basis of separation
is the relative volatility of the compounds, the technique fails in the case of
azeotropes i.e. mixtures wherein the relative volatility of the compounds is unity.
Thus for azeotrope separation, one may have to resort to the use of more cost
intensive processes such as azeotropic or vacuum distillation. Also, conventional
distillation cannot be used for the separation of solvent mixtures, which contain a
heat sensitive compound (commonly encountered in the food, perfumery and
pharmaceutical industries). Liquid liquid extraction, on the other hand suffers from
the major drawback of enhanced downstream processing due to the presence of an
additional solvent. In the food and pharmaceutical industries, the introduction of the
liquid extractant could also cause problems in terms of the purity of the final food or
drug product. Thus in cases, where the conventional technologies would fail to meet
the desired separation objectives, the use of alternate technologies may be required.
Recently, membrane based separation techniques have got lot of attention from
scientific community, due to their advantages in separation science.

Chapter-1 9
1.6. Membrane Based Separation processes

Membrane is a barrier, which separates two phases and restricts transport of

various chemicals in a selective manner. A membrane can be homogenous or
heterogeneous, symmetric or asymmetric in structure, can cany a positive or
negative charge or neutral or bipolar [20, 21]. Transport through a membrane can be
affected by convection or by diffusion of individual molecules, induced by an
electric field or concentration, pressure or temperature gradient.

In recent past, membrane based processes have become industrial products of

substantial technical and commercial importance due to the wide range of
applications. Such methods can be useful to produce potable water from seawater, to
treat industrial effluents [22], to recover hydrogen from off-gases or to fractionate
[23] and in pharmaceutical industry [24]. Membranes are also key elements in
artificial kidneys [25] and controlled drug delivery systems [26].

The growing significance of membranes and membrane processes as

efficient tools for laboratory and industrial scale mass separations is based on the
several properties, characteristic of all membrane separation processes, which make
them superior to many conventional mass separation methods. The mass separation
by means of a membrane is a physical procedure carried out at ambient temperature,
thus the constituents to be separated are not exposed to thermal stress or chemical
alteration. This is of particular importance for biochemical or microbiological
applications where often mixtures of sensitive biological materials have to be
separated. Furthermore, membrane processes are energy efficient and rather simple
to operate in a continuous mode. Significant difference occurs in the membranes
used viz., driving forces for the mass transport, the applications and also in their
technical and economical significance.

In some of the processes the membranes as well as the processes have

reached such a level that completely new developments cannot be expected. Some
examples of this are in microfiltration, ultrafiltration, reverse osmosis, dialysis or
electro-dialysis. In these processes only improvements and optimization of existing

Chapter-1 10
systems and their adaptation to special applications are to be expected. Other
processes, such as pervaporation and vapor permeation, are in the very beginning of
their industrial application and offer the possibility of totally new developments of
membranes and modules.

1.7. Classification of Membrane Based Separation Processes

Pressure driven membrane based processes can be classified into seven types
based on the size of the permeable species and concentration of solute.

A. Microfiltration:

Microfiltration (MF) membranes are used for separation of fine particles

from solutions. MF is a process mainly used for the separation of submicron size (<
0.1 pm) particulate matter from solution. This process also requires hydrostatic
pressure gradient across the membrane and the pressure used is of the order of 100
kPa. The pore sizes of the membranes decide the size of the particulate matter
retained. The process is similar to ultrafiltration and separation takes place by
sieving. Most MF membranes are symmetric. Most commonly cellulose nitrate or
acetate, poly (vinylidene difluoride) (PVDF), polyamides, polysulfone used as
membrane material in MF processes. MF processes are generally applied in
clarification, sterilization and slurry concentration. MF processes are typically
applied in the removal of bacteria from water samples [27] and removal of
submicron size suspended dust and particulate matters from gas streams [28].
Removal of chemical oxygen demand from effluent waters [29] is another important
application of the MF process.

B. Ultrafiltration:

The ultrafiltration (UF) is a membrane based separation process wherein the

solvent along with micro solutes permeates through the membrane and macro
solutes are retained by the membranes. This process is similar to sieving and the
driving force is the hydrostatic pressure across the membrane. Size or the molecular
weight difference of the macro solute retained by the membrane depends upon the

Chapter-1 11
pore size of the membranes. Micro solutes whose effective sizes are smaller than the
pore size of the membranes permeate along with the solvent whereas macro solutes
whose effective sizes are larger than the pore size of the membranes are retained.
The driving force used in ultrafiltration processes is of the order of 500 kPa or so.
The membranes used in UF processes are asymmetric, microporous and having pore
radius between 1 to lOnm.

UF processes are mostly used in separation of macromolecular solutions

[30] . The major areas of application are in purification of proteins and nucleic acids
[31] and virus removal from bio products [32]. UF is attractive because of the high
purity of separation of product, low process cost and ease of scale-up. Commonly;
polymers like polysulfone, polypropylene, nylon 6, PTFE and PVC are used as a
membrane material in UF processes.

C. Reverse Osmosis:

Reverse osmosis (RO) is a membrane-technology filtration method that

removes many types of large molecules and ions from solutions [33] by applying
pressure to the solution when it is on one side of a selective membrane. The result is
that the solute is retained on the pressurized side of the membrane and the pure
solvent is allowed to pass to the other side. To be "selective", this membrane should
not allow large molecules or ions through the pores (holes), but should allow smaller
components of the solution (such as the solvent) to pass freely. Membranes used in
reverse osmosis are asymmetric skin type and has pore radius ranging between 0.5
to 1.5 nm. Process of RO is mainly used in separation of salts and micro solutes
from solutions.

D. Electrodialysis:

Electrodialysis (ED) process is generally used for desalination of water. In

ED electrolytes are removed from one solution to the other. The cations and anions
permeate through cation selective: and anion selective membranes, respectively as a
result of applied electrical energy. Even though RO and ED are both useful for
desalination, there is a fundamental difference between the two techniques.

Chapter-1 12
 In RO, the solvent permeates through the membranes and solutes, both
electrolytes and non-electrolytes, are retained by the membranes while In ED,
electrolytes permeate through the membranes and, the solvent and non-electrolytes
generally do not permeate through the membranes. The solution from which
electrolytes are removed gets depleted of salt and the solution which receives the
solute gets enriched with salt.

E. Nanofiltration:

The process of Nanofiltration (NF) is slightly different from the reverse

osmosis process in the sense that the permeating species in this case is solvent as
well as low molecular solutes or low valence solutes. This process also operates with
hydrostatic pressure difference across a semi-permeable membrane having pore
sizes which are slightly larger than that of reverse osmosis membranes. The pore
sizes of NF membranes are in the range of 1 to 3nm. The hydrostatic pressure used
in this process can vary from 1.5 Mpa to 2MPa. This process is essentially used to
fractionate solutes based on valency of either cation or anion and also to separate
various organic solutes of low molecular weights [34], Membranes fabricated by
using polymer; cellulose acetate and aromatic polyamide are commonly used in NF
for removal of hardness and desalting.

F. Gas Separations:

A typical membrane process for gas separation operates with hydrostatic or

partial pressure and concentration gradient across the membrane. Gas separation
membranes are asymmetric and homogeneous. The feed gas mixture is fed to the
membrane at an elevated pressure, where it permeates across the membranes. The
other side of the membranes is held at a lower pressure. Separation is achieved
because of differences in the selective permeation rates of the feed gas components.

Components that permeate more rapidly across the membranes become

enriched in the permeate stream while the slower permeating components are
concentrated in the residual at high pressure. Important applications of gas
separation using membranes are in the production of high purity nitrogen from air,

Chapter-1 13
oxygen enrichment from air and recovery of helium from mixture of organic gases
[34].

G. Pervaporation:

Pervaporation (PV), name originates from a combination of the terms

permeation and vaporization; can be defined as, a membrane based separation
process by which azeotropic, closely boiling mixtures or isomers can separated on
their selective permeation followed by evaporation. PV is relatively new membrane
separation process and it was first developed in 1917 by Kober. Now days, PV
processes are generally used mainly in following applications:

a. Removal of water from organic solvent

b. Separation of closely boiling organic liquid mixtures

c. Separation of isomeric mixtures

d. Separation of azeotropic liquid mixtures

From above mentioned applications, separation of azeotropic mixtures is an

important category as; azeotropic mixtures are cannot be separated by using
conventional distillation method. For example; ethanol forms azeotropic mixture at
4% of its aqueous solution, isopropanol forms azeotropic mixture at 12.2% at its
aqueous solution. Conventional distillation method is not able to separate such type
of mixtures which can be efficiently separated by using PV technique.

Chapter-1 14
 Table: 1.2 Comparison of various membrane separation processes

Phases of
Membrane processes. Driving forces Separation mechanism
feed! permeate

Microfiltration Liquid •' Liquid Hydrostatic pressure Sieving

Ultrafilrration Liquid i Liquid Hydrostatic pressure Sieving
Hyperfiltration Liquid > Liquid Effective pressure Preferential sorption and
capillary flow

Dialysis Liquid1 Liquid Concentration gradient Sieving and hindered

diffusion
Electrodialysis Liquid/Liquid Electrical potential gradient Counter-ion transport
Reverse osmosis Liquid / Liquid Hydrostatic pressure Preferential sorption and
capillary flow

Perraporahon Liquid/Vapor Chemical potential gradient Solution-diffusion

Vapor permeation Vapor / Vapor Chemical potential gradient Solution-diffusion

Gas separation Gas / Gas Partial pressure difference Solution-diffusion and

sieving

1.8 Advantages of membrane technologies

The technologies of membrane separation have been developing to be the

top of process separation. The advantage of membrane separation has been found in
certain processes such as producing materials, separation, recovering, and drying
[35]. The advantages are:

❖ The membranes are highly selective and so it has high effectiveness in

separation process.

❖ Membrane processes are characterized by low energy consumption,

possibility of different module design and easy scale up. These
advantages make these processes superior to many other established
separation processes.

Chapter-1 15
 ❖ The membrane based separation processes are cost effective and
environment friendly.
❖ These polymers not only exhibit better thermal and mechanical
properties than natural polymers, but also present a wide range of gas
transport and separation properties.
❖ Membrane processes are able to recover minor but valuable
components from a main stream without substantial costs.
❖ The separation process of membrane do not used large or complex
machine that have to more from a part of plant to another part of plant.
It only consist some instrument that is easy to operate. This process
can be continuously used.

1.9. The future of membrane science and technology

In many applications today's membranes and processes are quite

satisfactory while in other applications there is a definite demand for further
improvements of both membranes and processes. For sea and brackish water
desalination by reverse osmosis, e.g. there are membranes available today that
are quite satisfactory as far as flux and salt rejection are concerned, and the
processes are proven by many years of operating experience. The same is true for
hemodialysers and hemofiltration. In these applications only marginal
improvements can be expected in the near future. In micro- and ultrafiltration or
electrodialysis the situation is similar.

The properties of present membranes are satisfactory. However, there are

other components such as the process design, process control, application know­
how, and long-term operating experience that are of importance in the use of
micro- and ultrafiltration in the chemical and food industry or in waste water
treatment. Here, concentration polarization and membrane fouling play a
dominant role and new membrane modules and process design concepts which
provide a better control of membrane fouling resulting in a longer useful life of the
membranes are highly desirable.

Chapter-1 16
 In other membrane processes such as gas separation, pervaporation, fuel
cell separators, membrane reactors, etc. the situation is quite different. Here, better
membranes, improved process design, and extensive application know-how and
long-term experience are mandatory to establish membrane processes as a proven
and reliable technology.

In addition to the established membrane processes and applications, new

membrane operations such as membrane contactors and membrane reactors are
growing at industrial level and becoming common unit operations in process
engineering, contributing also to the overall impact of membrane engineering on
any industrial production [36, 37]. It is also particularly important that all
membrane operations are well consistent with the requirements of the process
intensification strategy and of a sustainable industrial development. Chemical
process rationalization and miniaturization, the basic concepts of the process
intensification are now a goal in all manufacturing processes. With their intrinsic
properties of high energy efficiency and operational simplicity, high transport
selectivity, large operational flexibility, and environment compatibility, membranes
and processes are important tools for advanced molecular separations and chemical
transformations overcoming existing limits of the traditional industrial processes.

1.10. Review of pervaporation

Pervaporation is a membrane process for liquid separation. In pervaporation,

the liquid mixture to be separated is placed in contact with one side of a membrane
and the permeated product is removed as a low-pressure vapor from the other side
by liquids selective transporting through a homogeneous, nonporous membrane with
the evaporation of permeates. The partial vaporization of feed molecules and a phase
change of the permeate are important characteristics of this process. The separation
achieved is based on the sorption and diffusion differences between the feed
components, which are mainly controlled by the complicated interactions among the
feed components, the membrane material, and the permeate. Figure 1.2: illustrates
the schematic diagram of pervaporation process.

Chapter-1 17
 Pervaporation is a relatively new membrane separation process that has
certain common elements with reverse osmosis and gas separation. In 1906,
Kahlenberg first observed the selective transport of hydrocarbon/alcohol mixtures
through a thin rubber sheet [38], and in 1917, Kober introduced the term
“pervaporation” in his report about the selective permeation of water from aqueous
solutions of albumin and toluene through collodion (cellulose nitrate) films [39].
Later on, Schwob focused on the dehydration of water/alcohol mixtures through a
thin cellulose film. He compared two permeate flow rates; one was achieved when
the feed was in direct contact with the membrane and the other was when the
membrane was faced with the mixed vapor [40].

The latter process has been termed “vapor permeation” nowadays. In this
work, it was found that if the water in feed mixture was not more than 30wt%, the
membrane presented a larger permeation flux and without significant loss in
selectivity when the liquid directly contacted with the membrane. When the water
was beyond 30wt%, the membrane was extensively swollen by the feed liquid and
the selectivity became lower than that of vapor permeation. These early observations
have a practical contribution for the dehydration of alcohols in modem
pervaporation application. The exploring work has been continued by the precursors
such as Farber and Heisler [41,42].

Chapter-1 18
 Between 1958 and 1962, Binning and coworkers established the principles of
pervaporation and proposed the potential of this technology based on their research
on the separation of hydrocarbon mixtures through a non-porous polyethylene film
[43-45], These experiments were earned out at high temperatures up to 150°C, at
which the permeation rates were high enough to permit practical applications. Then-
results showed that aromatics and olefins permeated faster than paraffins, and the
linear hydrocarbons permeated faster than branched isomers, which suggested the
feasibility to increase the number of octane in gasoline by pervaporation. In
addition, they also reported the separation of other mixtures such as
methanol/benzene, alcohols/water and pyridine/water by pervaporation [46-49].

1.11. Background of Pervaporation:

As early as 1906, Kahlenberg reported some qualitative observations

concerning the selective transport of hydrocarbon/alcohol mixtures through thin
rubber sheet (50). The term Pervaporation was first introduced by Kober (51) who
observed that “a liquid in a colldion bag, which was suspended in the air,
evaporated, although the bag was tightly closed”. Farber (52) at the University of
Toronto presented the results of work using pervaportion for concentrating protein
solutions. Schwob (53, 54) dehydrated water/alcohol mixtures by means of thin (20
pm) regenerated cellulose film (Cellophane). Heisler et al. (55) reported their
findings on dewatering of ethanol solutions through regeneration of cellulose in
1956.

Initially, homogenous membranes were used for pervaporation. The low

magnitude of permeation flow- rates through these homogenous dense films seemed
to prevent its further development for industrial applications. The development of
the “phase inversion” membrane making method by Loeb and Sourirajan in the
1960’s -to manufacture high-flux asymmetric membranes provided a possible
solution to overcome the earlier problem of low flux (56).

The first major research effort in Pervaporation was undertaken in the later
1950s by brining and associates at the American Oil Company (Amoco) in Texan

Chapter-1 19
(57). They conducted a series of investigations on the separation of hydrocarbon
mixtures using cellulosic and polyethylene membranes. Binning et ah, (1958)
reported the use of membrane Pervaporation for dehydration of a ternary azeotrope
of isopropanol, ethanol-water from the overhead of a distillation column. The group
also separated an equi-volume mixture n-heptane and iso-octane through unnamed
“thin polymer films” (58). Several papers discussed azeotropic benzene/methanol
separation and reversal of selectivity with different membranes. The experiments
showed that aromatics and olefins permeate faster than paraffins, and linear
hydrocarbons permeate faster than branched isomer (58). This process was used to
improve the octane number of gasoline. More than 10 patents were issued to Amoco
in those years citing members of the research goup as inventors (59, 60).

Meanwhile, systematic studies on Pervaporation and vapor permeation

were stated in France by Neel and other (Fries and Neel, (61), Aptel et al.(62). Their
experiments clearly demonstrated that Pervaporation and distillation could be
associated to fractionate mixtures of close boiling-temperature liquids, or mixtures
leading to azeotropes. Thus, this new membrane technique became a competitor to
sophisticated and energy-consuming processes, such as extractive and low-pressure
distillation.

In addition to the development of better membrane materials, the energy

crisis in the 1970s refocused interest in separation technology that possessed a high
potential for energy savings. This greatly enhanced the commercialization of
pervaportion.

In the mid 1970s, Gesellschaft Filr Trenntechnik (FGT), a German

company commercialized an economical Pervaporation process for dehydrating
ethanol that produces high purities' rivaling those achieved by azeotropic distillation
(Fleming and Slater, (63). Following pilot trails in Europe, the first industrial
applications were in Brazil and the Philippines for the production of ethanol via
continuous fermentation of sugar cane, bagasse and sweet sorghum.

Chapter-1 20
 The fermented material contained 5 to 7% ethonal and it was concentrated
by primary distillation to a mash containing 80 to 85% ethanol, followed with
vacuum Pervaporation to 96 wt.% (Ballweg et al., 1982) (64). The primary
advantages for the GFT process were as follows. First, no additives were necessary
for the final separation. Second, energy demand was reduced, because only the
fraction of the liquid, which permeate across the membrane, has to be vaporized.
Third only a small vaccum pump was required, because the condensing permeate
continuously created a driving vaccum force. Fourth, closed -loop operation, with
only a small volume of recycled permeate, Fifth, much lower capital cost, Sixth,
recovery of the initial thermal energy supplied as low pressure steam (<90 psi).

In the late 1970s and continuing into early 1980s, other integrated distillation
/ Pervaporation plants were built in Europe and Asia. Most of these were of
moderate capacity, typically with ethanol recovery of 1000 to 50000 L/day (Fleming
and Slater, 1992) (63). As the cost of the perm selective membrane modules
decreased, and the selectivity increased (99.85% ethanol purity became easily
attainable). The integrated process gained industrial acceptance. Today, a number of
commercial Pervaporation plants exist for ethanol dehydration. In 1980, a 150000
L/day ethanol dehydration plant in Betheniville, France, became the largest
Pervaporation facility in the world (Rapin,1988) (65).

Applications of Pervaporation

The applications of Pervaporation can be classified into three categories.

• Dehydration of organic solvents

• Removal of dilute organics from aqueous streams
• Separation of organic mixtures

Chapter-1 21
1.12. Survey of Literature pertaining to the present study

Dehydration of isopropanol has received great attention from industries due

to the price of isopropanol and its uses in various industries. It is generally used as
solvent for oils, gums, waxes and variety of cosmetics and as a cleaning agent in the
semi conductors. Due to its vital role in various industries such as pharmaceutical,
paints, semi-conductor and LCD, most of the research efforts of the pervaporation
have concentrated on the separation of alcohol-water system. IPA is an important
basic solvent in the industry ranging among the top 10 organic intermediates.
Because of the small difference in the volatilities of water and IPA in dilute aqueous
solutions, azeotropic distillation is used instead of normal binary solutions so that
the process in an energy intensive process. From this point of view the pervaporation
separation of IPA/water mixture can be one of the alternative processes for saving

energy.

The application of PV as a means to achieve dehydration of solvents has

received a wide spread attention from chemical and pharmaceutical industries.
However, the recent technology improvements have lead to a rapid
commercialization of several novel membranes that are economical, safe and clean
to be used in the separation of azeotropic and close boiling liquid mixtures by the
PV technique [66].

Toti and Aminabhavi (67) prepared different viscosity grade NaAlg

membranes modified by solution casting method and cross-linked with GA in
methanol : water (75:25) mixture and used in PV dehydration of acetic acid and
isopropanol mixtures for feeds ranging 10-50 wt.% of water at308C. Cross-linking
reaction occurred between the -OH group of NaAlg and the -CHO group of GA due
to the formation of ether linkage by eliminating water, which is commonly observed
with most of the cellulose-based hydrophilic polymers (35, 36).

In order to further increase the PV performance of the membrane, low

viscosity grade NaAlg was modified by adding 10 wt.% of polyethyleneglycol
(PEG) in the presence of varying amounts (5 to20 wt.%) of PVA. Such modified

Chapter-1 22
membranes containing 10 wt.% PEG and 5 wt.% PVA showed the selectivity of 40
with a flux of 0.071 kg/m2 . h for 10 wt.% water containing feed mixture of acetic
acid.
Krishna Rao et al. (68) prepared NaAlg/HEC-g-acrylamide (AAm) blend
membranes to study the PV dehydration of acetic acid. These hydrophilic
membranes could recover only up to 89% of water from acetic acid for feed
mixtures containing 10 to 50 wt.% of water. Flux and selectivity to water have
increased with increasing amount of HEC-g-AAm grafted copolymer in the mixed
blend of NaAlg (54). A flux of 0.290 kg/m2 . h and a selectivity of 28 were
obtained, but these data are quite inferior to those found for other membranes.

R.S.Veerapur et.al.[69] prepared the Sodium alginate - magnesium

aluminum silicate mixed matrix membranes for pervaporation separation of water -
isopropanol mixtures. A .Krishnaiah et.al., [70] Studied the blend membranes of
sodium alginate and hydroxyethylcellulose for pervaporation - based enrichment of
t- butyl alcohol. K. Mallikarjuna Reddy et.al. [71] developed the Sodium alginate -
Ti02 mixed matrix membranes for pervaporation dehydration of tetrahydrofuran and
Isopropanol. Swayampakula Kalyani et.al.[12] conducted pervaporation studies for
the dehydration of ethanol-water mixtures through sodium alginate membranes.Toti
and Aminabhavi [73] obtained a highest flux of 74.7 g/m2h for 10%water in the feed

and the separation selectivity obtained in this case is 5 in the dehydration studies of
IPA using SA/PAAm-g-GG blend membranes. Membranes based on PAAm-g-SA
have been prepared by Toti and Aminabhavi [74] for the dehydration of IPA. They
reported the flux of 112.2 g/m2h where ;the water content in the feed is 70% and also
found a separation selectivity of 10.9 at the same feed composition at 30°C.

Kanti et al. (75) prepared polyion complex membranes by blending 84%

deacetylated CS and NaAlg followed by cross-linking with GA and tested for the PV
dehydration of ethanol. The membrane formed was washed with deionized water up
to 4-5 h followed by vacuum drying up to 5 h at 608C. Figure 3 displays the ionic
complexation reaction between cationic group (-NH3+C) of CS and anionic group (-
C002) of NaAlg as well as covalent cross-linking induced by the addition of GA.

Chapter-1 23
Cross-linked blend membranes could break the azeotrope containing 0.135 mol
fraction of water from the feed mixture giving a selectivity of 436 and a flux of
0.220 kg/m2 . h. Membrane selectivities were improved with a decrease in pressure,
but remained relatively constant for variable membrane thicknesses. Increasing the
membrane thickness decreased the flux, but higher permeate pressures caused
reductions in flux and selectivity. However, preferential interaction of water
molecules with the membrane material would cause the membrane to swell due to
absorption of liquid molecules in NaAlg matrix as well as membrane plasticization
effect, thereby allowing the unrestricted transport of both ethanol and water
molecules through the upstream layer.

Chitosan

Figure: 1.3 Ionic complexation reaction between cationic group of chitosan and the
anionic group of NaAlg.

Sodium alginate has received a great deal of attention due to its considerable
application either pure or composite form with other materials. SA is known for its
excellent film forming properties, currently this polymer was chosen for the
manufacture of membranes for PV dehydration studies [76]. These membranes were
extensively used in many industrial dehydration units.

Chapter-1 24
 They generally showed excellent selectivity towards water in organic
solvents, but with rather low permeabilities, especially where the organic solvent are
short chain alcohols. Although SA is known as semi-crystalline polymer it seems
that there were no detailed studies on the con-elation bet its crystallinity and its
transport properties in PV.

SA is a water-soluble bio-compatible polymer [77] consequently; much

attention has been paid to the applications of SA membranes for pervaporation
[78,79] dehydration of organic solvents. SA is the most selective polymer in PV
with regard to the dehydration alcohol/water mixture [80], SA has been successfully
utilized with the other polymer such as CS for PV separation of organic water
mixtures [81,82], Zhen Huang et al, [83] studied the dehydration of ethanol using
various zeolite (3A, 4A, 5A NaX and NaY ) filled SA composite membranes and
concluded that zeolite filled membranes showed higher separation factor, higher
fluxes and higher selectivity than unfilled SA membranes . Recent works [84-86] on
IPA and butanol dehydration demonstrated with high water perm selectivity and
durability suing commercial SA based multi layer membranes. The crosslinked SA
membranes have been frequently investigated for membrane based separations
because their hydroxyl groups have strong interactions with water through hydrogen
bonding [87],

A complete survey of the literature for the preparation of SA/SPI blend

membranes has been widely collected. Many efforts have been made in the literature
to increase the SA membrane performance by blending it with different natural
polymer [88],

Silva.et.al, (89) A physico-chemical characterization of blended membranes

composed by chitosan and soy protein has been carried out in order to probe the
interactions that allow membranes to be formed from these biopolymer mixtures.
These membranes are developed aiming at applications in wound healing and skin
tissue engineering scaffolding.

Chapter-1 25
 The investigations suggested that chitosan and soy may have participated in a
specific intermolecular interaction. The proton spin-lattice relaxation experiments in
the rotating frame on blended membranes indicated that independently of the
preparation conditions, the blend components are not completely miscible possibly
due to a weak polymer-protein interaction. It was also shown that the blended
systems showed a rougher surface morphology which was dependent of soy content
in the blend system.

Jun-Feng Su et.al.. (2010) (90) Edible films based on carboxymethy

cellulose (CMC) and soy protein isolate (SPI), compatibilized by glycerol, were
prepared by solution casting. The effects of CMC content on blend structure,
thermal stability, water solubility and water sorption, and mechanical properties
were systematically investigated. According to differential scanning calorimeter
(DSC) analysis, CMC/SPI blends add a single glass transition temperature (Tg)
between 75 and 100 °C , indicating that CMC/SPI form one phase blends.
Increasing the CMC content improved the mechanical properties and water
sensitivity of blend films. The results indicate that the structure and properties of SPI
edible films were modified and improved by blending with CMC.

Rupei Tang.et.al.,(2003) (91) To improve the mechanical and water vapor

barrier properties of soy protein films, the transparent films were prepared by
blending 5 wt % soy protein isolate (SPI) alkaline water solution with 2 wt %
carboxymethylated konjac glucomannan (CMKGM) aqueous solution and drying at
30 °C. The results demonstrated a strong interaction and good miscibility between
SPI and CMKGM due to intermolecular hydrogen bonding. The thermostability and
mechanical and water vapor barrier properties of blend films were greatly enhanced
due to the strong intermolecular hydroge bonding between SPI and CMKGM. The
tensile strength and breaking elongation of blend films increased with the increase of
CMKGM content: the maximum values achieved were 54.6 MPa and 37%,
respectively, when the CMKGM content was 70 wt %. The SPI-CMKGM blend
films provide promising applications to fresh food packaging.

Chapter-1 26
 Jun-Feng Su..et.al,.(2007) (92) Novel blend films of soy protein isolate (SPI)
and poly(vinyl alcohol) (PVA) compatibilized by glycerol were fabricated by
preparing a solution, and then casting it on a Teflon-coated metal sheet. Mechanical,
biodegradation and water vapor permeability of the blend properties were
systematically investigated with various methods. The blend plastics were softened
and became semi-rigid contributing to the plasticization of glycerol and the
crystalline partion of PVA was destroyed by glycerol Water vapor permeability of
SPI/PVA/glycerol showed the minimum at the component of SPI/PVA (100/35)
compatibilized by 3.5% of glycerol.

Mu L., Zhao H., et.al.,(2011) (93) Protein-polysaccharide conjugates were

generally prepared by dry-heating. However, it was time-consuming and the sample
gained was inhomogeneous. A faster way of preparing protein-polysaccharide
conjugates is needed. Accordingly, soy protein isolates (SPI)-Acaeia gum (GA)
conjugates prepared by the wet-heating method were studied in the present work.
Physicochemical properties of SPI-GA conjugates were also determined. The results
showed that the wet-heating method could improve the rate of the graft reaction of
protein and polysaccharide. The solubility of SPI-GA conjugates was significantly
(P < 0.05) higher than that of unreacted SPI-GA mixtures and SPI at the same pH
values. The emulsion activity index (EAI) of the grafted SPI increased remarkably.
The time course of the development of the graft reaction of SPI with GA was also
shown by SDS-PAGE.

Na Cao et.al (2007) (94) Mechanical, swelling, and optic properties of

composite films prepared from soy protein isolate (SPI) and gelatin were
investigated. With increasing gelatin ratio in composite films, tensile strength (TS),
elongation to break (EB), elastic modulus (EM) and swelling property of the
SPI/gelatin composite films increased. In addition, the films became more
transparent, and easier to handle. When the ratio of SPEgelatin was 4:6-2:8, the TS,
EB, and other properties of composite film approached those of gelatin film and

Chapter-1 27
were better than those of SPI film. Particularly, the composite film was more
economic than gelatin film, so it could be used as edible film instead of gelatin film
for package. When the ratio of SPI:gelatin was 4:6, the influences of concentration
of glycerin, pH value of SPI film-forming solution, thermal-treatment temperature of
SPI film-forming solution and NaCl on mechanical and optic properties, and water
content of composite films were also studied.

It can be anticipated that a mixture of NaAlg and SPI probably will present
the advantages of both components. However, application of NaAlg/SPI blends in
the field of membrane separation is not reported in the earlier literature. In this study
miscibility studies of NaAlg / SPI blends at various blend compositions was studied
and were used for pervaporation dehydration of IPA/water mixture. These polymer
blends have both inherently ionic-crosslinking structure and ionized carboxyl
groups, which could be proved with good selectivity and hydrophilicity,
respectively. So, it is expected that membranes made of NaAlg /SPI may be able to
greatly improve its permeation flux in PV dehydration while maintaining its
selectivity.

The key to the success of process is the fabrication of suitable membranes

yielding both high permeability and selectivity [95], Since most polymer membranes
suffer from the inherent drawback of trade-off effect between permeability and
selectivity [96, 97]. Many physical and chemical methods were introduced to modify
the existing polymer material, trying to cross the trade off hurdle meet the practical
application requirements. Among them, blending and incorporation of solid fillers
are the two most frequently employed methods due to their simplicity and
versatility. Blending one polymer into another polymer can significantly alter
polymer chain mobility through the intermolecular interaction which results in the
increase of the permeation flux, and decreases the separation factor for blend
membranes [98-100], On the other hand, incorporating solid filler into polymer can
remarkably improve the solubility property through the preferential adsorption
which often results in the increase in separation factor and decrease the permeation
flux.

Chapter-1 28
1.13. Aim and Scope of the Present work

There is a huge demand for alternative separation technologies, which are

more economical and safe than ordinary and extractive distillation for the separation
of aqueous -organic azeotropes. The study attains a great deal of significance since
the proposed PV technique posses the following advantages over conventional
separation technologies.

a) Very economical
b) Low capital, maintenance costs
c) High safety and environmentally clean
d) Membrane modules can be arranged and replace as per need.

The scope of the present study is to prepare blend membranes and for the
dehydration of water- Isopropanol. NaAlg is an effective polymer material for PV
dehydration because of its high hydrophilicity and good chemical resistance. Since
NaAlg has poor stability in aqueous solutions. It is corsslinked and blended with
Soya protein used to create a stable blend membranes with good mechanical
properties and selective permeability to water. In the present study NaAlg-Soya
protein isolate blending membranes cross-linked with GA were used. The hydroxyl
groups of NaAlg & SPI react readily with aldehydes and hence crosslinking reaction
takes place easily. Since GA an aldehyde is useful in chemical crosslinking reaction
and would be more effective with more resistant membrane.

In the present investigation, we have prepared blend membranes for the

dehydration of water -Isopropanol. This will impart excellent transport
characteristics to the blend membranes for an effective separation of water -
Isopropanol, there exists a strong intermolecular interaction between the
components due to the presence of dipole-dipole interactions as evidenced by a large
negative excel volume data. Such mixtures are difficult to separate by conventional
techniques; because they form azeotropic mixtures at lower composition of water
inhibiting their separation by conventional methods .Separation of such mixtures by
simple distillation requires entertainer as well as large amount of energy.

Chapter-1 29
 The present research also explores the separation performance for varying
water composition in the binary feed mixture, and blend membranes respectively.
Further the membranes were characterized using various techniques. Formation of
ionic interactions and the constituents present in the membrane was analyzed by X-
ray diffractometry, Fourier transform infrared spectroscopy (FT-IR). Thermal
stability and morphological properties of the membranes was investigated using,
Thermo gravimetric analysis (TGA) and Scanning electron microscopy (SEM),
respectively.

Membranes were subjected to sorption studies to evaluate the extent of

interaction and degree of swelling in different compositions of water /IPA and
water/ethanol mixtures ranging from 5 to 20 wt % of water in the feed at different
temperatures 30, 40 and 50° C . The influence of SPI content and feed composition
on membrane performance like flux and selectivity was also investigated.

Chapter-1 30
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