2 Synthetic Membranes for Membrane Processes

2.1 Introduction
According to Wikipedia [I], a membrane is a thin, tvpicallv planar structure or ma-
terial that separates two environments or phases and has a nite volume. It can be
referred to as an interphase rather than an interface. Membranes selectivelv con-
trol mass transport between phases or environments. Again, according to Wikipedia,
membranes can be divided into three groups: (I) biological membranes, (2) articial
membranes, and (3) theoretical membranes.
Biological membranes include:
1. Cell membranes and intracellular membranes
2. Mucous membranes
3. S-laver
4. Serous membranes and mesothelia that surround organs, including:
a) Te peritoneum that lines the abdominal cavitv
b) Te pericardium that surrounds the heart
c) Te pleura that surrounds the lungs
d) Te periosteum that surrounds bone
e) Te meninges that surround the brain (the dura mater, the arachnoid, and
the pia mater)
Articial membranes are used in:
1. Reverse osmosis
2. Filtration (microltration, ultraltration)
3. Pervaporation
4. Dialvsis
5. Emulsion liquid membranes
6. Membrane-based solvent extraction
7. Membrane reactors
8. Gas permeation
9. Supported liquid membranes
Tis book is devoted to svnthetic, or articial, membranes. In particular, our fo-
cus will be on polvmeric svnthetic membranes, since most industrial membranes be-
long to this categorv. Before entering the main subject of this book, i.e., atomic force
6 2 Synthetic Membranes for Membrane Processes
microscopv, the current status of svnthetic polvmeric membranes is outlined. Tus,
in the following pages, we will provide some information about the preparation of
membranes, the properties of membranes, and their applications.
2.2 Membrane Preparation
Svnthetic membranes are fabricated in two main geometries:
1. Flat sheetutilized in the construction of at sheet, disc, spirallv wound, plate,
and frame modules
2. Cvlindricalutilized in tubular and capillarv, or hollow ber, modules
Membranes can be prepared from both ceramic and polvmeric materials. Ce-
ramic materials have several advantages over polvmeric materials, such as higher
chemical and thermal stabilitv. However, the market share of polvmeric membranes
is far greater thanceramic membranes as the polvmeric materials are easier toprocess
and less expensive. A handful of technical polvmers are currentlv used as membrane
materials for 93 of all practical applications [2]. Polvmeric materials that are used
to prepare separation membranes are mostlv organic compounds. A number of dif-
ferent techniques are available to prepare svnthetic membranes.
2.2.1 Membranes with Symmetric Structure
Although most of the practicallv useful membranes are asvmmetric, as explained
later, some of the membranes have svmmetric structures. Tev are prepared in the
following wavs:
Track etching A sheet of polvmeric lm moves underneath a radiation source and
is irradiated bv high-energv particles. Te spots that are subjected to bombardment
of the particles are degraded or chemicallv altered during this process. Ten, the lm
undergoes an etching process in an alkaline or hvdrogen peroxide bath (depending
on the material), where the polvmer is etched along the path of high-energv particles.
Precipitationfromthevapor phase Acast polvmer solutionthat consists of polv-
mer and solvent is brought into a nonsolvent vapor environment saturated with sol-
vent vapor. Te saturated solvent vapor suppresses the evaporation of solvent from
the lm; the nonsolvent molecules diuse into the lm causing polvmer coagulation.
2.2.2 Membranes with Asymmetric Structure
Most membranes used in industries have an asvmmetric structure. Figure 2.I shows
schematicallv a tvpical cross-sectional view of an asvmmetric membrane [3]. It con-
sists of two lavers: the top one is a verv thin dense laver (also called the top skin laver),
and the bottomone is a porous sublaver. Te top dense laver governs the performance
(permeation properties) of the membrane; the porous sublaver onlv provides me-
chanical strength to the membrane. Te membranes of svmmetric structures do not
possess a top dense laver. In the asvmmetric membrane, when the material of the top
2.2 Membrane Preparation 7
Fig. 2.1. Cross-sectional viewof an asymmet-
ric membrane. Reprinted from [3], with kind
permission from the author
laver and porous sublaver are the same, the membrane is called an integrally skinned
asvmmetric membrane. On the other hand, if the polvmer of the top skin laver is dif-
ferent from the polvmer of the porous sublaver, the membrane is called a composite
membrane. Te advantage of the composite membrane over the integrallv skinned
asvmmetric membrane is that the material for the top skin laver and the porous sub-
laver can be chosen separatelv to optimize the overall performance. Tere are various
methods for the preparation of asvmmetric membranes, which are described in the
sections that follow.
2.2.2.1 Phase Inversion Technique for Preparation
of Integrally SkinnedAsymmetric Membranes
Drywet phase inversion technique (Loeb-Sourirajan method) A number of
methods can be used to achieve phase inversion. Among these, the drvwet phase in-
version technique and thermallv induced phase separation (TIPS) are the most com-
monlv used in membrane manufacturing. Te drvwet phase inversion technique,
also called the Loeb-Sourirajan technique, was used bv Loeb and Sourirajan in their
development of the rst cellulose acetate membrane for seawater desalination [4]. In
this method, a polvmer solution is prepared bv mixing polvmer and solvent (some-
times even nonsolvent). Te solution is then cast on a suitable surface bv a doctor
blade to a precalculated thickness. Afer a partial evaporation of the solvent, the cast
lm is immersed in a nonsolvent medium called a gelation bath. Due to a sequence
of two desolvation steps, i.e., evaporation of the solvent and solventnonsolvent ex-
change in the gelation bath, solidication of the polvmer lm takes place. It is desir-
able to choose a solvent of strong dissolving power with a high volatilitv. During the
rst step of desolvation bv solvent evaporation, a thin skin laver of solid polvmer is
formed instantlv at the top of the cast lm due to the loss of solvent. In the solvent
nonsolvent exchange process that follows, the nonsolvent diuses into the polvmer
solution lm through the thin solid laver while the solvent diuses out. Te change
in the composition of the polvmer solution lm during the solventnonsolvent ex-
change process, ofencalled a compositionpath, is illustrated schematicallv inFig. 2.2
(lines A, B, and C each represent a composition path).
Te top skin laver can also be made porous bv lowering the polvmer concentra-
tion in the casting solution and the solvent evaporation period. Tis is called, here-
afer, the porous skin laver. Asvmmetric membranes can also be made in a tubular
form using a casting bob assemblv and a hollow ber spinneret [3].
8 2 Synthetic Membranes for Membrane Processes
Fig. 2.2. Triangular diagram of polymer (P),
solvent (S), and nonsolvent (N). Reprinted
from[3], withkindpermissionfromtheauthor
Thermallyinducedphaseseparationmethod Inthis method, phase inversionis
introduced bv lowering the temperature of the polvmer solution. Apolvmer is mixed
with a substance that acts as a solvent at a high temperature and the polvmer solution
is cast into a lm. When the solution is cooled, it enters into an immiscible region
due to the loss of solvent power. Because the solvent is usuallv nonvolatile, it must
be removed with a liquid that is miscible with the solvent but not miscible with the
polvmer.
2.2.2.2 Preparation of Composite Membranes
Dip coating An integrallv skinned asvmmetric membrane with a porous skin laver
(called hereafer a substrate membrane) is prepared from a polvmer solution bv ap-
plving the drvwet phase inversion method. Te membrane is then dried according
to the method described later, before it is dipped into a bath containing a dilute so-
lution of another polvmer. When the membrane is taken out of the bath, a thin laver
of coating solution is deposited on the top of the substrate membrane. Te solvent is
then removed bv evaporation, leaving a thin laver of the latter polvmer on top of the
substrate membrane.
Interfacial polymerization Tis method, developed bv Cadotte and the coworkers
of FilmTech in the I970s, is currentlv most widelv used to prepare high performance
reverse osmosis and nanoltration membranes [6]. Athin selective laver is deposited
on top of a porous substrate membrane bv interfacial in situ polvcondensation. Tere
are a number of modications of this method primarilv based on the choice of the
monomers [7]. However, for simplicitv, the polvcondensation procedure is described
bv a pair of diamine and diacid chloride monomers.
A diamine solution in water and a diacid chloride solution in hexane are pre-
pared. A porous substrate membrane is then dipped into the aqueous solution of di-
amine. Te pores at the top of the porous substrate membrane are lled withthe aque-
ous solution in this process. Te membrane is then immersed in the diacid chloride
solution in hexane. Since water and hexane are not miscible, an interface is formed
at the boundarv of the two phases. Polvcondensation of diamine and diacid chloride
2.2 Membrane Preparation 9
Fig. 2.3. Steps in the formation of a composite membrane via interfacial polymerization. Reprinted
from [3], with kind permission from the author
takes place at the interface, resulting in a verv thin laver of polvamide. Te prepara-
tion of composite membranes bv interfacial in situ polvcondensation is schematicallv
presented in Fig. 2.3.
2.2.2.3 Membrane Surface Modifcation
As mentioned above, the top skin laver governs the performance of a separation
membrane. Te surface deposition of contaminants fromsolutions or fromgas mix-
tures is also aected bv the surface properties of the membrane. Tis is particularlv
important when decline in the membrane ux with a prolonged operating period is
observed, since it is ofen caused bv the contaminant deposition. Hence, manv at-
tempts have been made to modifv the membrane surface, aimed at prevention of
contaminant deposition and maintenance of high ux. Several methods of surface
modication are described below.
Chemical modifcation Te surface of a membrane can be modied bv chemical
reactions. For example, when the surface of a polvamide composite membrane is
brought into contact with a strong hvdrouoric acid solution, the top polvamide laver
becomes slightlv thinner bv a chemical reaction with hvdrouoric acid. As a result,
the ux increases considerablv while the rejection of sodium chloride is unchanged
or slightlv increased [8].
Plasma polymerization When a vacuum is maintained inside a tubular reactor
and a high frequencv electric eld is applied outside, a glow discharge is generated
inside the reactor (Fig. 2.4). Plasma that consists of various ions, radicals, electrons,
and molecules is formed in the glow discharge. When a porous substrate membrane
is placed in the plasma, the surface of the membrane is subjected to various changes
corresponding to the propertv of plasma. Te substrate surface can be etched and/or
chemicallv active sites can be introduced to the surface, and, upon contact with or-
ganic compounds, an irregular polvmerization can occur at the substrate surface.
Tis is called plasma polvmerization [9].
10 2 Synthetic Membranes for Membrane Processes
Fig. 2.4. Reactor for plasma treatment. Reprinted from [3], with kind permission from the author
Graft polymerization Te surface of a porous substrate membrane is irradiated
with -ravs, which causes the generation of radicals on the membrane surface. Ten,
the membrane is immersed in a monomer solution. Te graf polvmerization of
the monomers is initiated at the membrane surface. Bv choosing a verv hvdrophilic
monomer, the hvdrophilicitv of the surface is increased considerablv.
Surfacemodifcationbysurfacemodifyingmacromolecules (SMMs) Ina polv-
mer blend, thermodvnamic incompatibilitv between polvmers usuallv causes demix-
ing of polvmers. If the polvmer is equilibrated in air, the polvmer with the lowest
surface energv (the hvdrophobic polvmer) will concentrate at the air interface and
reduce the svstems interfacial tension as a consequence. Te preferential adsorp-
tion of a polvmer of lower surface tension at the surface was conrmed bv a number
of researchers for the miscible blend of two dierent polvmers. Based on this con-
cept, surface modifving macromolecules as surface-active additives were svnthesized
and blended into polvmer solutions of polv(ether sulfone) (PES). Depending on the
hvdrophobic [I0, II] or hvdrophilic [I2] nature of the SMMs, the membrane surface
becomes either more hvdrophobic or more hvdrophilic than the base polvmeric ma-
terial.
2.2.3 Membrane Drying
Te wet cellulose acetate membranes prepared for reverse osmosis purposes can be
used for gas separation when thev are dried. Te water in the cellulose acetate mem-
brane cannot be evaporated in air, however, since the asvmmetric structure of the
membrane will collapse. Instead, the multi-stage solvent exchange and evaporation
method is applied. In this method, a water-miscible solvent such as ethanol rst re-
places the water in the membrane. Ten, a second volatile solvent such as hexane re-
places the rst solvent. Te second solvent is subsequentlv air-evaporated to obtain
a drv membrane [I3, I4]. Te reason for replacing water with hexane is to reduce the
capillarv force inside the pore so that it will not collapse during the drving process.
2.3 Membranes for Separation Processes 11
2.3 Membranes for Separation Processes
2.3.1 Membranes for the Separation of Solutions and Solvent Mixtures
Membranes for the separation of solutions and liquid mixtures mav be distinguished
on the basis of pore sizes as reverse osmosis (RO, below I nm), ultraltration (UF,
2I00 nm), and microltration (MF, I00 nm to 2 m), although this classication is
verv arbitrarv. Pore sizes of nanoltration (NF) membranes are between RO and UF
membranes.
2.3.1.1 Reverse Osmosis Membranes
An RO membrane acts as a barrier to ow, allowing selective passage of a particu-
lar species (solvent) while other species (solutes) are retained partiallv or completelv.
Solute separation and permeate solvent (water in most cases) ux depend on the
material selection, the preparation procedures, and the structure of the membrane
barrier laver [3, I3]. Cellulose acetate (CA) is the material for the rst generation
reverse osmosis membrane. Te announcement of CA membranes for sea water de-
salination bv Loeb and Sourirajan in I960 triggered the applications of membrane
separation processes in manv industrial sectors. CA membranes are prepared bv the
drvwet phase inversion technique. Another polvmeric material for RO is aromatic
polvamide [I6].
In aromatic polvamide polvmers, aromatic rings are connected bv an amide link-
age, CONH. While the aromatic ring attached to NH is metasubstituted, the
ring attached to CO is the mixture of meta- and parasubstitutions, which gives
more exibilitv to the polvmeric material. Aromatic polvamide remains one of the
most important materials for reverse osmosis membranes since the thin selective
laver of composite membranes is aromatic polvamide svnthesized bv interfacial in
situ polvmerization.
2.3.1.2 Nanofltration Membranes
Most NF membranes are negativelv charged. In interfacial polvcondensation, trime-
sovl (triacid) chloride is ofen mixed with phthalovl (diacid) chloride in the acidic
component of the polvcondensation reaction. Although most carboxvlic groups are
consumed toformamide linkage, a small portionof the carboxvlic groups donot par-
ticipate in the reaction, becoming the source of the electric charge. Since COOHbe-
comes COO

upon dissociation, the membranes are negativelv charged. Because of

the negative charge, anions are preferentiallv rejected bv nanoltration membranes.
Another method of preparing nanoltration membranes is to dip-coat a thin
laver of sulfonated polv(phenvlene oxide) (SPPO) [I7], sulfonated polvsulfone
(SPS) [I8], or carboxvlated polvsulfone [I9] on a porous substrate membrane. Te
sulfonic acid groups in SPPO and SPS also become negativelv charged with SO
3

groups upon dissociation. Sulfonic acid is a stronger acid than carboxvlic acid.
2.3.1.3 Ultrafltration Membranes
Ultraltration is primarilv a size-exclusion-based, pressure-driven membrane sepa-
ration process. UF membranes tvpicallv have pore sizes in the range of 2300 nm
and retain species in the molecular range from 3000 to 300 000 Da [20], while sol-
12 2 Synthetic Membranes for Membrane Processes
vent (water) passes through the membrane. UF membranes have a porous skin laver.
Te most important UF membrane properties are the membrane productivitv (ux)
and extent of separation (rejection of various feed components).
In contrast to the polvmeric materials for reverse osmosis and nanoltration
membranes, for which the macromolecular structures have much to do with perme-
ation properties such as salt rejection characteristics, the choice of membrane mate-
rial for ultraltration does not depend on the materials inuence on the permeation
properties.
Membrane permeation properties are largelv governed bv the pore sizes and the
pore size distributions of UFmembranes. Rather, thermal, chemical, mechanical, and
biological stabilitv are considered of greater importance. Tvpical UF membrane ma-
terials are polvsulfone (PS), polv(ether sulfone), polv(ether ether ketone) (PEEK),
cellulose acetate and other cellulose esters, polvacrvlonitrile (PAN), polv(vinvlidene
uoride) (PVDF), polvimide (PI), polv(etherimide) (PEI), and aliphatic polvamide
(PA). All these polvmers have a T
g
higher than I43

C except for cellulose esters.
Tev are also stable chemicallv and mechanicallv, and their biodegradabilitv is low.
Te membranes are made bv the drvwet phase inversion technique.
2.3.1.4 Microfltration Membranes
Polvmeric materials for MF membranes cover a verv wide range, from relativelv
hvdrophilic to verv hvdrophobic materials. Tvpical hvdrophilic materials are polv-
sulfone, polv(ether sulfone), cellulose (CE) and cellulose acetate, polvamide, polv-
imide, polv(etherimide) and polvcarbonate (PC). Tvpical hvdrophobic materials are
polvethvlene (PE), polvpropvlene (PP), polvtetrauoroethvlene (PTFE, Teon) and
polv(vinvlidene uoride).
Hvdrophilic MF membranes can be made bv the drvwet phase inversion tech-
nique, which can also be used to make PVDF membranes. On the other hand, other
hvdrophobic microltration membranes are made bv the thermallv induced phase
separation technique. In particular, semicrvstalline PE, PP, and PTFE are stretched
parallel to the direction of lm extrusion so that the crvstalline regions are aligned in
the directionof stretch, while the noncrvstalline regionis ruptured, forming long and
narrow pores. Hvdrophobic membranes do not allow penetration of water into the
pore until the transmembrane pressure drop reaches a threshold called the liquid en-
trv pressure of water (LEPw). Tese membranes can therefore be used for membrane
distillation. Te track-etching method is applied to make microltration membranes
from PC.
An especiallv important characteristic of a microltration membrane is uniform
pores with as manv of them per unit area as possible, and with the thinnest possible
laver where these pores are at their smallest. Te use of MF membranes is the quan-
titative separation of suspended matter in the 0.II0 m size range from liquids and
gases.
2.3.2 Membranes for Gas and Vapor Separation
Te concept of separating gases with polvmeric membranes is more than I00 vears
old, but the widespread use of gas separation membranes has occurred onlv within
2.3 Membranes for Separation Processes 13
the last 2030 vears. Separation is achieved because of dierences in the relative
transport rates of feed components. Components that diuse more rapidlv become
enriched in the low pressure permeate stream, while the slower components are con-
centrated in the retentate, or residue, stream. Te membrane process that separates
components based on their relative rates of permeation distinguishes it from equi-
librium processes such as distillation or extraction.
Gas and vapor separation membranes are classied into two categories. In the
rst, rubberv polvmers such as silicone rubber, natural rubber, and polv(4-methvl-
I-pentene) are used to take advantage of their high permeabilities, even though se-
lectivities are rather moderate. Production of enriched oxvgen for medical purposes
is performed bv this tvpe of membrane with an oxvgen/nitrogen selectivitv of about
two. Asvmmetric membranes made from glassv polvmers such as cellulose acetate
and other cellulose derivatives, polvcarbonate, aromatic polvamide, aromatic polv-
imides, and polv(phenvlene oxide) (PPO) and its derivatives belong to the second
categorv.
Tese asvmmetric membranes are made bv the drvwet phase inversion tech-
nique. Membranes must be dried before being used. Solvent exchange is necessarv
to drv cellulose acetate membranes. Tese membranes take advantage of the high
selectivitv of glassv polvmers. Te selective dense laver at the top of the membrane
must be verv thin so that a high ux can be achieved. Tev are used in a wide range of
industrial gas separation processes such as hvdrogen recoverv fromvarious chemical
svntheses, sour gas removal from natural gas and production of nitrogen-enriched
air. For the asvmmetric membranes to be eective in gas separation, the thin selective
laver at the top of the membrane should be perfect. Tis requirement is more strin-
gent in gas separation membranes than liquid separation membranes since defective
pores cannot be automaticallv closed when the surface is in contact with drv gas. In
contrast, defective pores of ROand pervaporation (PV) membranes can be closed bv
the swelling of the top skin laver when it is brought into contact with feed liquid.
Since it is dicult to make a selective skin laver defect-free, a method was pro-
posed bv Henis and Tripodi to seal defective pores. Teir method was applied to
asvmmetric polvsulfone membranes, which led to the production of the commercial
Prism membrane [2I].
According to the method, a relativelv thick silicone rubber laver is coated on
a thin selective laver of an asvmmetric polvsulfone membrane. Te thickness of sil-
icone rubber is about I m while the eective thickness of the selective polvsulfone
laver is one tenth of I m. While being coated, silicone rubber penetrates into the
pores to plug them. Tus, feed gas is not allowed to leak through the defective pores.
Te selectivitv of the membrane approaches that of the defect-free polvsulfone laver.
Moreover, since the permeabilities of silicone rubber for gases are orders of magni-
tudes higher than those of polvsulfone, the permeation rate is not aected verv much
even when a relativelv thick silicone rubber laver is coated.
Membranes for vapor removal from air have a structure similar to the Prism
membrane, but thev are prepared on a dierent principle [22]. Aromatic
polv(etherimide) is used to produce a porous substrate membrane bv the drvwet
phase inversion method. Tis polvmer was chosen over polvsulfone/polv(ether sul-
14 2 Synthetic Membranes for Membrane Processes
fone) due to the higher durabilitv of polv(etherimide) to organic vapors. Unlike an
asvmmetric polvsulfone substrate for the Prismmembrane, the top laver of the asvm-
metric polv(etherimide) membrane has a large number of pores, the size of which
is equivalent to those of ultraltration membranes. When a laver of silicone rub-
ber is coated on the top laver of the porous substrate membrane, the silicone rubber
laver will govern the selectivitv, and the porous support will provide onlv mechanical
strength to the composite membrane. Since the permeabilities of water and organic
vapors through the silicone rubber laver are much greater than those of oxvgen and
nitrogen, these membranes are eective in dehumidication of air and removal of
organic vapors from air.
2.3.3 Membranes for Pervaporation and Membrane Distillation
Pervaporation and membrane distillation (MD) are distinguished from the above
membrane separation processes since phase change, fromliquid to vapor, takes place
in the process.
2.3.3.1 Pervaporation
Pervaporation is characterized bv the imposition of a barrier (membrane) laver be-
tween a liquid and a vaporous phase, with a mass transfer occurring selectivelv across
the barrier to the vapor side. Separation occurs with the ecacv of the separation ef-
fect being determined bv the phvsiochemical structure of the membrane.
Pervaporation membranes were developed for the dehvdration of ethanol and
other organic solvents. Terefore, the dense selective laver is made of polvvinvl al-
cohol that is one of the most hvdrophilic materials. Water is preferentiallv sorbed
to polvvinvl alcohol and also preferentiallv transported. To suppress the excessive
swelling of polvmer in water, polvvinvl alcohol is partiallv cross-linked bv dialdehv-
des such as glutaraldehvde [23].
Te dense polvvinvl alcohol laver is supported bv a porous PAN substrate mem-
brane. Polvelectrolvte material [24] and chitosan [23], a natural product, are also po-
tentiallv useful for dehvdration bv pervaporation. Silicone rubber membranes devel-
oped for the removal of organic vapors from air can also be used for the removal of
volatile organic compounds (VOCs) from water bv pervaporation [23]. Because of
the high hvdrophobic nature of silicone rubber, VOCs are preferentiallv sorbed and
transported through the membrane.
2.3.3.2 Membrane Distillation
Membrane distillation is similar to pervaporation since phase change is involved in
the process. When feed liquid (usuallv water) is in contact with a nonwetted porous
hvdrophobic membrane, water does not enter into the pores because the feed liquid
is maintained below a threshold pressure, the liquid penetration pressure of water.
Onlv water vapor permeates through the pores from the feed to the permeate side.
Te driving force is the vapor pressure drop fromthe feed to the permeate side, since
the permeate temperature is maintained below the feed temperature. Commercial
hvdrophobic membranes made of polvpropvlene, polv(vinvlidene uoride) and polv-
2.4 Membrane Applications 15
tetrauoroethvlene, either in capillarv or at-sheet form, are used for MD, although
these membranes were primarilv prepared for microltration purposes. With a salt
solution, for example NaCl in water, onlv water has a vapor pressure, i.e., the va-
por pressure of NaCl can be neglected, which means that onlv water will permeate
through the membrane, and consequentlv verv high selectivities are obtained.
2.3.4 Membranes for Other Separation Processes
While all the above mentioned membrane separationprocesses utilize the transmem-
brane pressure drop as the driving force, there are other membrane separation pro-
cesses based on dierent driving forces.
2.3.4.1 Electrodialysis
Membranes for electrodialvsis (ED) are either positivelv or negativelv charged. Ionic
species in the solution are transported through the membrane bv the electrical po-
tential dierence between the two sides of the membrane. When a membrane is pos-
itivelv charged, it is called an anion exchange membrane since onlv anions are al-
lowed to permeate through the membrane. A negativelv charged membrane is called
cationic since onlv cations are allowed to permeate through the membrane. Te base
polvmeric material is polvstvrene cross-linked bv divinvlbenzene. Ouaternarv am-
monium cations are attached to some aromatic rings of anionic membranes, while
sulfonic groups or carboxvlic groups are attached to some aromatic rings of cationic
membranes [26].
2.3.4.2 Dialysis
Dialvsis is the separation of smaller molecules from larger molecules, or dissolved
substances fromcolloidal particles, ina solutionbv selective diusionthrougha semi-
permeable membrane. Dialvsis is a rate-governed membrane process in which a mi-
crosolute is driven across a semipermeable membrane bv means of a concentra-
tion gradient. Te microsolute diuses through the membrane at a greater rate than
macrosolutes also present in the feed solution. Ordinarv dialvsis is referred to as dif-
fusion of neutral molecules. If electrolvtes are separated with neutral membranes,
or with charged membranes, then the Donnan eects arising from the unequal dis-
tribution of ions interfere with the normal dialvsis process. Tis tvpe of dialvsis is
called Donnan dialvsis. In the medical eld, it is the process used for cleaning blood,
articiallv, with special equipment. Hemodialvsis membranes have ultraltration ca-
pacities ranging from 3 to 70 mLh
I
m
2
mmH
I
g
. Donnan dialvsis makes use of ion
selective membranes to provide improved selectivitv.
2.4 Membrane Applications
Te major applications of membranes for membrane separation processes are sum-
marized in Table 2.I.
16 2 Synthetic Membranes for Membrane Processes
Table 2.1. Applications of synthetic membranes
Membranes Applications
Reverse osmosis 1. Sea water and brackish water desalination
2. Waste water treatment (industrial and municipal, pulp and paper, textile
waste water)
3. Production of boiler qualitv water for steam generation
4. Petroleum industrv
5. Recoverv of plating chemicals fromwastewaters and process waters in the
electroplating and metal-nishing industrv
Nanoltration 1. Water treatment
2. Product and chemical recoverv
3. Concentration/dewatering
4. Fractionation of monovalent and divalent cations
5. Water sofening
Ultraltration 1. Electrodialvsis pretreatment
2. Electrophoretic paint
3. Cheese whev treatment
4. Iuice clarication
5. Recoverv of textile sizing agents
6. Wine clarication
7. Separation of oil/water emulsion
8. Concentration of latex emulsion from wastewater
9. Dewaxing
10. Deasphalting
11. Egg-white preconcentration
12. Kaolin concentration
13. Water treatment
14. Anitv membranes
15. Reverse osmosis pretreatment
Microltration 1. Purication of uids in semiconductor manufacturing industrv
2. Clarication and biological stabilization in the beverage industrv
3. Sterilization (in the food and pharmaceutical industries)
4. Analvsis
Gas separation 1. Hvdrogen recoverv
a) Svnthesis gas ratio adjustment (H
2
/CO)
b) H
2
recoverv from hvdroprocessing purge streams
c) H
2
recoverv from ammonia plant purge streams and other petro-
chemical plant streams
2. Oxvgen/nitrogen separation
3. Helium recoverv
4. Removal of acid gases from light hvdrocarbons
5. Biogas processing
6. Separation of organic vapors from air
Pervaporation 1. Removal of organics from water
2. Water removal from liquid organics
3. Organic/organic separation
2.5 Membrane Characterization 17
Table 2.1. continued
Membranes Applications
Vapor permeation Removal of organics from air
Electrodialvsis 1. Desalination of brackish water
2. Production of table salt
3. Waste water treatment
4. Concentration of RO brines
5. Applications in the chemical, food, and drug industries
Dialvsis 1. Hemoltration and hemodialtration
2. Donnan dialvsis
3. Alcohol reduction of beverages
2.5 Membrane Characterization
Te performance of membranes depends on their properties, which mav be quanti-
ed bv membrane characterization. Te methods for membrane characterization are
listed below.
Characterization of the bulk membrane polymer Durabilitv of the membrane
in the operational environment depends on the thermal, mechanical, and chemical
properties of the membrane polvmer. Tev are characterized bv dierential scanning
calorimetrv (DSC), tensile strength measurement bv contacting the membrane with
solutions, and the gases to be treated. Wide angle X-rav spectroscopv (WAXS) is also
used to measure the crvstallinitv of the polvmer, on which manv other polvmeric
properties depend.
Characterization of the membrane surface It should be emphasized that the
properties of the membrane surface stronglv aect membrane performance. Contact
angle is ofen used as a measure of surface hvdrophilicitv or hvdrophobicitv. X-rav
photoelectron spectroscopv (XPS) provides the data on atomic compositions at the
membrane surface. Recentlv, attentions have been focused on the nodular structure
as well as the roughness at the membrane surface that can be measured bv atomic
force microscopv (AFM).
Pore size and pore size distribution It is obvious that the pore size and the pore
size distributionof the membrane aect membrane performance. Anumber of meth-
ods can be used to determine the pore size and the pore size distribution. Conven-
tional methods include bubble point method, mercurv porometrv, thermporometrv,
permporometrv, and gas adsorption. Transport data of gases and solutions with so-
lute probes can also be used to determine the pore size and the pore size distribution.
Pores can also be observed bv scanning electron microscope (SEM) and transmission
electron microscope (TEM). Atomic force microscope can observe the pores onlv on
the membrane surface.
18 2 Synthetic Membranes for Membrane Processes
References
1. Membrane. (2007) Wikimedia Foundation Wikipedia. http://en.wikipedia.org/wiki/Membrane
2. Peinemann K(2004) Next generation membrane materials. In: Abstracts of the I3th annual meeting
of the NAMS, Honolulu, 2630 Iune 2004
3. Matsuura T (I994) Svnthetic membranes and membrane separation processes. CRC, Boca Raton,
p I3
4. Loeb S, Sourirajan S (I963) Adv Chem Ser 38:II7
5. Sourirajan S, Matsuura T (I983) Reverse osmosis/ultrafiltration process principles. National Re-
search Council of Canada, Ottawa, p 802
6. Rozelle LT, Cadotte IE, Cobian KE, Kopp CVIr (I977) Nonpolvsaccharide membrane for reverse
osmosis: NS-I00 membranes. In: Sourirajan S (ed) Reverse osmosis and svnthetic membranes:
theorv, technologv, engineering. National Research Council of Canada, Ottawa, p 249
7. Peterson RI (I993) I Membr Sci 83:8I
8. Kulkarni A, Mukherjee D, Gill WN (I994) Chem Eng Commun I29:33
9. Hirotsu T (I987) Ind Eng Chem Res 26:I287
10. Suk DE, Chowdhurv G, Narbaitz RM, Santerre IP, Matsuura T, Glazier G, Deslandes Y (2002)
Macromolecules 33:30I7
11. Khavet M, Suk DE, Narbaitz RM, Santerre IP, Matsuura T (2003) I Appl Polvm Sci 89:2902
12. Hester IF, Banerjee P, Won YY, Akthakul A, Acar MH, Maves AM (2002) Macromolecules 33:7632
13. Lui A, Talbot FDF, Sourirajan S, Fouda AE, Matsuura T (I988) Sep Sci Technol 23:I839
14. Gantzel PK, Merten U (I970) Ind Eng Chem Process Des Dev 9:33I
15. Llovd D (I983) Membrane materials science: an overview. In: Llovd DR (ed) Materials science of
svnthetic membranes. ACS Svmposium Series 269. American Chemical Societv, Washington, DC,
p I
16. Hoehn HH (I983) Aromatic polvamide membranes. In: Llovd DR (ed) Materials science of svn-
thetic membranes. ACS Svmposium Series 269. American Chemical Societv, Washington, DC, p 8I
17. Matsuura T (200I) Reverse osmosis and nanofiltration bv composite polvphenvlene oxide mem-
branes. In: Chowdhurv G, Kruczek B, Matsuura T (eds) Polvphenvlene oxide and modified
polvphenvlene oxide membranes. Kluwer, Dordrecht, p I8I
18. Allegrezza AEIr, Parekh BS, Parise PL, Swiniarski EI, White IL (I987) Desalination 64:283
19. Guiver MD, Tremblav AY, Tam CM (I989) Reverse osmosis membrane from novel hvdrophilic
polvsulfone. In: Sourirajan S, Matsuura T (eds) Advances in reverse osmosis and ultrafiltration.
National Research Council of Canada, Ottawa, p 33
20. Kulkarni SS, Funk EW, Li N (I992) Ultrafiltration. In: Ho WSW, Sirkar KK (eds) Membrane hand-
book. Van Nostrand, New York, p 393
21. Henis IMS, Tripodi MK (I98I) I Membr Sci 7:233
22. Behling RD, Ohlrogge K, Peinemann KV (I989) The separation of hvdrocarbons from waste vapor
streams. In: Fouda AE, Hazlett ID, Matsuura T, Iohnson I (eds) Membrane separations in chemical
engineering. AIChE Svmposium Series 272, New York, p 68
23. Koops GH, Smolders CA (I99I) Estimation and evaluation of polvmeric materials for pervapo-
ration membranes. In: Huang RYM (ed) Pervaporation membrane separation processes. Elsevier,
New York, p 233
24. Tsuvumoto M, Karakane H, Maeda Y, Tsugava H (I99I) Desalination 80:I39
25. Feng XS, Huang RYM (I996) I Membr Sci II6:67
26. Strathmann H (I992) Electrodialvsis. In: Ho WSW, Sirkar KK (eds) Membrane handbook. Van
Nostrand, New York, p 2I9