Professional Documents
Culture Documents
maintenance of a vacuum. Vacuum pumps are, in gen- mixtures using univariate regression and two- and three-
eral, not amenable to miniaturization, since they must way partial least squares. Analyst 122: 631}638.
possess the physical means to transport molecules Demir C, Hindmarch R and Brereton RG (1996) Procrustes
from inside the system to the outside environment. The analysis for the determination of number of signiRcant
only restriction is the insistence on maintaining vacu- masses in gas chromatography}mass spectrometry.
Analyst 121: 1443}1449.
um, with the assumption that many samples will be
Harrison AG (1992) Chemical Ionization Mass Spectro-
analysed by the same mass spectrometer. If a miniatur- metry, 2nd edn. Boca Raton: CRC Press.
ized mass spectrometer has a total evacuated volume Hillenkamp F, Karas M, Beavis RC and Chair BT (1991)
of 1 mL (not outside the reasonable scale), then a va- Matrix-assisted laser desorption/ionization mass spec-
cuum reservoir of 100 mL sufRces for pumping by trometry of biopolymers. Analytical Chemistry 63:
virtue of expansion. Essentially the vacuum is a rechar- 1193A}1203A.
geable resource. Removing of the vacuum hardware as Karjalainen EJ and Karjalainen UP (1996) Data Analysis for
a physical limitation to the size of the mass spectro- Hyphenated Techniques. Amsterdam: Elsevier Science.
meter will be a genuine innovation in the Reld. Hope- Martinsen DP and Song BH (1985) Mass Spectrometry
fully, this same overview written ten years from now Reviews 4(4): 461}490.
will document the applications of new miniaturized Owens KG (1992) Applied Spectroscopy Reviews 27(1):
1}49.
chromatography}mass spectrometry systems.
Smith RD, Olivares JA, Nguyen NT and Udseth HR (1998)
Analytical Chemistry 40: 436}441.
See Colour Plate 12.
Vairamani M, Mirza UA and Srinivas R (1990) Mass Spec-
trometry Reviews 9(2): 235}258.
Further Reading Van der Greef J and Niessen WMA (1992) Int. J. Mass
Brakstad F (1995) Chemometrics and Intelligent Laborat- Spectrom. Ion Proc. 118}119: 857}873.
ory Systems 29(2): 157}176. Zenobi R and Knochenmuss R (1999) Mass Spectrometry
Cole RB (ed.) (1997) Electrospray Ionization Mass Spectro- Reviews 17: 337}336.
metry: Fundamentals, Instrumentation, and Applica- Zhang Z and McElvain JS (1999) Optimizing spectroscopic
tions. New York: Wiley-Interscience. signal-to-noise ratio in analysis of data collected by
Demir C and Brereton RG (1997) Calibration of gas a chromatographic/spectroscopic system. Analytical
chromatography}mass spectrometry of two-component Chemistry 71(1): 39}45.
MEMBRANE SEPARATION
R. W. Baker, Membrane Technology & similar membranes and membrane module designs
Research Inc. (MTR), Menlo Park, CA, USA are used in all of these process areas, the ways by
which the separations are performed and the process
Copyright ^ 2000 Academic Press applications are very different. A brief overview
of each process is given here; more detailed descrip-
Introduction tions of the individual processes are given elsewhere
in the encyclopedia.
Since the 1970s industrial membrane separation tech-
nology has developed into a US$1}2 billion per year
business. The market is fragmented, but can be
History
divided into six principal industrial process areas: The concept of the ideal semipermeable membrane
microRltration, ultraRltration, reverse osmosis, elec- able to separate two species with the theoretical min-
trodialysis, gas separation and pervaporation. Dialy- imum work has been used by thermodynamicists for
sis, another membrane separation technique, is lim- more than 150 years, but attempts to use membranes
ited to two biomedical processes, haemodialysis (arti- for practical separations did not begin until the 1900s,
Rcial kidneys) and blood oxygenators (artiRcial when Bechhold devised a technique for preparing ni-
lungs). The market for these two biomedical applica- trocellulose membranes of graded pore size. Later
tions is another US$2;109 per year. Further mem- workers, particularly Zsigmondy, Bachmann, Elford
brane separation applications, including membrane and Ferry, reRned these preparative techniques
contactors, membrane reactors and coupled and facil- and membranes were used to separate a variety of
itated transport, are under development. Although laboratory solutions by dialysis and microRltration.
SEPSCI=1=TSK=VVC=BG
190 I / MEMBRANE SEPARATION / Derivatization
By the 1930s, microporous membranes were produc- proximately 20% polymer is cast as a thin Rlm on
ed commercially on a small scale. The Rrst ion ex- a nonwoven fabric web and is then precipitated by
change membranes were made at about the same immersion in a bath of water. The water very rapidly
time; these were used by Teorell, Meyer and Seivers precipitates the top surface of the cast Rlm, forming
to develop their theory of ion transport. This work the selective skin. This skin then slows down the entry
led eventually to the development of electrodialysis. of water into the underlying polymer solution, which
By the 1960s, therefore, the elements of modern precipitates much more slowly, forming a more por-
membrane science had been developed, but mem- ous substructure. A scanning electron micrograph
branes were only used in laboratories and in a few showing the porous substructure and the selective
small, specialized industrial applications. There was skin of a Loeb}Sourirajan membrane is shown in
no signiRcant membrane industry, and total sales for Figure 1. The selective layer thickness is typically less
all applications probably did not exceed US$10 mil- than 0.2 m.
lion. Membrane processes suffered from three About one-third of the reverse osmosis and almost
problems that prohibited their widespread use: they all ultraRltration membranes currently produced are
were too slow, too expensive and too unselective. made by the Loeb}Sourirajan technique. This type of
Partial solutions to each of these problems have since membrane is also widely used in gas separation pro-
been developed, and sales of membranes and mem- cesses.
brane separation equipment have grown several hun- In recent years, new approaches have been de-
dred-fold. Currently, several tens of millions of veloped to produce anisotropic membranes with even
square metres of membranes are produced each year, thinner selective layers than those made by the
and a membrane industry has been created. Loeb}Sourirajan method. Selective layers only a few
The problem of slow permeation rates through tens of nanometers in thickness, and effectively free of
membranes was largely overcome in the late 1960s imperfections, have been claimed for these so-called
and early 1970s by the development of imperfection- thin-Rlm composite membranes. Thin-Rlm composite
free ultrathin membranes. These membranes are an- membranes can be made by a number of methods, of
isotropic structures and consist of a thin selective which two are particularly important: coating with
surface Rlm supported by a much thicker micropor- a dilute polymer solution and interfacial polymeriz-
ous substrate to provide mechanical strength. Because ation. In the coating method, which was developed
the selective surface Rlm is very thin, these mem- Rrst, a very dilute solution of the polymer is prepared
branes have high Suxes. in a volatile solvent, such as hexane. A thin Rlm of
The problem of packing a large membrane area this polymer solution is deposited on the microporous
into a low-cost module has also been solved since the support surface by immersing and then slowly with-
1980s. The earliest module designs were plate-and- drawing the support from the solution. As the solvent
frame or tubular units similar to conventional heat evaporates, an extremely thin polymer Rlm is left be-
exchangers. These designs are still used in some pro- hind. This technique is used to manufacture ultrathin
cesses, such as ultraRltration, in which the ability to membranes for gas separation and pervaporation.
clean fouling deposits from the membrane surface is The second important method for preparing com-
important. However, the cost of both designs is rela- posite membranes is interfacial polymerization. In
tively high, and in most processes they have been this method, an aqueous solution of a reactive mono-
displaced by capillary, hollow-Rne-Rbre and spiral- mer, such as a diamine, is deposited in the pores of
wound module designs. a microporous support membrane. The membrane is
The problem of low selectivity remains one of the then immersed in a water-immiscible solvent solution
principal limitations of membrane processes. No gen- containing a multivalent reactant, such as a triacid
eral solution has been found, although substantial chloride in hexane, which causes the monomer to
improvements have been made since the 1950s. polymerize and cross-link. Polymerization is conRned
to the interface of the two immiscible solutions, so
a thin, highly selective layer is formed. The procedure
Ultrathin Membranes is illustrated in Figure 2. The interfacial polymeriz-
The Rrst useful ultrathin membranes were cellulose ation technique is used to produce most of today’s
acetate reverse osmosis membranes produced by reverse osmosis membranes.
Loeb and Sourirajan, two researchers at the Univer-
sity of California at Los Angeles. The development of Membrane Modules
these thin, and hence high Sux, membranes led to the
reverse osmosis industry in the 1960s. In the The principal module designs } plate-and-frame, tu-
Loeb}Sourirajan technique, a solution containing ap- bular, hollow-Rbre and spiral-wound } are illustrated
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 191
Figure 1 Scanning electron micrograph of the cross-section of a Loeb}Sourirajan reverse osmosis membrane. The development of
this type of anisotropic membrane was a critical breakthrough in the development of membrane technology.
Figure 2 Preparation of ultrathin composite membranes by reaction of an amine dissolved in water and an acid chloride dissolved in
hexane. The chemistry shown is widely used to prepare seawater desalination reverse osmosis membranes. (Reproduced with
permission from Roselle LT et al. (1977). In: SouriraH jan (ed.) Reverse Osmosis and Synthetic Membranes.)
SEPSCI=1=TSK=VVC=BG
192 I / MEMBRANE SEPARATION / Derivatization
in Figures 3 and 4. In the plate-and-frame design can support the applied pressure. Each tube is be-
shown in Figure 3A a series of membrane discs separ- tween 0.5 and 2 cm in diameter and up to Rve tubes
ated by spacers and support plates are held between can be housed in a single support tube. Tubular mod-
two end plates connected by a tension rod. The ge- ules are now only used in ultraRltration applications
ometry of the plates is such that solution entering one for which good Sow distribution across the membrane
end of the module passes sequentially over all the surface with no stagnant areas is required to control
membrane area. Solution that permeates the mem- membrane fouling. In this application up to 20 tubes
brane is collected in a permeate collection channel. are connected in series as shown in Figure 3B.
Tubular modules shown in Figure 3B consist of a por- Plate-and-frame and tubular membranes were wide-
ous support tube, which is coated on the inside sur- ly used in the early days of the modern membrane
face with the selective membrane. The porous sup- era, but by the 1980s had been largely displaced by
port tube nests inside steel or strong plastic tubes that hollow-Rbre, capillary or spiral-wound membrane
Figure 3 Schematic of a reverse osmosis plate-and-frame module (A) and a tubular ultrafiltration membrane module (B). These two
module designs were used in the first large industrial membrane systems but are now limited to a few niche applications.
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 193
Figure 4 Schematic illustrating hollow-fibre (A) and spiral-wound (B) membrane modules. Most large-scale membrane processes
use one of the designs shown.
modules, which are much less expensive to produce (later the OfRce of Water Research and Techno-
per square metre of membrane area. Capillary and logy), resulted in a number of spiral-wound module
hollow-Rne-Rbre membranes are quite similar, dif- designs. The design shown in Figure 4 is the most
fering principally in the diameter of the Rbre used. common, consisting of a membrane envelope wound
Both types are produced by a spinning process much around a perforated central collection tube. The mod-
like conventional Rbre spinning. As a result, the cost ule is placed inside a pressure vessel, and feed solution
of producing the membrane per square metre is quite is circulated axially down the module across the mem-
low. Most of the cost of producing hollow-Rbres is brane envelope. A portion of the feed permeates into
incurred in the Rbre potting operation when Rbres are the membrane envelope, spirals towards the centre of
mounted inside the module shell. Currently, in capil- the module and exits through the collection tube.
lary modules, the feed Suid circulates through the Rbre The Sat-sheet membranes used in spiral-wound
lumen (bore side) as shown in Figure 4A. In hollow- modules usually have higher Suxes than capillary and
Rbre modules, the feed Suid circulates around the outer hollow-Rbre membranes made from the same
surface (shell side) of the Rbres as shown in Figure 4B. material. This is because it is difRcult to make
Spiral-wound modules were originally developed hollow-Rbre selective skins as thin as Sat-sheet skins.
for reverse osmosis applications but are now used in For this reason, although spiral-wound modules are
ultraRltration and gas separation processes as usually two to Rve times more expensive on a square
well. This work, carried out by Fluid Systems Inc. metre basis than hollow-Rbre membranes, they are
under sponsorship of the OfRce of Saline Water competitive in many applications.
SEPSCI=1=TSK=VVC=BG
194 I / MEMBRANE SEPARATION / Derivatization
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 195
Microfiltration Finely Water, dissolved Suspended solids, Pressure Developed (&US$700 million per
microporous solutes bacteria difference year). Removal of suspended solids,
0.1}10 m 5}50 psi bacteria in pharmaceutical, electronics
industries
Ultrafiltration Finely Water, dissolved Macromolecules, Pressure Developed (&US$150 million per
microporous salts colloids difference year). Removal of colloidal material
1}100 nm 20}100 psi from wastewater, food process streams
Reverse Dense Water Dissolved salts Pressure Developed (&US$200 million per
osmosis solution- difference year). Drinking water from sea, brack-
diffusion 100}1000 psi ish or groundwater; production of ultra-
pure water for electronics and pharma-
ceutical industries
Electrodialysis Electrically Water Ions Voltage Developed (&US$200 million per
charged films difference year). Drinking water from brackish
1}2 V water; some industrial applications too
Dialysis Finely Dissolved salts, Blood Concentration Developed (&US$1.3 billion per year
microporous dissolved gases differences for artificial kidney; US$500 million per
10}100 nm year for artificial lung)
Gas separation Dense, Permeable gases Impermeable Pressure Developing (&US$150 million per
solution- and vapours gases and difference year). Nitrogen from air, hydrogen from
diffusion vapors 100}1000 psi petrochemical/refinery vents, carbon
dioxide from natural gas, propylene and
VOCs from petrochemical vents
Pervaporation Dense, Permeable Impermeable Vapour Developing (&US$10 million per year).
solution- micro-solutes micro-solutes pressure Dehydration of solvents (especially
diffusion and solvents and solvents 1}10 psi ethanol)
the laboratory or early commercial stage. In the fol- Above 10 m the separation medium is considered to
lowing sections each of these membrane technology be a conventional Rlter.
areas is described brieSy. More detailed descriptions UltraRltration/microRltration membranes fall into
of the more important processes are given elsewhere two broad categories: screen membrane and depth
in the encyclopedia. membrane Rlters, as shown in Figure 7. Screen Rlters
are anisotropic with small surface pores on a more
Micro\ltration open substructure. The surface pores in screen mem-
brane Rlters are uniform and show a sharp cutoff
The process MicroRltration, ultraRltration and re- between material that is completely retained by the
verse osmosis are related membrane processes dif- membrane and material that penetrates the mem-
fering in the size of the material retained by the brane. Retained material accumulates on the mem-
membrane. As shown in Figure 6, reverse osmosis brane surface. Depth membrane Rlters have a much
membranes can generally separate dissolved micro- wider distribution of pore sizes and usually have
solutes with a molecular weight below 500 by a solu- a more diffuse cutoff than screen membrane
tion-diffusion mechanism. When the molecular Rlters. Very large particulates are retained on the
weight of the solute exceeds 500, the separation surface of the membrane, but smaller particulates
mechanism of the membrane is molecular Rltration, entering the membrane are trapped at constrictions or
in which separation characteristics are determined by adsorbed onto the membrane surface. Screen Rlters
the size of the particles in the mixture and the dia- are usually used in ultraRltration applications (see
meter of the pores in the membrane. By convention, next section). The membrane pores are normally very
membranes having pore sizes up to approximately small, on the order of 5}50 nm in diameter. Partic-
0.1 m in diameter are considered to be ultraRltration ulates and colloidal matter retained at the membrane
membranes. MicroRltration membranes are those surface are removed by a tangential Sow of the feed
with pore diameters in the range of 0.1 to 10 m. solution. In this type of process, 80}90 vol% of the
SEPSCI=1=TSK=VVC=BG
196 I / MEMBRANE SEPARATION / Derivatization
Figure 6 Pore sizes of reverse osmosis, ultrafiltration, microfiltration and conventional filtration membranes.
feed solution permeates the membrane as a clean directly before the Rnal membrane. PreRlters are not
Rltrate. The remaining solution containing the rejec- absolute Rlters, but trap most of the very large partic-
ted material is collected as a concentrated residue. ulates and many of the smaller ones before the feed
Depth Rlters are usually used in microRltration solution reaches the Rner membrane Rlter. This re-
applications. The surface membrane pores can be duces the particle load that the Rner membrane must
quite large, on the order of 1}10 m in diameter, but handle, and thus increases its useful life.
many smaller restrictions occur in the interior of the
membrane. This means that bacteria or virus particles Applications The primary market for microRltra-
as small as 0.2 m in diameter are completely pre- tion membranes is disposable cartridges for sterile
vented from penetrating the membrane. MicroRltra- Rltration of water for the pharmaceutical industry
tion membranes are usually used as an in-line Rlter. and Rnal point-of-use polishing of ultrapure water for
All of the feed solution is forced through the mem- the electronics industry. The cost of microRltration
brane by an applied pressure. Retained particles are compared with the value of the products is small.
collected on or in the membrane. Cold sterilization of beer, wine and other beverages is
The lifetime of microRltration membranes is often another emerging market area. In these processes
improved by using a more open preRlter membrane the microRltration cartridge removes all yeast and
Figure 7 Separation of particulates can take place at the membrane surface according to a screen filtration mechanism (A) or in the
interior of the membrane by a capture mechanism as in depth filtration (B).
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 197
Ultra\ltration
The process UltraRltration is intermediate between
microRltration and reverse osmosis. The most reten-
tive ultraRltration membrane has a substantial rejec-
tion to microsolutes, such as rafRnose (Mr 504),
while the most open ultraRltration membrane will be
just able to retain a molecule of relative molecular
mass one million. In practice, the distinction between
ultraRltration, reverse osmosis and microRltration is
vague, and it is possible to prepare membranes cover-
ing the entire range of reverse osmosis, ultraRltration
and microRltration by making small changes in mem-
Figure 8 Molecular weight cuttoff curves of various ultrafiltra-
brane preparation procedures. tion membranes. (Amicon Corporation trade literature.)
Essentially all ultraRltration membranes are screen
Rltration membranes and separate the retained mater-
ial because of the small pores in their top surface layer achieved between circulation of solution past the
(see Figure 7A). Membranes are characterized by membrane surface, which removes the gelled mater-
their molecular weight cutoff, which is usually ial, and the Sux of permeate through the membrane,
deRned as the molecular weight at which the mem- which brings fresh material to the membrane surface.
brane retains more than 95% of the test solute. The Therefore, in ultraRltration, only a portion of the feed
deRnition is ambiguous, because Sexible-backboned,
linear molecules can penetrate membranes more eas-
ily than rigid, globular molecules, such as dissolved
proteins. In addition, despite the claims of the manu-
facturers, no ultraRltration membrane has a perfectly
sharp molecular weight cutoff. All membranes
contain a range of pore sizes and the passage of
molecules through the pores is completely unhindered
only for very small molecules. Typical molecular
weight cutoff curves for a series of commercial
membranes are shown in Figure 8.
UltraRltration systems generally operate at pres-
sures of 20}100 psi (140}690 kPa). Osmotic pressure
effects are not signiRcant in ultraRltration, and
high operating pressures are not required to produce
high Suxes. Moreover, because of their porous struc-
ture, ultraRltration membranes compact under pres-
sures above 100 psi (690 kPa).
The most important problem associated with ultra-
Rltration membranes is surface fouling. The problem
is illustrated in Figure 9. Material unable to pass
through the membrane accumulates at the surface,
forming a solid gel-like Rlm that acts as a barrier to
the Sow of permeate through the membrane. The
thickness of the fouling Rlm is controlled by the
sweeping action of the feed solution past the mem-
brane surface. This circulating Sow of solution Figure 9 Schematic of ultrafiltration illustrating the dynamic
hydrodynamically scrubs the membrane surface, con- process of deposition and removal of particulate and colloidal
tinuously removing the surface Rlm. Thus a balance is material from the surface of the membrane.
SEPSCI=1=TSK=VVC=BG
198 I / MEMBRANE SEPARATION / Derivatization
solution permeates the membrane; the remaining ly lost. This permanent loss results from deposits of
solution, containing the retained material, is removed fouling material inside the membrane, which cannot
as a concentrated residue stream. be removed even by vigorous cleaning. The fouling
If the feed solution circulation rate across the mem- material gradually accumulates until even the Sux of
brane surface is increased, the thickness of the fouling a freshly cleaned membrane is less than 50% of the
layer on the membrane surface decreases, and higher original value. At this time, the membrane is due for
permeate Suxes through the membrane are obtained. replacement. A typical ultraRltration membrane life-
However, at some point the increased energy cost time is 1}3 years.
involved in recirculating the feed solution offsets Because of membrane fouling, the Sux of ultraRl-
the savings produced by the higher membrane Suxes. tration membranes depends highly on the composi-
With highly fouling solutions, energy consumption of tion of the feed solution and the process operating
30}100 kWh per 1000 gallons (30}100 MJ m\3) of conditions. In the removal of trace particulates for the
permeate produced is typical. The resulting electric preparation of ultrapure water, the feed solution is
energy expense represents a large fraction of the oper- already clean, and Suxes higher than 50}100 gal per
ating cost of an ultraRltration plant. Increasing the ft 2 per day (85}170 L per m2 per day) are achieved.
operating pressure of the membrane system to force With more concentrated and contaminated solutions,
more permeate through the membrane is not a viable such as food processing streams, industrial waste-
method of increasing the membrane Sux because this waters, or electrocoat paint wastes, typical Suxes are
only produces a thicker gel layer on the membrane 10}30 gal per ft 2 per day (17}50 L per m2 per day).
surface so that the Sux remains constant or even
declines. Applications UltraRltration membranes were ori-
Even when most of the layer of deposited material ginally developed for the laboratory market and
on the membrane surface is continuously removed, found an application in the concentration and desalt-
a portion remains and gradually densiRes. This results ing of protein solutions. Later, Abcor and Romicon
in decreased permeate Sux through the membrane developed the industrial ultraRltration market. The
with time. Periodically, ultraRltration membrane Rrst major application was the ultraRltration of elec-
modules are cleaned by washing with a membrane- trocoat paint. The process is illustrated in Figure 11.
cleaning solution. This restores the Sux to almost its In electrocoat paint operations metal parts are im-
original value, after which the Sux begins to decline mersed in a tank containing 15}20% of the paint
again. The process is illustrated in Figure 10. Unfor- emulsion. After coating, the piece is removed from
tunately, cleaning of badly fouled membranes does the tank and rinsed to remove excess paint. The
not completely restore the Sux to the starting value so ultraRltration system removes ionic impurities from
that a proportion of the membrane Sux is permanent- the paint tank carried over from earlier operations
and provides clean rinse water for the countercurrent
rinsing operation. The concentrated paint emulsion is
recirculated back to the tank. Tubular and capillary
Rbre membrane modules are generally used in these
plants because the feed solution easily fouls the mem-
brane. Other large applications of ultraRltration are
the concentration of milk whey in the food industry
to recover milk proteins and to remove lactose and
salts in the membrane Rltrate, and the concentration
of oil emulsions in the metal Rnishing industry. Al-
though some ultraRltration plants treat industrial
waste streams, this is not a common application be-
cause the process is expensive. The preparation of
ultrapure water by ultraRltration for the electronics
industry is a newer, but growing, application. Bio-
technology applications are, as yet, small.
The problem of membrane fouling in ultraRltration
systems requires expensive, energy-consuming pumps
to recirculate the feed solution. Costs of ultraRltra-
Figure 10 Ultrafiltration flux as a function of time for an electro- tion systems are on the order of US$5}10 per
coat paint latex solution. Fouling causes flux decline in a matter of 1000 gal of permeate, precluding its use in large,
days. Periodic cleaning is required to maintain high fluxes. low-value applications such as wastewater treatment.
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 199
Figure 11 Flow schematic of an electrocoat paint ultrafiltration system. The ultrafiltration system removes ionic impurities from the
paint tank carried over from the chromate/phosphate cleaning steps and provides clean rinse water for the countercurrent rinsing
operation.
Therefore, ultraRltration is limited to the type of osmosis, a pressure is applied to the salt solution that
high-value streams listed above. Development of is even higher than the osmotic pressure of the solu-
more fouling-resistant membranes and better module tion. This applied pressure reverses the osmotic water
designs could allow wider use of the process. Sow, and water Sows from the salt solution to the
pure water side of the membrane. Therefore, reverse
Reverse Osmosis
osmosis is a method of desalting saltwater solutions.
The process The processes of osmosis and reverse Equilibrium osmotic pressures are directly propor-
osmosis are illustrated in Figure 12. In normal osmo- tional to salt concentration and are surprisingly
sis, a membrane is used to separate water from a salt large. For example, the osmotic pressure for sodium
solution. If the membrane is semipermeable, that is, chloride is approximately 100 psi (690 kPa) for a 1%
it allows the passage of water but does not pass salt, salt solution.
the small difference in water concentration (salt solu- Two parameters affect the performance of re-
tion) will cause water to Sow into the salt side of the verse osmosis membranes. The Rrst is the Sux or Sow
membrane. This Sow will continue until the hydros- per unit area per time, J, of water through the mem-
tatic pressure head on the salt solution exactly bal- brane, usually described by the equation:
ances the Sow of water across the membrane. This
balance is known as osmotic equilibrium. In reverse J"A(P!) [1]
Figure 12 Osmotic effects across a semipermeable membrane. (Reprinted with permission from Roper and Lightfoot (1995) Journal
of Chromatography 702: 3I26, with permission from Elsevier Science.)
SEPSCI=1=TSK=VVC=BG
200 I / MEMBRANE SEPARATION / Derivatization
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 201
brackish water or seawater. Another 40% are used to US$1}2 per 1000 gal of treated water produced.
produce ultrapure water for electronics, pharmaceut- Well-maintained plants have useful membrane life-
icals and power generation. The remainder are used times of 3}5 years.
in small niche applications such as pollution control
and food processing. Seawater desalination Seawater contains about
3.5% dissolved salt, which means membranes with
Brackish water desalination The salinity of brack- salt rejections above 99.3% are required to produce
ish groundwater is usually between 1500 and potable water. Today’s membranes can easily meet
5000 mg L\1. The World Health Organization rec- these targets, and many seawater desalination plants
ommends that drinking water should contain less are now operating. Because of the high osmotic pres-
than 500 mg L\1 salt, so up to 90% of the salt must sure of seawater (&350 psi (2415 kPa)) these plants
be removed from these waters. This is easily achieved operate at pressures of 800}1000 psi (5520}
by reverse osmosis. A typical process Sow scheme is 6900 kPa). Typical seawater reverse osmosis plants
shown in Figure 14. Frequently brackish water is have a capital cost of US$4}5 gal per day capacity and
contaminated with suspended solids, so Socculation, produce desalted water for a cost of about US$5 per
sand Rltration, and a Rnal cartridge Rlter are used to 1000 gal of product. These costs mean the process is
remove these components Rrst. Adjustment of pH most competitive for systems below 10 million gal
and addition of antiscalants may also be necessary to per day capacity. Above this range economies of scale
prevent calcium, magnesium or silica precipitating on tend to favour multi-effect evaporation plants
the membrane as water is removed and the feed often built to use the waste heat from electric power
becomes more concentrated. The water may also be stations.
sterilized by addition of chlorine to prevent bacterial
growth on the membrane. Even when these elaborate Ultrapure water With the development of the elec-
and costly feed water pretreatment steps are used, tronics industry, a large market has emerged for re-
some fouling of the membrane still occurs. Therefore, verse osmosis plants to produce ultrapure water con-
periodically the plant is taken off-line and the taining (1 ppb total ions from water normally con-
membranes are cleaned by circulating a hot cleaning taining 50}100 ppm total ions. Typical operating
solution. Typical operating pressures for these sys- pressures for the reverse osmosis systems used in these
tems are in the 200}300 psig range. Plant capital plants are low, on the order of 100}150 psi (690}
costs are in the range US$1.00}2.00 per gal per day 1035 kPa). The reverse osmosis plant removes
(plant) capacity, and operating costs are about 98}99% of the salts and dissolved particles in the feed
Figure 14 Flow schematic of a brackish water reverse osmosis plant. The plant contains seven pressure vessels each containing six
membrane modules. The pressure vessels are arranged in a Christmas tree array to maintain a high feed velocity through the modules
as treated water is removed in the permeate.
SEPSCI=1=TSK=VVC=BG
202 I / MEMBRANE SEPARATION / Derivatization
water. Carbon adsorption and ion exchange units are membranes, the migrating ions become concentrated
used to remove the remaining contaminants. in each alternate cell in the stack. Thus, ions removed
from the aqueous feed solution are concentrated into
Electrodialysis two separate streams.
The process Electrodialysis is a process in which
electrically charged membranes are used to separate
Applications
ions from aqueous solutions under the driving force
of an electrical potential difference. The process, Brackish water Brackish water desalination is the
illustrated in Figure 15, utilizes an electrodialysis largest application of electrodialysis. The competitive
stack built on the Rlter press principle. The stack technologies are ion exchange for very dilute solu-
consists of 200}400 alternate cationic and anionic tions (below 500 ppm) and reverse osmosis for solu-
membranes between two electrodes; the aqueous feed tions above 2000 ppm salt. In the 500}2000 ppm
solution Sows through the cells between each pair of range, electrodialysis is almost always the lowest cost
membranes. When an electrical potential differ- process. One advantage of electrodialysis when ap-
ence is applied between the two electrodes, positively plied to brackish water desalination is that a large
charged cations in the feed solution move toward the fraction, typically 80}95% of the brackish feed, is
cathode. These ions easily pass through the negatively recovered as potable water. However, these high re-
charged cation exchange membranes, but are retained coveries mean that the concentrated brine stream
by the positively charged anion exchange membranes. produced is 5}20 times more concentrated than the
Similarly, negatively charged anions migrate towards feed. Precipitation of insoluble salts in the brine can
the anode, pass through the anion exchange mem- limit the water recovery.
brane and are retained by the cation exchange mem- Since the Rrst electrodialysis plants were produced
brane. Because of the arrangement of ion-selective in the early 1950s, several thousand brackish water
Figure 15 Schematic diagram of a plate-and-frame electrodialysis stack. Alternating cation- and anion-permeable membranes are
arranged in a stack of up to 100 cell pairs.
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 203
electrodialysis plants have been installed around the the power plant is then used to concentrate the salt
world. Modern electrodialysis units are generally further by evaporation.
fully automated and require only periodic operator
attention. This has encouraged installation of many Gas Separation
small trailer-mounted plants. However, a number of The process The study of gas permeation through
very large plants with production rates of 10 mil- membranes has a long history dating back to the
lion gal per day or more have also been produced. work of Thomas Graham in the mid-nineteenth cen-
The power consumption of an electrodialysis plant tury. However, the Rrst systematic studies with poly-
is directly proportional to the salt concentration in mers of the type used today did not begin until 100
the feed water, and varies from 4 kWh per 1000 gal years later.
(4 MJ m\3) for 1000 ppm feed water to 10}15 kWh The mechanism of gas permeation developed in
per 1000 gal (10}15 MJ m\3) for 5000 ppm feed the 1950s and 1960s was the solution-diffusion
water. About one-quarter to one-third of this power model. In this model, the rate of diffusion through the
is used to drive the feed water recirculation pumps. polymer membrane is governed by Fick’s law of diffu-
sion. For simple gases, it can be shown that Fick’s law
Seawater A second major application of elec- leads to the expression
trodialysis is the production of table salt by concen-
tration of seawater. This process is only practised in Dkp
Japan, which has no other domestic salt supply. The J" [4]
l
process is heavily subsidized by the government.
Total production is approximately 1.2 million tons
where J is the membrane Sux (cm3(STP)/cm2 s), k is
per year of salt, with more than 500 000 m2 of mem-
the Henry’s law sorption coefRcient linking the
brane used in the plants.
concentration of gas in the membrane material to the
A Sow scheme for one such seawater salt-produc-
pressure of the adjacent gas (cm3(STP)/cm Hg), p is
tion plant is shown in Figure 16. A cogeneration
the partial difference across the membrane, l is
power plant produces the power required for the
the membrane thickness (cm), and D is the permeant
electrodialysis operation, which concentrates the salt
diffusion coefRcient (cm2 s\1), a measure of the
in seawater to about 18}20 wt%. Waste steam from
permeant’s mobility in the membrane. This expres-
sion can be further simpliRed to
Pp
J" [5]
l
P1 D1 k1
1,2" " ; [6]
P2 D2 k2
SEPSCI=1=TSK=VVC=BG
204 I / MEMBRANE SEPARATION / Derivatization
Separation Status
H2/N2, CO, CH4, etc. &500 units installed. Various hydrogen recovery applications in refineries, petrochemical and
ammonia plants
CO2/CH4 &200 units installed, some very large (5000}50 000 scfm) to separate carbon dioxide from
natural gas
N2/air &5000 units installed, most small in the 50}500 scfm range (98}99.5% nitrogen)
Organic solvent vapour/air, N2 &100 units installed. Diverse applications include gasoline vapour recovery at oil terminals,
recovery of monomers from reactor vents
H2O/air Many thousands of small modules sold for drying compressed air
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 205
SEPSCI=1=TSK=VVC=BG
206 I / MEMBRANE SEPARATION / Derivatization
GmbH, Germany) installed the Rrst commercial per- hydration systems have been for ethanol dehydration,
vaporation plant. That plant separated water from but applications to other solvents, including iso-
concentrated alcohol solutions; GFT has since instal- propanol, glycols, acetone and methylene chloride,
led more than 50 such plants. The ethanol feed to the have also been studied.
membrane generally contains &10% water. The The only other commercial pervaporation applica-
pervaporation process removes the water as the per- tion is the separation of dissolved VOCs from water.
meate, producing pure ethanol with less than 1% Relatively hydrophobic composite membranes, such
water, and avoiding all the problems of azeotropic as silicone rubber coated on a microporous polyimide
distillation. support membrane, are used. Extremely high separ-
Spurred on by this success, a great deal of ef- ation factors can be obtained for the more hydropho-
fort is being made to apply pervaporation to other bic VOCs such as toluene, benzene, chlorinated
difRcult separations. Exxon, for example, pur- solvents, esters and ethers. Frequently the VOC in the
sued the separation of hydrocarbon mixtures contain- condensed permeate is enriched 100- to 1000-fold
ing aromatics and aliphatics, a major separation over the feed. Target applications include removal of
problem in reRneries. Another application is the sep- VOCs from industrial wastewater streams and the
aration of dissolved volatile organic compounds recovery of volatile Savour and aroma components
(VOCs) from water, developed by Membrane Tech- in the food processing industry. The GC traces in
nology and Research, Inc. Figure 21 illustrate the concentration and recovery of
orange juice Savours from the water evaporated from
Applications To date, the largest application of per- orange juice obtained by pervaporation.
vaporation is the dehydration of ethanol or iso- The current commercial pervaporation processes
propanol. This process has been pioneered by GFT, involve the separation of organics and water. This
now a division of Sulzar, using polyvinyl alcohol separation is relatively easy, because organic solvents
composite membranes that are far more permeable to and water have very different polarity and ex-
water than alcohol. A Sow scheme of a GFT plant hibit distinct membrane permeation properties. No
combining distillation and pervaporation to produce commercial pervaporation systems have yet been de-
dry alcohol is shown in Figure 20. The distillation veloped for the separation of organic/organic mix-
column produces an ethanol overhead stream con- tures. However, current technology now makes de-
taining 85}90% ethanol which is fed to the per- velopment of pervaporation for these applications
vaporation system. To maximize the vapour pressure possible, and the process is being actively developed
driving force across the membrane the pervaporation by a number of companies. The Rrst pilot-plant
module usually operates at a temperature of results for an organic}organic application } the
105}1303C, corresponding to a need stream vapour separation of methanol from methyl t-butyl
pressure of 2}6 atm. The permeate vapour is cooled ether/isobutene mixtures } was reported by Separex
and condensed at 0 to !103C. The permeate con- in 1988. This is a particularly favourable application,
tains 40}50% ethanol which is recycled to the distil- and available cellulose acetate membranes achieve
lation column; the residue stream is better than a good separation. More recently, Exxon started
99.5 wt% ethanol. Most of the installed solvent de- a pervaporation pilot plant for the separation of
Figure 20 Flow scheme of an integrated distillation/pervaporation plant for ethanol recovery from fermentors.
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 207
Applications
Haemodialysis (artiTcial kidney) The kidney is
a key component in the body’s waste disposal and
acid}base regulation mechanism. Approximately 1 in
every 10 000 persons will suffer irreversible kid-
ney failure, which before 1960 was invariably fatal.
Now a number of treatments, of which haemodialysis
is by far the most important, can maintain these
patients. As many as 800 000 patients worldwide are
treated by haemodialysis devices. Each patient is di-
alysed two to three times per week with a dialyser
that contains about one square metre of membrane
Figure 21 HPLC traces showing recovery of flavour and aroma
components from orange juice evaporation condensate by per- area. Economies of scale allow the membrane mod-
vaporation. ules to be produced at about US$15 each. The devices
are generally disposed of after one or two uses. As
aromatic/aliphatic mixtures, using polyimide/poly- a result the market is about US$1.3;109 per year,
urethane block copolymer membranes. making this the largest membrane separation process
in terms of sales per year and membrane area used.
The Rrst successful artiRcial kidney was construc-
Dialysis
ted by Kolf and Berk in Holland in 1945. Over the
The process Dialysis was the Rrst membrane pro- next 20 years Kolf and others developed a number of
cess to be used on an industrial scale with the devel- improved devices, and by the 1960s the process began
opment of the Cerini dialyser in Italy. The production to be widely used. Early dialysers used coiled tubes or
of rayon from cellulose expanded rapidly in the plate-and-frame designs. The development of hollow-
1930s, and a need arose to recover sodium hydroxide Rbre dialysers reduced costs considerably, making
from hemicellulose/sodium hydroxide solution by- widespread use of the process possible. Each Rbre
product streams formed in the process. A Rnely dialyser contains 0.5}2.0 m2 of membrane formed as
microporous membrane was used to separate the con- Rbres 0.1}0.2 mm in diameter. A typical dialyser
centrated hemicellulose solution from water. The module (Figure 23) contains several thousand Rbres
smaller sodium hydroxide molecules diffuse in a 2 in (5 cm) diameter tube 1}2 ft (30}60 cm)
across the membrane down a concentration gradient long. Blood Sows down the bore of the Rbre, and an
to produce an uncontaminated product stream, as isotonic saline solution is circulated around the
shown in Figure 22. outside. Urea, creatinin and other metabolites in
With the development of ultraRltration and micro- the blood diffuse through the membrane to the
Rltration membranes in the 1960s and 1970s, indus- dialysate solution. The process must be carried out
trial applications of dialysis largely disappeared be-
cause dialysis membranes were slow and unselective
compared to the newer technologies. However, in the
medical area, two very large applications have been
SEPSCI=1=TSK=VVC=BG
208 I / MEMBRANE SEPARATION / Derivatization
SEPSCI=1=TSK=VVC=BG
Sepsci*1*TSK*Venkatachala=BG
I / MEMBRANE SEPARATION 209
SEPSCI=1=TSK=VVC=BG
210 I / PARTICLE SIZE SEPARATIONS / Derivatization
plants. The long-term goal of the process is to replace Baker RW, Cussler EL, Eykamp W et al. (1991) Membrane
packed towers in conventional absorber}stripper Separation Systems. Park Ridge, NJ: Noyes Data Corp.
operations. Practical problems related to membrane Bakish R (ed.) (1991) Proceedings of the International
fouling and lifetime are the principal limitations. Conference on Pervaporation Processes in the Chemical
Industry, Heidelburg. Englewood, NJ: Bakish Materials
Corp.
The Future Bakish R (ed.) (1992) Proceedings of the International
Conference on Pervaporation Processes in the Chemical
Since the 1970s there has been a period of very rapid Industry, Ottawa. Englewood, NJ: Bakish Materials
growth for the membrane separation industry. Total Corp.
sales for all membrane applications have grown ap- Bakish R (ed.) (1995) Proceedings of the International Co-
proximately 400-fold to the US$3}4;109 per year nference on Pervaporation Processes in the Chemical In-
level. In the areas of microRltration, ultraRltration, dustry, Reno, NV. Englewood, NJ: Bakish Materials Corp.
reverse osmosis, electrodialysis and dialysis, the tech- Brock TD (1983) Membrane Filtration. Madison, WI: Sci.
nology is relatively mature. SigniRcant growth is still Tech. Inc.
Cheryan M (1986) UltraTltration Handbook. Lancaster,
occurring, however, as membranes continue to dis-
PA: Tecnomic Pub. Company.
place more conventional separation techniques. The Crespo JG and BoK ddeker KW (eds) (1994) Membrane Pro-
most rapidly expanding area is gas separation, which cesses in Separation and PuriTcation. Dordrecht:
has grown to a US$150;106 per year business in just Kluwer Academic.
a few years. Gas separation is poised to grow a fur- Ho WS and Sirkar KK (eds) (1992) Membrane Handbook.
ther two- or three-fold as the technology is used more ew York: Van Nostrand Reinhold.
widely in the reRnery, petrochemical and natural gas Mulder M (1991) Basic Principles of Membrane Techno-
processing areas. If the development of ceramic oxy- logy. Dordrecht: Kluwer Academic.
gen-permeable membranes for syngas membrane re- Parekh BS (ed.) (1988) Reverse Osmosis Technology. New
actors is successful, a membrane process that could York: Marcel Dekker.
change the basis of the chemical industry would then Paul DR and Yampol’skii YP (eds) (1994) Polymeric Gas
Separation Membranes. Boca Raton, FL: CRC Press.
be available.
Porter MC (ed.) (1990) Handbook of Industrial Membrane
Technology. Park Ridge, NJ: Noyes Publications.
Further Reading Rautenbach R and Albrecht R (1989) Membrane Processes,
Chichester: John Wiley & Sons.
Amjad Z (1993) Reverse Osmosis. New York: Van Nos- Toshima N (ed.) (1992) Polymers for Gas Separation. New
trand-Reinhold. York: VCH.
J. Janc\ a, Universite& de La Rochelle, La Rochelle, minerals recovery and gave us a very detailed report
France on the sophisticated technologies of his epoch. This
Copyright ^ 2000 Academic Press late medieval period saw a true expansion of science
and technology in Europe. Winston Churchill once
said: ‘2from this date, 1492, a new era in the history
Historical Development of mankind takes its beginning’. As many metal re-
In 1556, an extraordinary book entitled De Re Metal- covery processes used at that time were based on
lica, Libri XII appeared in Basel. The author was various separations of particulate matter and De Re
a German physician, naturalist and mineralogist, call- Metallica, Libri XII seems to be the Rrst printed
ing himself Georgius Agricola (originally called review of separation technologies, it is Rtting to ac-
Georg Bauer), living in JaH chymov, Bohemia, from knowledge Agricola’s publication priority in this Reld
1494 to 1555. Agricola described, in a fascinating and to consider his book as the beginning of a modern
manner, the contemporary advances in metals and scientiRc approach to particle size separations.
The reproduction of a rendering in Figure 1 taken
1
This article does not deal with the important particle separ- from Agricola’s book shows a surprisingly sophisti-
ation techniques of filtration, flotation and the use of membranes cated device for gold (and other metals) recovery by
which are dealt with elsewhere in the Encyclopedia. ‘panning’ or ‘sluicing’ which used gravity and
SEPSCI=1=TSK=VVC=BG