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Ind. Eng. Chem. Res.

2001, 40, 1277-1300 1277

REVIEWS

Progress and New Perspectives on Integrated Membrane Operations


for Sustainable Industrial Growth
Enrico Drioli* and Maria Romano
Institute on Membranes and Modeling of Chemical Reactors, CNR, and Department of Chemical Engineering
and Materials, University of Calabria, 87030 Arcavacata di Rende (CS), Italy

Membrane science and technology has led to significant innovation in both processes and products
over the last few decades, offering interesting opportunities in the design, rationalization, and
optimization of innovative productions. The most interesting developments for industrial
membrane technologies are related to the possibility of integrating various of these membrane
operations in the same industrial cycle, with overall important benefits in product quality, plant
compactness, environmental impact, and energetic aspects. Possibilities for membrane engineer-
ing might also be of importance in new areas. The case of transportation technologies is of
particular interest. The purpose here is to present a summary review of the extent to which
membrane processes have been integrated into industrial practice. Some of the most interesting
results already achieved in membrane engineering will be presented, and predictions about future
developments and the possible impact of new membrane science and technology on sustainable
industrial growth will be analyzed.

Introduction streams commercially feasible. Billions of cubic meters


of pure gases are now produced via selective permeation
Membrane science and technology has led to signifi- in polymeric membranes.
cant innovation in both processes and products, par-
ticularly appropriate for sustainable industrial growth, The combination of molecular separation with a
over the past few decades. chemical reaction, or membrane reactors, offers impor-
tant new opportunities for improving the production
The purpose here is to present a summary review of
efficiency in biotechnology and in the chemical industry.
the extent to which membrane processes have been
In 1997, five large petrochemical companies announced
integrated into industrial practice.
a research project devoted to the development of inor-
The preparation of asymmetric cellulose acetate mem-
ganic membranes to be used in syngas production. At
branes in the early 1960s by Loeb and Sourirajan is
about the same time, an $84 million project, partly
generally recognized as a pivotal moment for membrane
supported by the U.S. Department of Energy (DOE),
technology. They discovered an effective method for
that has Air Products and Chemical Inc. working
significantly increasing the permeation flux of polymeric
together on the same objective has been promoted. The
membranes without significant changes in selectivity,
availability of new high-temperature-resistant mem-
which made possible the use of membranes in large-
branes and of new membrane operations as membrane
scale operations for desalting brackish water and sea-
contactors offers an important tool for the design of
water by reverse osmosis and for various other molec-
alternative production systems appropriate for sustain-
ular separations in different industrial areas. Today,
able growth.
reverse osmosis is a well-recognized basic unit opera-
tion, together with ultrafiltration, cross-flow microfil- The basic properties of membrane operations make
tration, and nanofiltration, all pressure-driven mem- them ideal for industrial production: they are generally
brane processes. In 1999, the total capacity of reverse athermal and do not involve phase changes or chemical
osmosis (RO) desalination plants was more than 10 additives, they are simple in concept and operation, they
millions m3/day, which exceeds the amount produced by are modular and easy to scale-up, and they are low in
the thermal method,1 and more than 250 000 m2 of energy consumption with a potential for more rational
ultrafiltration membranes were installed for the treat- utilization of raw materials and recovery and reuse of
ment of whey and milk. byproducts. Membrane technologies, compared to those
Composite polymeric membranes developed in the commonly used today, respond efficiently to the require-
1970s made the separation of components from gas ments of so-called “process intensification”, because they
permit drastic improvements in manufacturing and
processing, substantially decreasing the equipment-size/
* Corresponding author: IRMERC-CNR c/o Department of
Chemical Engineering and Materials, via Ponte P. Bucci,
production-capacity ratio, energy consumption, and/or
87030 Arcavacata di Rende (CS), Italy. Tel.: (39) 0984- waste production and resulting in cheaper, sustainable
492039/492025. Fax: (39) 0984-402103. E-mail: technical solutions.2
e.drioli@unical.it. The possibilities of redesigning innovative integrated
10.1021/ie0006209 CCC: $20.00 © 2001 American Chemical Society
Published on Web 02/13/2001
1278 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Table 1. Sales of Membranes and Modules in Various phenomena controlling the adsorption and desorption
Membrane Processes5 of penetrants and other species at the membrane
1998 sales surfaces, with the correct flow-dynamic analysis of the
(millions of growth tangential flow and concentration profile built up in the
membrane process U.S. dollars) (%/year) bulk solutions upstream and in the membranes down-
microfiltration 900 8 stream and with the reology of often concentrated non-
ultrafiltration 500 10 Newtonian fluids, that permits the design of correct
reverse osmosis 400 10 membrane separation units.
gas separation 230 15
electrodialysis 110 5
Membrane operations show potential in molecular
electrolysis 70 5 separations, clarifications, fractionations, concentra-
pervaporation >10 ? tions, etc. in the liquid phase, in the gas phase, or in
miscellaneous 30 10 suspensions.
They cover practically all existing and requested unit
membrane processes in various industrial sectors char- operations used in process engineering. All of the
acterized by low environmental impacts, low energy operations are modular, easy to scale-up, and simple to
consumption, and high quality of final products have design. Other important aspects are the lack of moving
been studied and in some cases realized industrially. parts; ability to work totally unattended; lower cost;
Interesting examples are in the dairy industry and operational flexibility; and, when necessary, portability.
in the pharmaceutical industry. Research projects are Coupling of molecular separations with chemical
in progress in the leather industry and in the agrofood reactions can be realized in a simple unit efficiently,
industry based on the same concept. having ideal reaction surfaces where the products can
In this review, some of the most interesting results be continuously removed and the reagents continuously
already achieved in membrane engineering will be supplied at stoichiometric values.
presented, and predictions about future developments These overall properties make membrane operations
and the possible impact of new membrane science and ideal for the design of innovative processes where they
technology on sustainable industrial growth will be will carry on the various necessary functions integrated
analyzed. eventually with other traditional unit operations, opti-
Actual possibilities and future perspectives of medical mizing their positive synergic effects.
and biomedical applications of membrane technology are It is interesting to mention that statistical analysis
not discussed in this work. This theme is the object of carried out by Electricité de France on 174 different
another recent paper.3 membrane installations in France using MF, UF, RO,
The continuous interest and growth of the various and ED mainly in small- and medium-sized industries
new industrial processes related to life sciences, as found a normal percentage of satisfaction between 70
evidenced also by the strategies and reorganization and 95%, one of the highest positive responses received
adopted by large chemical groups worldwide in this area in this kind of analysis. This result is, in part, surprising
(e.g., Aventis, Novartis, Vivendi Water, etc.) will also because of the high innovative content of the technology
require significant contributions from membrane engi- and the lack of education still existing on their basic
neering. We will, however, not concentrate our analysis properties. It is, however, consistent with the important
on this subject in this review. contributions that membrane operations can make in
terms of cost reduction, quality improvement, pollution
Membrane Operations control, etc.
Various membrane operations are available today for Several examples of successful applications of mem-
a wide spectrum of industrial applications. Most of them brane technology as alternatives to traditional processes
can be considered as basic unit operations, particularly can be mentioned.
the pressure-driven processes such as microfiltration Ion-Exchange Membranes. The use of ion-ex-
(MF), ultrafiltration (UF), nanofiltration (NF), and RO; change membrane cells in chloro-soda production rep-
electrodialysis (ED) is another example of a mature resents, for example, an interesting case study for
technology.4 Their worldwide sales are reported in Table analyzing the possibilities of membrane operations and
1.5 one of the first successes in terms of their electrochemi-
The significant variety of existing membrane opera- cal application in minimizing environmental impacts
tions is based on relatively simple, compact, and largely and energy consumption. The technology is based on the
clarified fundamental mechanisms characterizing trans- discovery and utilization of fluorinated polymeric mem-
port phenomena in the dense or microporous membrane branes stable in a specific environment, such as Nafion.
phases and at the membrane-solution interface. The Today, membrane systems in which the anodic and
understanding and prediction of transport phenomena cathodic species are directly produced in separate
in the membrane phase is today at least qualitatively compartments without mixing and final separation
possible, also theoretically through the newly available problems permit one to overcome the limitations of
tools provided by molecular simulation.6,7 traditional mercury cells, related to the need for Hg
Much progress has been made in this area in recent recovery, and of diaphragm cells, in which the separa-
years in the design of polymeric materials, such as tion and concentration of final products still create
polyimides, etc., and in the calculation of the diffusion difficulties. All new chloro-soda installations are now
coefficients of simple gases in the dense phase. An practically based on this design, which represents a
interesting agreement can be found between the theo- typical rationalization of the process, removing all of the
retical and experimental values.8,9 pollution problems that characterized chloro-soda pro-
It is the integration of advanced knowledge about ductions in the past.
transport phenomena in dense or microporous thin In principle, other molecular halogens could be pro-
phases, combined with the understanding of interfacial duced from their respective gases. The direct production
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1279

Table 2. Worldwide Desalination Production Capacitya


total capacity % of world MSF MEE VC RO ED
country (m3/day) production (%) (%) (%) (%) (%)
Saudi Arabia 5 250 000 25.9 67.5 0.3 1.2 31.0 1.9
U.S. 3 100 00 15.2 1.7 1.8 4.5 78.0 11.4
United Arab Emirates 2 200 00 10.7 89.8 0.4 3.0 6.5 0.2
Kuwait 1 500 00 7.6 95.5 0.7 0.0 3.4 0.3
Japan 746 000 3.7 4.7 2.0 0.0 86.4 6.8
Libya 685 000 3.4 67.7 0.9 1.8 19.6 9.8
Qatar 570 000 2.8 94.4 0.6 3.3 0.0 0.0
Spain 530 000 2.6 10.6 0.9 15.1 20.4 19.2
Italy 520 000 2.6 43.2 1.9 15.1 20.4 19.2
Bahrain 310 000 1.5 52.0 0.0 1.5 41.7 4.5
Oman 190 000 0.9 84.1 2.2 0.0 11.7 0.0
a Phase-change processes: MSF (multistage flash), ME (multi-effect evaporation), VC (vapor condensation). Single-phase processes:

RO (reverse osmosis), ED (electrodialysis).

Table 3. Costs Related to Various Sea Water Desalination Processes


electric energy cost for 1 m3
energy equivalent scale of of freshwater
processa maturity consumption (kWh/m3) application produced (ECU)
MSF very thermal 10-14.5 small-large 0.6-1.9
ME partly thermal 6-9 small-medium 0.5-2.0
VC partly mechanical 7-15 small 0.6-2.4
RO yes mechanical 4-8 small-large 0.4-1.4
a Phase-change processes: MSF (multistage flash), ME (multi-effect evaporation), VC (vapor condensation). Single-phase processes:

RO (reverse osmosis), ED (electrodialysis).

of essentially dry chlorine gas would also reduce oxygen industry.12 Recently, in X-ray diagnosis, the use as
formation, which allows the reaction to be run at much contrast media of new nonionic iodinated compounds as
higher current densities, with much less purification opacifying agents was studied and introduced to the
and drying required compared to the chlorine produced markets as a substitution for the traditional iodinated
by other systems. ionic compounds. However, the preparation and, par-
Reverse Osmosis and Nanofiltration. As already ticularly, the final purification of these products were
mentioned, desalination of seawater and brackish water much more complex and expensive than for those
has been at the origin of the interest for membrane previously used. In particular, the neutral iodinated
operations, and the research efforts on reverse osmosis agents cannot be isolated by precipitation in water
membranes have had an impact on all of the progress because of their high solubilities. The problems to be
in membrane science and technology. Evaporation solved were particularly the removal of ionic species,
plants have been substituted with RO systems in usually inorganic salts present in the final reaction
different part of the world (Table 2).10 mixture and the recovery of valuable reagents present
The relatively low energy consumption is one of the in excess and of the water-soluble reaction media. A
reasons for this success (Table 3). In seawater desalting, technique was developed based on the treatment of the
in fact, the global energy consumption of RO, with a raw solutions of the contrast media with a complex
recovery factor of 30% and energy recovery, has been series of operations such as removal of the solvent
5.32 kWh/m3 corresponding to a primary energy con- (DMAC or DMF) by evaporation; extraction of the
sumption of 59.94 kJ/kg.11 residual reaction medium by a chlorinated solvent;
Costs for brackish water desalination are 60-70% elution of the aqueous phase on a system of cationic and
lower than those for seawater desalination. anionic ion-exchange resins; concentration by evapora-
RO desalination is not only devoted to the production tion; and crystallization of the crude residue to remove
of drinkable water but today is also strategic in various the last impurities. Various drawbacks are present in
industrial sectors and particularly in ultrapure water this system. A much better system has recently been
production for the electronic industry. It is interesting realized based on the use of two nanofiltration stages
to realize that, in Japan, the largest part of the water operating on highly concentrated raw solutions contain-
produced by RO is for the electronics industry, in which ing the contrast media, inorganic salts, organic com-
the country has worldwide leadership. pounds with a relatively low mass (about 200), and the
Reverse osmosis has not generally been used until solvents (Figure 1).
recently in the purification, separation, or concentration
of chemicals, particularly because of osmotic limitations The first NF unit operates in diafiltration mode and
and the low chemical and thermal resistance of the the retentate, partially concentrated and purified with
existing membranes. respect to contrast media, is recycled at the first stage
The recent development of nanofiltration and low- after dilution with a small amount of deionized makeup
pressure reverse osmosis membranes with interesting water; the permeate (water, inorganic salts, solvents,
selectivities and fluxes, as well as higher chemical and etc.), which still contains small amounts of the iodinated
thermal resistances, has been rapidly utilized in the compound, proceeds toward the second NF unit. The
realization of innovative processes in various industrial permeate from this second step is completely contrast
sectors. agent free.
An interesting case studied in Italy is represented by The degree of purification that can be reached is such
the preparation of Iopamidol in the pharmaceutical that the total amount of residual impurities in the final
1280 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 1. Recovery of Iopamidol by membrane process.12

recycled retentate does not exceed 10% of the initial possibilities of recovering solvents from the oil-micelle
amount and is generally on the order of 5%. mixture and from air exist today with membrane
The process is simple, economical, and environmen- operations that might significantly reduce these losses.
tally acceptable; it permits the elimination of acid and A reduction of the solvent content of the oil-micelle
basic reactants necessary for the regeneration of the mixture from 70 to 40% has been demonstrated, with
resins; and it avoids the use of toxic organic solvents, an energy saving of about 50%. An important aspect of
etc. the utilization of membrane operations in this area will
Also, the integrated membrane processes proposed for be the possibility of using other solvents such as
chromium recovery in the leather industry13 and for the alcohols. Their higher evaporation heats make them
treatment of secondary textile effluents for their direct unattractive in traditional evaporation units.
reuse,14 which will be described and discussed later in Better solvent-resistant membranes, eventually in-
this work, show efficient applications of nanofiltration organic ones, however, will be necessary for large-scale
and low-pressure reverse osmosis operations. applications in this area.
Microfiltration and Ultrafiltration. Recently, in Cross-flow microfiltration can also be used success-
the food industry, membrane technology made realistic fully for the removal of long-chain traces of saturated
the possibility of cold sterilization. Tetra Pak (Bacto- fat that are present in, e.g., sunflower oil.15
Catch System) developed a cross-flow microfiltration Considerable advances in UF and MF technologies in
system that debacterizes fresh milk, avoiding any water purification processes for drinking water produc-
thermal treatment and taste alteration. An industrial tion have been achieved to such a point that, presently,
process using this technology is already in operation at more than 1 000 000 m3/day of water are treated using
Villefranche (Lyon) producing 2000 L/day of fresh milk these membrane operations.16,17 The employment of
registered with the trade name Marguerite (Figure 2). integrated membrane systems in the production of
The skimmed milk, obtained by whole milk centrifuga- drinking water is growing rapidly with excellent results.
tion, is sterilized at low temperature by microfiltration. The reliability of the reverse osmosis membrane is
Then, it is mixed with pasteurized cream. After homog- greatly increased when UF or MF operationsswhich
enization and cooling, a debacterized whole milk is emerged in the past decade as an efficient way to
obtained using a process alternative to the classical remove suspended solids and organic and microbiologi-
UHT (ultrahigh-temperature) treatment. cal contaminantssare used in the pretreatment step.
Similar products have also recently been commercial- Furthermore, economical considerations have shown
ized in Italy by Parmalat S.p.A. that multiple membrane systems are more competitive
The current systems for cleaning oil-water streams than conventional processes, resulting in the reduction
via cross-flow microfiltration or ultrafiltration are very of capital and operating costs.
reliable and compact. They can decrease the oil content In addition to the already-mentioned membrane
of water from 10-30 mass % to less than 5 ppm. operations, gas separation, pervaporation, and some
Nitrogen blanketing helps to prevent oxidation of oils others membrane processes, which have recently shown
during mechanical oilseed pressing, while also reducing significant possibilities for their application in various
explosion risks in extraction and during desolventizing. industrial areas, must be cited; among these, a class of
New possibilities exist, however. Solvent recovery, membrane-based unit operations identified as mem-
dehydration of solvents, use of membrane reactors, brane contactors, membrane bioreactors, and catalytic
winterization, and fractionation of fats are interesting membrane reactors will be discussed.
cases. More than two million tons of extraction solvents, Gas Separation. Membrane processes for gaseous
mainly hexane, is used in the U.S. alone. Its recovery mixture separation are, today, technically well-consoli-
is by distillation and condensation. It is estimated that, dated and apt to substitute for traditional techniques.18
also in the most modern units, 0.7 kg of hexane per ton Separation of air components, natural gas dehumidi-
of seed is still released into the environment. The fication, and separation and recovery of CO2 from biogas
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1281

Figure 2. Flow sheet of an industrial system for the debacterization of fresh milk by cross-flow microfiltration (Villefranche, Lyon,
France).

and of H2 from industrial gases are some examples in relatively low purity (0.5-5% O2). Single-stage operation
which membrane technology is applied at the industrial is preferred. Oxygen is the third largest commodity
level. chemical in the U.S. with annual sales in excess of $2
The gas separation business was evaluated in 199619 billion. Whereas nitrogen membrane separation has
at $85 million in the U.S., with growth of about 8% per been a great success, oxygen separation using mem-
year. branes is still underdeveloped. The major reason for this
Asymmetric polymeric membranes, used for gas mix- is that most of the industrial oxygen applications require
ture separations, are made either as plane sheets and purity higher than 90%, which is easily achieved by
assembled in spiral-wound modules or as hollow fibers. adsorption or cryogenic technologies but not by mem-
These modules are made and commercialized by various branes. Today’s limited application of membrane-based
companies all over the world. Although the kind of oxygen generation systems operate either under feed
module used is declared, the type of polymer is still compression or permeate vacuum mode (Figure 3). Both
protected as industrial know-how. methods of separating oxygen are inferior to the adsorp-
In Table 4, some permeability and selectivity data for tion separation processes using various zeolites.
the various polymers used in the manufacture of the New materials are being developed that could possibly
most commercial membranes are reported.20,22 have higher permeabilities than conventional solid
The separation of air components or oxygen enrich- electrolytes, in which ionized atoms are transported
ment has advanced substantially during the past 10 through the crystalline lattice under a driving force
years. The oxygen-enriched air produced by membranes provided by partial pressure differences over the mem-
has been used in various fields, including chemical and brane (pressure-driven process) or by electrical potential
related industries, the medical field, food packaging, etc. gradients (electrochemical pumping).
In industrial furnaces and burners, for example, injec- Mixed conductors with high electronic and oxygen ion
tion of oxygen-enriched air (25-35% oxygen) leads to conductivities could be used as a membrane alternative
higher flame temperatures and reduces the volume of to solid electrolytes for oxygen separation. In such ma-
parasite nitrogen to be heated; this means lower energy terials, both oxygen ions and electronic defects are
consumption. Mixtures containing more than 40% v/v transported in an internal circuit in the membrane ma-
of O2 or 95% v/v of N2 from the air can be obtained. terial. Promising oxygen permeation fluxes have been
Industrial nitrogen is used in the chemical industry to obtained in many perovskite systems, e.g., La-Sr-Co-
protect fuels and oxygen-sensitive materials. Fe-O,23,24 Sr-Fe-Co-O,25,26 and Y-Be-Co-O.27
Membranes today dominate the fraction of the nitro- In particular, in the ITM-oxygen systems, simulta-
gen market for applications less than 50 tons/day and neous conduction of ions and electrons in the same
1282 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Table 4. Permeability and Selectivity Data of Some Polymers Used in the Manufacture of Commercial Membranes for
Gas Separationa
permeability coefficient, selectivity
barrer (ideal) (-)
CO2 O2 N2 CO2/N2 O2/N2
poly[1-(trimethylsilyl)-1-propyne] 28 000 7730 4970 5.60 1.55
poly(dimethylsiloxane) 4550 781 351 13.0 2.22
poly(dimethylsilmethylene) 520 91.0 35.9 14.5 2.53
poly(cis-isoprene) 191 37.5 14.5 13.2 2.60
poly(butadiene-styrene) 171 32.9 10.3 16.6 3.19
natural rubber (at 25 °c) 153.0 - 9.43 16.2 -
ethyl cellulose 5.0 12.4 3.4 22.1 3.65
polystyrene 12.4 2.9 0.52 23.8 5.58
butyl rubber 5.18 - 0.324 16.0 -
poly(ethyl methacrylate) 7.01 1.9 0.33 21.2 5.76
poly(phenylene oxide) (at 25 °c) 75.7 - 3.81 19.9 -
bisphenol A polycarbonate 6.8 1.6 0.38 17.9 4.21
cellulose acetate 4.75 0.82 0.15 31.7 5.47
bisphenol A polysulfone 4.6 1.2 0.19 24.2 6.32
PMDA-4,4′-ODA polymide 2.7 0.61 0.1 27.0 6.10
poly(methyl methacrylate) 0.62 0.14 0.02 31.0 7.00
poly(vinyl chloride) (at 25 °C) 0.157 - 0.0118 13.3 -
PEEK-WC (at 25 °C) 2.75 0.5 0.1 27.5 5.00
polyphosphazeny (at 25 °C) 5.76-10.2 0.955-1.72 - 21.2-30.5 3.71-5.05
a At 35 °C unless otherwise specified.

Figure 3. Oxygen production systems.

Figure 4. Integrated oxygen and power production.

material obviates the need for an external electrical conductivity of the material studied is mainly equal to
circuit to provide the driving force for the separation, the electronic conductivity.
with a significant reduction in cost. The driving force Because this oxygen-ion-conducting membrane must
for the separation process is the partial pressure dif- operate at temperatures above 700 °C, an effective
ference across the membrane. High-pressure air (100- means of recovering the energy contained in the non-
300 psia) is required to achieve a significant flux of O2 permeate, oxygen-depleted stream is required. An ef-
across the membrane. The oxygen flux is directly ficient and cost-effective means to accomplish this is to
proportional to the pressure gradient and inversely integrate the membrane system with a gas turbine
proportional to the membrane thickness. The pressure (Figure 4).28
of the oxygen product is typically only a fraction of an A technology known as OTM syngas (oxygen trans-
atmosphere. port membrane synthesis gas) utilizes these ion-
These dense inorganic perovskite type membranes, conducting membranes able to separate oxygen from air
today manufactured in tubular configurations, transport with a high flux in the same temperature region
oxygen as lattice ions at elevated temperatures with required for the reforming of natural gas. This technol-
infinite selectivity ratios in O2 separations. The ionic ogy was presented in 1997 by an alliance of five
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1283

Figure 5. Scheme of a plant for H2 recovery from ammonia synthesis.

international companies including AMOCO, BP Chemi- Table 5. Economic and Technical Advantages for a 1000
cals, PRAXAIR, SASOL, and STATOIL. Philippe Pe- ton/day Ammonia Plant30
troleum joined the alliance in 1998. The new process, ammonia recovery (scrubbing) 4 ton/day
still under development, integrates the separation of heat saving 522-836 kJ/ton of
oxygen from air, steam reforming, and natural gas NH3 produced
oxidation into one step, eliminating the need for a additional ammonia production 50-55 ton/day
separate oxygen plant. The new technology offers the increase in ammonia production 20-50 ton/day
(at constant natural gas consumption)
possibility of reducing the energy and capital costs of reduction in natural gas production
syngas production. Considering that 60% of the cost for (at constant production rate)
manufacturing any product from natural gas is related
to synthesis gas production, the interest of this innova- stoichiometric as well as nonstoichiometric H2/(CO)x
tion technology is evident. ratio methanol plants at differential pressures up to 70
Various plants for the recovery of hydrogen from the bar. Figure 6 shows the flow diagram of such a hydrogen
purge of the synthesis of ammonia have been realized recovery unit installed for demonstration purposes.31,30
today.29 The unit modules are in general arranged in a Before entering the gas permeators, the feed is scrubbed
“one-stage-two-unit” form. One of the first plants of this in order to reduce the methanol content to levels below
type has been realized by Permea in Louisiana (Figure 100 ppm. From a bleed stream of 4000 mol/h, for
5).30 The first unit, consisting of eight hollow-fiber example, a recovery of 2000 mol/h of hydrogen has been
modules [total feed capacity about 3800 m3(stp)/h] is achieved.
operated with a transmembrane pressure difference of Gas mixture dehumidification is a process of great
60 bar, the permeate leaving at a pressure of about 70 industrial interest, especially for natural gas purifica-
bar. At this pressure, the permeate can be fed to the tion and air dehumidification. An efficient membrane
second stage of the synthesis feed compressor. The system for air dehumidification called the Cactus Mem-
retentate of the first unit is fed to the second unit where brane Air Dryer, developed in the late 1980s, has been
the permeate leaving the modules at 25 bar is mixed commercialized by Permea.32 When the Cactus dryer is
with fresh feed (suction side of the first stage of the fed with compressed air, water vapor and a small
compressor). The retentate is utilized for heating pur- amount of oxygen pass through the walls of the hollow
poses. Gas pretreatment consist of conventional scrub- fiber, while nitrogen, argon, and most of the oxygen
bing to reduce the ammonia content of the bleed from continue through the hollow core of the fibers to the end
2% (molar) to less than 200 ppm in order to avoid of the separator. A small amount of the slower gases
membrane swelling and, as a consequence, damage of passes through the fiber, and this is used to sweep the
the membrane. The economical and technical advan- water vapor through the separator. Cactus membranes
tages related to this membrane system for the recovery work on the principle of dew point depression. For
of hydrogen are shown in Table 5. example, a membrane might be sized for inlet conditions
Methanol synthesis is another process based on a of 100 psig and 100 °F inlet dew point to achieve a 0 °F
gaseous feed; in purge recovery, a water scrubber is also pressure dew point. If inlet conditions change, e.g.,
used with a similar purpose, and it pays for itself in compressed air with a lower inlet dew point is supplied,
terms of the recovered methanol. The methanol/water the separator will provide dry air at an even lower dew
mixture is simply sent to the existing crude methanol point.
distillation column. Hydrogen recovered from this purge The removal of hydrogen sulfide (H2S) and carbon
can result in energy savings, and if additional carbon dioxide (CO2) from natural gas is an ideal application
oxide is available, it can be used to obtain increased for membranes (Figure 7); both H2S and CO2 permeate
methanol production. PRISM separators operate on through membranes at a much higher rate than meth-
1284 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 6. Hydrogen recovery from the bleed of a methanol synthesis.

Figure 7. Removal of H2S and CO2 from natural gas.

ane, enabling a high recovery of the acid gases without


significant loss of pressure in the methane pipeline
product gases.
These membrane processes are going to substitute for
the more traditional methods of hydrocarbon stream
purification. Through a comparison of the separation
cost for the membrane process with that for the dietha-
nolamine (DEA) gas-absorption process, it was found
Figure 8. Recovery of CO2 from exhaust gas and reuse to produce
that the membrane process is more economical than the chemicals by hydrogenation.
DEA gas-absorption process in the range of CO2 con-
centrations in the feed between 5 and 40 mol %. When
the feed also contains H2S, the cost for reducing the CO2 cal plants. The CO2 separated might be converted by
and H2S concentrations in the feed to pipeline specifica- reacting it with H2 in methanol, starting a C1 chemistry
tions increases with increasing H2S concentration (1000 cycle.
to 10 000 ppm). If membrane processes are not economi- As schematized in Figure 8, a membrane reactor
cally competitive because of the high H2S concentration might be ideally used to carry out hydrogenation reac-
in the feed, the separation cost could be significantly tions for chemical production using CO2 recovered from
lowered by using hybrid membrane processes. In such exhaust gases by membrane separation.
processes, the bulk of CO2 and H2S is separated from The separation and recovery of organic solvents from
sour natural gas with membranes, and the final puri- gas stream is also rapidly growing at the industrial
fication to pipeline quality gas is performed by means level.
of suitable gas-absorption processes.33 Despite the high Polymeric rubbery membranes that selectively per-
levels of H2S in the feed, membrane selectivities are meate organic compounds (VOC) from air or nitrogen
maintained.34 have been used. Such systems typically achieve greater
The possibility of utilizing membrane technology in than 99% removal of VOC from the feed gas and reduce
solving problems such as the greenhouse effect related the VOC content of the stream to 100 ppm or less. The
to CO2 production has also been suggested. technology has been applied to the recovery of high-
Membranes able to remove CO2 from air, having a value organic vapors such as vinyl chloride monomer,
high CO2/N2 selectivity, might be used at any large-scale methyl chloride, and methyl formate.
industrial CO2 source as a power station in petrochemi- Membrane systems are competitive with carbon ad-
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1285

Figure 9. Flow diagram of compression/condensation and membrane separation for MVC recovery.

Figure 10. Flow sheet of two-stage recovery system of unreacted monomer and other volatile hydrocarbons from the nitrogen used
during polymer particle degassing (MTR).

sorption or condensation for streams containing more treatment facility, e.g., a catalytic incinerator, gas
than 5000 ppm, particularly if high VOC recovery is engine, or pressure swing adsorption unit. These plants
required. are equipped with a modified plate and frame configu-
The typical industrial applications of vapor recovery ration.36
are off-gas treatment in gasoline tank farms, gasoline A case of a vapor recovery unit based on membrane
station vapor return, and end of pipe solvent recovery technology is that commissioned in a gasoline tank farm
in the chemical and pharmaceutical industries. Another in Munich for the treatment of the off-gasses generated
interesting example of an industrial application is VOC from the storage, handling, and distribution of gasoline.
recovery by the compression-condensation and vapor The plant capacity was 300 m3/h. The only external
permeation method, presented schematically in Figure available energy source was the electrical power supply.
9. This is a scheme of the process developed in Anwil This was planned in the framework of a pilot project
(Wloclawed, Poland), which has been built by MTR for the reduction of emissions at the BP tank farm
(U.S.) for the recovery of monovinyl chloride (MVC). Hamburg-Finkenwerder. The VRU has a capacity of
The recovery of ethylene and propylene from nitrogen 1500 m3/h and a hybrid system of a membrane stage
in polyolefin plant vent streams has been suggested and and a gas engine. Two gas engines coupled with a
realized at the industrial level by DSM in Geleen, The generator are permanently in operation to supply the
Netherlands. basic electrical power of the side. The gas engines are
To recover the unreacted monomer (up to 25%) and designed to switch the fuel feed from natural gas to
other volatile hydrocarbons from the nitrogen used retentate of the membrane stage over a period of VRU
during polymer particles degassing, MTR35 developed operating time.
a two-stage operation in which the mixture of N2 and A commercially successful application is a hybrid
propylene is first compressed and later directed into a system of a membrane stage with pressure swing
membrane vapor separation unit, as shown in Figure adsorption (PSA) (Figure 11). The liquid ring compres-
10. The spiral-wound membrane modules (8 in. diam- sor operating with gasoline as the service liquid sucks
eter, 20 m2 surface area) used are 10-100 times more the hydrocarbon (HC) contaminated air from the gas-
permeable to organic vapors than to air or nitrogen. ometer. The off-gases are compressed and fed into a
In 1989, the first vapor recovery unit (VRU) based scrubber. Gasoline from the tank farm is used as a lean
on membrane technology was commissioned for off-gas absorbent. The HC concentration of the feed gas leaving
treatment in a gasoline tank farm. At present, various the scrubber depends on the operating temperature and
membrane VRU’s are in operation or under construc- pressure. The layout of the membrane stage (membrane
tion. The capacity of these units ranges from 100 to 2000 area and permeate pressure) is governed by the permis-
m3/h. These are single-membrane stages of hybrid sible HC intake concentration of the PSA unit. Two
systems of a membrane stage combined with a post- parallel PSA units are installed and operated alter-
1286 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 11. Membrane stage with integrated pressure swing adsorption.

Table 6. Practical Applications of Pervaporation


application details
separation and/or dehydration of water/organic azeotropes
(water/ethanol, water/2-propanol, water/pyridine)
separation of water from organic/aqueous mixtures
dehydration of organic solvents
shifting of the reaction equilibrium (e.g., esterification)
removal of chlorinated hydrocarbons
separation of organics from the fermentation broth
removal of volatile compounds from aqueous and
separation of aroma compounds
gas streams
wine and beer dealcoholization
removal of VOCs from air
separation of azeotropes (e.g., ethanol/cyclohexane,
separation of organic/organic mixtures methanol/MTBE, ethanol-ETBE)
separation of isomers (e.g., xylenes)

Table 7. Comparison of the Dehydration Costs of Ethanol from 99.4 to 99.9 vol % by Different Techniques
vapor entrainer molecular sieve
permeation pervaporation distillation adsorption
utilities ($/ton) ($/ton) ($/ton) ($/ton)
vapor - 12.80 120.00 80.00
electricity 40.00 17.60 8.00 5.20
cooling water 4.00 4.00 15.0 10.00
entrainer - - 9.60 -
replacement of 19.00 30.60 - 50.00
membranes and
molecular sieves
total costs 63.00 64.0 152.60 145.20

nately. One is in the adsorption phase while the other Pervaporation. Some applications of pervaporation
is in the desorption and regeneration phase. A bypass processes are listed in Table 6.
of the clean stream is used as a purge gas for regenera- Dehydratation of ethanol by PV was the first indus-
tion. To maintain a low vacuum, the vacuum pump at trial-scale application proposed by GFT in the 1980s.
the downstream side of the membrane stage can be a Today, more than 40 industrial pervaporation plants
liquid ring pump with mineral oil as the service liquid built by Sulzer Chemtech Membrantechnik (former
or a rotary vane vacuum pump. This vacuum pump is GFT) are in operation worldwide. They are used for the
also used to support the desorption of the PSA column. dehydration of different solvents and/or solvent mix-
The adsorber material is activated carbon, a carbon tures.
molecular sieve, or an inorganic molecular sieve. A In many practical applications, it might be more
typical VRU combined with a PSA is installed at Shell economical to use pervaporation or vapor permeation
in Ludwigshafen.36 only to break the azeotrope and to concentrate the
Other interesting applications of the technology might retentate further by the above-azeotropic distillation
be in the separation of light hydrocarbons from refinery (Table 7).
waste gas streams, the recovery of natural gas liquids Another successful example of PV is its application
and hydrogen, or the separation of propane, butane, and in the enhancement of chemical reaction efficiency.
higher hydrocarbons from methane in the processing of Examples of such reactions are esterification or phenol-
natural gas for dew point control. acetone condensation. The first industrial plant for the
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1287

Figure 12. Pervaporation-enhanced MTBE production.

Figure 13. Membrane system for CO2 recovery from fermentation broth.

pervaporation-enhanced ester synthesis was built in Membrane Contactors. In these systems the mem-
1991 by GFT for BASF. brane function is to facilitate diffusive mass transfer
A possible application of the removal of organic between two contacting phases, which can be liquid-
solutes could be the treatment of industrial and mu- liquid, gas-liquid, gas-gas, etc.39 The traditional strip-
nicipal water supplies contaminated with carcinogenic ping, scrubbing, absorption, and liquid/liquid extraction
halogenated organic compounds. Such a process would processes can be carried out in this new configuration.
also be attractive for the extraction of organics. With respect to conventional systems, membrane
The possibility of recovering volatile organic com- contactors can guarantee some advantages such as
pounds from gases by pervaporation has been demon- nondispersion of the phases in contact, independently
strated and applied recently at the industrial level.37 variable flow rates without flooding limitations, lack of
The elimination of volatile solutes from dilute aqueous phase-density difference limitations, lack of phase sepa-
solutions might be possible by pervaporation. ration requirements, higher surface area/volume ratios,
Separation of organic/organic mixtures represents the and direct scale-up due to a modular design.
least-developed application and the largest potential Traditional liquid-supported membranes in which a
commercial impact of pervaporation, but considerable carrier is immobilized in the microporous hydrophobic
developments in membrane materials and processes structure of the polymeric membranes are the most
remains to be done. The first industrial application of traditional and well-developed example of a membrane
PV to organic/organic separation was the separation of contactor system.
methanol from a methyl tert-butyl ether (MTBE) stream Other applications, however, have been studied and
in the production of octane enhancer for fuel blends realized today or are under investigations. Interesting
(Figure 12). examples include the removal of trace of oxygen (at
Flexibility with respect to part-load performance and levels of <10 ppb) from water for ultrapure water
changing product and feed concentrations is one of the preparation for the electronics industry,40 the removal
advantages of pervaporation over other separation of CO2 from fermentation broth (Figure 13), and the
processes. This is especially useful in the production of supply of CO2 as a gas to liquid phases (carbonation of
fine chemicals and in the pharmaceutical industry, soft drinks).41 The flow sheet of a water carbonation
where solvents are used and almost no single waste process is presented in Figure 14. Additional examples
solvent is generated continuously. include the removal of alcohol from wine and beer, the
Pervaporation-based hybrid processes offer significant concentration of juice via osmotic or membrane distil-
potential for new economical and efficient solutions to lation,41 the nitrogenation of beer,42 the degassing of
some classical separation problems.38 organic solutions, and water ozonation.43
1288 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 14. Simplified flow sheet for the water carbonation process.

In particular, in the carbonation process, hollow fibers using this new concept, and important phenomena such
have generally been used for industrial units. During as oil combustion might be optimized.
operation, an aqueous liquid flows over the shell side
(outside) of the hollow fiber. A strip gas or vacuum, Membrane Reactors
either separately or in combination, is applied on the
lumen side of the hollow fiber and flows counter current. The possibility of combining molecular separation and
Because of its hydrophobic character, the membrane chemical transformations in a single unit soon attracted
acts as an inert support to allow intimate contact the interest of membrane engineers.49 The first studies
between the gas and liquid phases without dispersion. on such reactors were devoted to the immobilization of
The interface is immobilized at the pores by applying a biocatalysts on polymeric membranes. Recently, high-
higher pressure to the aqueous stream than the gas temperature reactions have been the objective of im-
stream. The result is fast diffusive transfer of dissolved portant studies. Both areas will be analyzed in the
gases from or to the liquid phase. following pages.
Since 1993, a bubble-free membrane-based carbon- Membrane Bioreactors. Biocatalytic membrane
ation line has processed about 112 gal/min of beverage reactors are interesting with respect to conventional
by membrane contactors having a total interfacial area membranes as they combine selective mass transport
of 193 m2 (Pepsi bottling plant in West Virginia).40 with chemical reactions. The selective removal of prod-
Permea commercializes beer dispensing systems known ucts from the reaction site increases conversion of
as CELLARSTREAM Dispense Systems using PULSAR product-inhibited or thermodynamically unfavorable
gas/liquid contactors, which increase or decrease the reactions.
amount of carbon dioxide and nitrogen in draft beer for Biocatalysts can be used suspended in solution and
optimal presentation.42 compartmentalized by a membrane in a reaction vessel
Membrane distillation and osmotic distillation can be or immobilized within the membrane matrix itself.50
considered examples of membrane contactors for real- Since the advent of what has been called solid-phase
izing the concentration of aqueous solutions with non- biochemistry, the advantages of immobilized biocatalytic
volatile solutes as salts and sugars.44-47 In the mem- preparations over homogeneous-phase enzymatic/cel-
brane distillation process, two liquids or solutions at lular reactions have been exploited to develop new and
different temperatures are separated by a porous mem- less-expensive processes.
brane acting as a barrier between the two phases, which Synthetic membranes provide an ideal support for
must not wet the membrane (this implies that hydro- biocatalyst immobilization because of a wide available
phobic membranes must be used in the case of aqueous surface area per unit volume and the possibility for the
solutions). Because of the temperature gradient, a vapor development of new immobilization procedures. En-
pressure difference exists across the membrane, and it zymes are retained in the reaction side, do not pollute
is the driving force inducing vapor molecule transport the products, and can be continuously reused. Im-
through the pores from the high-vapor-pressure side to mobilization has also been shown to enhance enzyme
the permeate side. In the case of osmotic distillation, stability. Moreover, provided that membranes of suit-
the vapor molecule transport is due to a vapor pressure able molecular weight cutoff are used, chemical reaction
driving force provided by having a low-vapor-pressure and physical separation of biocatalysts (and/or sub-
solution on the permeate side of the membrane, e.g., a strates) from the products can take place in the same
concentrated salt solution. unit. Substrate partition at the membrane/fluid inter-
The formation of emulsions or dispersions character- face can be used to improve the selectivity of the
ized by very uniform dimensions of droplets or micro- catalytic reaction toward the derived products with
bubbles can be realized using the same technology. minimal side reactions. Membranes are also attractive
The membrane emulsification process is applied for retaining in the reaction volume the expensive
mainly in the preparation of food emulsions. Moreover, cofactors that are often required to carry out some
microbubble formation increases the stability of the enzymatic reactions.
system by minimizing coalescence phenomena. An At the 1997 Achema conference in Frankfurt, Ger-
interesting study evidenced the relationship existing many, statements on the impact that innovative biore-
between membrane pore diameter and droplet size.48 actors, and particularly those based on the hollow-fiber
The formulation of various products might be realized design, have in setting new performance standards were
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1289

clearly presented. For example, hollow-fiber bioreactors processes is relatively high, but the investments are
in which cells attach into a capillary-type space have substantial. Pure hydrogen can be produced at signifi-
been designed to mimic biological processes more closely cantly lower temperatures by integrating into the reac-
than any other reactor system. Through the fibers, tor a membrane that selectively removes hydrogen
nutrients such as glucose and oxygenase are fed to the during conversion. Potential savings in membrane
cells, and wastes such as CO2 and H2O are removed. reformer and downstream processing costs compared to
Roche Diagnostic declared the use of such reactors to conventional steam reforming apparatuses must, in
produce monoclonal antibodies for diagnostic tests. many cases, be weighed against additional costs associ-
Membrane bioreactor technology can also be applied ated with recompression of the hydrogen permeate
to produce pure enantiomers, in that a membrane stream.
separation process can be combined with an enantiospe- Ag membranes were initially suggested for their H2
cific reaction to obtain a so-called “enantiospecific permeability. Howevere, they present the same prob-
membrane reactor”. As for general membrane reactors, lems that characterize Pd membranes, also having a
the result is a more compact system with higher much lower permeability.
conversion. This technology can respond to the strongly Solid oxide membranes have recently been suggested
increasing demand for pharmaceuticals, food additives, for large-scale applications in syngas production.57
feeds, flavors, fragrances, agrochemicals, etc., as opti- Studies carried out in the U.S. showed the possibility
cally pure isomers.51 of preparing membranes with improved mechanical and
Recently, the results achieved in the production of a thermal characteristics, able to operate, for example, at
chiral intermediate used for the preparation of an 900 °C for over 21 days.
important calcium channel blocker, diltiazem, were
discussed in the open literature,52 confirming the pos- Integrated Membrane Processes
sibilities of membrane reactors also in the large-scale
Traditionally, the various membrane operations (RO,
production of biotechnological products.
UF, MF, etc.) have been introduced in industrial pro-
Phase-transfer catalysis can also be realized in mem- duction lines as an alternative to other existing units.
brane reactor configurations, immobilizing the ap- Reverse osmosis instead of distillation and ultrafiltra-
propriate catalysts in the microporous structure of the tion in place of centrifugation are typical examples.
hydrophobic membranes. The possibility of redesigning overall industrial pro-
Biphasic membrane reactors have been extensively duction by the integration of various already developed
studied with lipases entrapped or bonded on the mem- membrane operations is becoming of particular interest,
brane surface, which confirms the possibilities of the because of the synergic effects that can be reached, the
approach,53,54 as already discussed. simplicity of the units, and the possibility of advanced
Catalytic Membrane Reactors. The development levels of automatization and remote control that can be
of catalytic membrane reactors for high-temperature realized. The rationalization of industrial production by
applications became realistic only in the last few years use of these technologies permits low environmental
with the development of high-temperature-resistant impacts, low energy consumption, and higher quality
membranes. In particular, the earlier applications of final products. New products also often become
involved mainly dehydrogenation reactions, where the available.
role of the membrane was simply hydrogen removal. These results are related to the introduction of new
The earlier studies carried out, particularly in the technologies from the very early stages of the same
Soviet Union on palladium and palladium alloys, con- material transformations and not at the end of the pipe,
firmed the existence of membranes able to permeate H2 as was often done in the past.
with high selectivity. Both capital and operative cost The leather industry might be an interesting case
savings were anticipated, as units for hydrocarbon study because of (1) the large environmental problems
separation from the streams were avoided and the related to its operation, (2) the low technological content
possibility of operating at lower temperatures because of its traditional operations, and (3) the tendency to
of reactor yield enhancement was realized. The fact that concentrate a large number of small-medium industries
the membranes separate intermediates and products in specific districts. More than 2000 companies are in
from the reacting zone, avoiding possible catalyst de- operation in Italy, which is recognized as a world leather
activation or secondary reactions, is also of practical leader for the quality of the leather produced. The
interest. The kinetic mechanisms might be modified or traditional flow sheet of the tanning process in its humid
controlled by the presence of appropriate membrane phase consists of about 20 steps operating in a discon-
systems, which can also act only on a reactive interface tinuous cascade system. The possibility of rationalizing
with no permselectivity, optimizing phase-transfer ca- the overall process by introducing advanced molecular
talysis.55 separation systems such as ultrafiltration, cross-flow
Palladium membrane costs and availability, their filtration, microfiltration, nanofiltration, and reverse
mechanical and thermal stability, and poisoning and osmosis was suggested and has recently also become the
carbon deposition problems are still obstacle to the objective of an Italian National Research Program
large-scale industrial application of these dense metal coordinated and carried out by a consortium represent-
membranes, also when prepared in a composite config- ing most of the companies in the country. In Figure 15
uration.56 is presented an ideal process based on integrated
Hydrogen can be produced by steam reforming and membrane operations.58,59
shift conversion of natural gas or other hydrocarbons. The innovative integrated scheme suggested in Figure
In conventional steam reformers, high conversions of 15 allows the pollution problems of the leather industry
natural gas, on the order of 85-90% or even higher, are to be faced by solving or minimizing them one by one
obtained at reformer outlet temperatures of around where they originate, thereby avoiding the need for huge
850-900 °C. The energy efficiency of steam reforming wastewater treatments at the end of the overall produc-
1290 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 15. Flow sheet of some humid phases of the tanning process integrated with membrane operations.

tion line. The fact that membrane operations act by the recovered chromium solution can be further con-
physical mechanisms without modification of the chemi- centrated by traditional techniques. These recovered
cal procedure at the origin of the final high quality of solutions were used in sheepskin retanning and tanning
the leather should also be mentioned. operations; the skins showed improved physical and
The possibility of also introducing an enzyme mem- chemical characteristics compared to those obtained
brane reactor as an alternative to the traditional chemi- with the traditional chromium solutions. The permeate
cal dehairing process and for the optimization of the from the nanofiltration unit, considering its high content
degreasing step has also been considered. The recovery of chlorides, might be used in the pickling phase,
of the proteins produced in dehairing in the retentate realizing an interesting closed-loop process. In Figure
of an ultrafiltration unit and the recovery and reuse in 16, the schematic flow sheet of chromium recovery is
the same process of the excess of sodium sulfide used shown.
and separated in the permeate became realistic when
The possibility of a membrane-based posttreatment
UF tubular membranes able to operate at the high pH
(>12) characterizing the dehairing bath were prepared of secondary textile wastewater for the direct reuse of
commercially. It is interesting to consider that around polished effluent within the dyeing process was also
40% of the overall pollution in leather processing recently verified by tests at the pilot scale.14 A first
originates in the dehairing step, where only 10% of the treatment scheme examined requires two filtration
overall liquid stream is generated. The problem of steps: membrane microfiltration followed by nanofil-
chromium used in the tanning step has always been tration. The preliminary filtration on ceramic MF
crucial for its negative environmental impact. The modules reduces the fractions of pollutants (suspended
exhaust chromium coming from the tanning bath can solids and colloids) that can induce a rapid fouling in
be recovered and concentrated by a two-stage process the nanofiltration membrane. An addition of high
based on MF or UF as a pretreatment and nanofiltration concentrations of aluminum polychloride (10-70 mg/
as a concentration technique.13 The concentrated chro- L) is necessary to obtain satisfactory performance of the
mium solutions obtained by NF have an improved treatment system. Permeate quality confirms the pos-
quality with respect to those obtained by the conven- sibility of reusing the secondary effluent for textile
tional recovery process of chemical precipitation because industry purposes, but approximate preliminary calcu-
of the optimally low ratio of organic lipolytic component/ lations on this coupled membrane process indicate that,
chromium characterizing the new product. If necessary, at present, this process cannot be transferred to a full-
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1291

Figure 16. Scheme of the proposed process for reuse of exhausted chromium solutions from tanning operations.

scale plant, because of the high price of the ceramic MF distillation are integrated has been realized. It consists
membranes and the need for high dosing of coagulants. of UF and RO pretreatment stages, an osmotic distil-
A second treatment scheme studied requires a clari- lation unit, and a single-stage brine evaporator. This
fication-flocculation step followed by multimedia filtra- plant concentrates fresh juices up to 65-70°Brix and
tion prior to a low-pressure reverse osmosis operation. has a capacity of 50 L/h. Being athermal, osmotic
The clarification-flocculation/filtration is aimed at re- distillation allows for concentration of the juices without
moving the colloidal fraction that promotes fouling of product deterioration or loss of flavors.60
RO membranes. A polished effluent of high quality Hogan et al.61 reported a total process cost of osmotic
(COD < 0.10 mg/L; conductivity < 40 mS; negligible distillation concentration on the order of $1.00/L of
residual color) that can be reused in textile mills is concentrate. From 1 L of fresh juice, it is possible to
obtained. Costs for the complete polishing by low- achieve about 200 mL of 70°Brix concentrate. The value
pressure RO are comparable to the costs of conventional of this concentrate is between $2.50 and $7.50/L. From
secondary wastewater treatment and are quite afford- these data, the economical advantages of the integrated
able (on the order of 0.20-0.25 Euro) even for the Italian membrane process seem evident.
situation, where price of water is much lower than in The coupling of RO and membrane distillation for
most industrialized countries.14 obtaining high recovery factors has been also tested in
Interesting cases of integrated membrane processes fruit juice concentration.62
can also be found in the agrofood industry, in water The potential for osmotic distillation flux enhance-
desalination, in biotechnological production, etc. ment in grape juice concentration by ultrafiltration
In the dairy industry, single-membrane operations pretreatment has recently been investigated.63
such as UF in the treatment of wheys, cross-flow Today, the integration concept finds interesting suc-
microfiltration in the stabilization of milk, and RO in cess in the use of membrane operations for brackish
the concentration of milk or in lactose concentration water treatment. Large-scale applications after many
have been widely applied in the past year. As already years of trials with other membranes have recently been
mentioned, an overall quantity of about 250 000 m2 of successfully realized.
UF membranes were already installed in 1999 and For instance, at the end of 1999, the world’s largest
around 165 000 m2 of RO membranes. integrated membrane system was put into operation by
Successful application of integrated membrane opera- PWN Water Supply Company North Holland in The
tions in fruit juice concentration (in an osmotic distil- Netherlands for drinking water production from lake
lation process) has been developed by the Australian water. Ultrafiltration and reverse osmosis are the most
company The Wingara Wine Group (Melbourne, NSW). essential process elements of this treatment plant,
A hybrid pilot plant in which UF/RO and osmotic having a capacity of 18 000 000 m3/year.64
1292 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 17. Water reuse using MF/UF pretreatment for RO.

In Bahrain, the Addur SWRO desalination plant is exergetic analysis of the overall integrated production
planned for rehabilitation utilizing ultrafiltration mem- lines, if not of the complete system, is recommended.66
branes instead of the traditional flocculation-clarifica- The total energy requirements can be estimated on
tion process65 in water pretreatment. the basis of the overall supply of electrical energy of
The traditional seawater or brackish water desalina- pump engines and external equipments and the thermal
tion process can be reconsidered by optimizing the energy supplied.
pretreatment by MF and/or UF and by adding NF before The energy analysis must be elaborated in order to
the RO step. The introduction of a membrane distilla- include all real involved variables, which generally are
tion stage operating on the RO retentate might permit very numerous and variously aggregated. It is necessary
recovery factors on the order of 87-88% (while the RO to establish the exact size of the unit operations and of
unit alone worked with around a 40% of recovery factor) all of the flows of mass and energy of the process. The
at costs that might be acceptable in various situations. block diagram of the operating phase of interest, con-
Typically, the process systems for wastewater treat- nected to the recovery operation (Figure 18), or the block
ment are designed with reverse osmosis operation as diagram of all of the productive process, integrated with
the final treatment step and require several process the new operation, can help to report, in a compact way,
steps, a large land area, and high capital investment all of the pertinent information for the elaboration of
and operating costs. Microfiltration and ultrafiltration the estimation.
membranes simplify the conventional water reuse pro- The layout of the “traditional” process and the layout
cess by treating effluent directly from the secondary of the alternative process, both completed with all
clarifier, with a simpler process that is easy to operate, information relative to the fluxes of matter and energy,
requires less land area, and is less vulnerable to process can then be compared.
disruption (Figure 17).
Because membrane operations utilize primarily elec-
There are also some advantages in combining a
trical energy, the benefit estimate can be done using
membrane bioreactor with a reverse osmosis step. This
the “substitution coefficient” introduced by Electricité
process solution increases the life of the RO membrane
de France;67 this coefficient compares the primary
and overall facility productivity. A new commercial
energy saved to the electrical energy consumed in cycles
membrane bioreactor for wastewater treatment already
that utilize electricity-consuming operations in substitu-
used in this type of integrated membrane system is
tion for conventional thermal operations. The substitu-
known as the ZenoGem (ZENON Inc.) process. This unit
tion coefficient is defined as the ratio between the
consists of a biological reactor integrated with immersed
primary energy (thermal) saved in the new process with
membranes that form an absolute barrier to solids and
respect to the conventional process and the amount of
bacteria and retain them in the process tank.
electrical energy consumed, relative to the conventional
The benefit of using biocatalytic membrane reactors
process: CS ) C1 - C2/E2 - E1, where CS is the
combined with other membrane processes, such as
substitution coefficient, C is the consumption of thermal
microfiltration, ultrafiltration, reverse osmosis, mem-
primary energy (MJ or Mcal), E is the consumption of
brane extraction, etc., for the production and processing
electrical energy (kWh), and 1 and 2 are the relative
of bioreactive compounds is also apparent. This integra-
indexes of the conventional and innovating process,
tion is particularly important for products obtained by
respectively.
fermentation processes, such as organic acids, antibiot-
ics, etc., and in the processing of food and beverages, Taking into account that 1 kWh of electrical energy,
such as wine, fruit juices, milk, etc. available at the utilization site, requires to burn, in a
power station, 10.5 MJ of primary energy from a
combustible source (oil, gas, coal, etc.), the substitution
Energy Requirements (or process innovation) results are advantageous when
One of the significant and recognized benefits of CS is greater than 10.5 MJ/kWh (2.5 Mcal/kWh).
membrane operations is their low direct energy con- Other than energy, recovered and recycled materials
sumption (in general electricity) because of the absence are also involved; therefore, it is necessary to evaluate
of phase transformations. An important possibility for their indirect energy content. For example, one should
reducing indirect energy consumption through the also consider the energy consumed for the production
recycling and reuse of raw materials or secondary of a material and, therefore, intrinsically associated with
products and minimization of the formation of wastes it; the energy used for disposal of a material in dumping;
also characterizes these techniques. For a correct evalu- the energy used for an inertization treatment of a
ation of the total energy involved, an energetic and material, if required; etc. Considering that a substance,
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1293

Figure 18. General scheme of a system on which an energy balance can be planned.

Table 8. Total Substitution Coefficients Evaluated for Some Processes Integrated with Membrane Operations
CS
membrane process analyzed (MJ/kWh)
recovery and recycling of water in the textile industry 35.3
recovery and recycling of a monomer in the chemical industry 30.8
recovery and recycling of the sulfide in the tanning industry 36.0
saving of thermal energy and fat substance recovery in the dairy industry 21.7
thermal energy savings in tomato juice concentration 137.9

to be produced, needs a certain amount of energy, Table 9. Some New Investigated Membranes and
recycling a substance means, in addition to an economic Membrane Materials
saving, also an indirect energy saving corresponding to thermostable polymeric membranes
the amount of primary energy that would be utilized (PEEK, PPS, PEEK-WC, PEEK-WC functionalized, etc.)
for its production. polymeric membranes resistant to hostile environments
(HYFLON AD, etc.)
The results summarized in Table 8 indicate clearly
H2 permselective dense membranes
the energetic advantages of some suggested membrane (Pd-based, dense SiO2, etc.)
operations.68 O2 permselective dense membranes
(Brownmillerite, solid oxides, etc.)
New Membranes porous infiltrated composite membranes for MRs
(dense silica/γAl2O3 composite membranes,
More and more complicated and special separation VMgO/ZrO2/RAl2O3, perovskites/RAl2O3,
problems of liquid and gaseous mixtures in industry and VmgO/RAl2O3, VPO/RAl2O3, etc.)
inorganic nanofiltration membranes
biomedical or medical technology require tailored fin- (ZrO2 on ceramic support)
ished products made from potential membrane materi- hollow-fiber ceramic membranes
als available on the market. The range of application
fields involves widely spread uses in micro-, ultra-, and by Bayer). It is characterized by a maximum long-term
nanofiltration, dialysis, membrane electrolysis, or re- stability of 190 °C. Hollow fibers produced from PEEK
verse osmosis, as well as in fields such as high- and PPS show textile-like properties, so that flexible
temperature gas separation, hydrogen recovery from modules with large membrane areas and small volume
syngases, and also oxygen-enriched air. Accordingly, the filling can be realized for the purposes of gas separation.
number of investigated and established membrane Regarding separation performance, permeability, and
materials has also simultaneously grown. Some ex- thermal and mechanical stability, PEEK membranes
amples are listed in Table 9. are better than the PPS ones.69
Among the variety of new thermoplastics developed Modified PEEK (PEEK-WC), an amorphous polymer
up to now are some special polymers that have been exhibiting mechanical and electrical properties equal to
shown to be particularly suitable for membrane produc- or better than those shown by traditional PEEK, is also
tion. For example, the aromatic poly(etheretherketone) soluble in DMA, DMF, chlorohydrocarbons, etc., which
called Vitrex (PEEK produced by ICI) shows a remark- makes possible its use for asymmetric membrane for-
able long-term temperature stability of 250 °C, where mation with the phase inversion procedure.70 Interest-
the modulus of elasticity remains sufficient even at 150 ing results have been obtained with PEEK-WC dense
°C. Because of its mechanical and chemical stability, membranes showing high O2/N2 selectivity and good
Vitrex represents a suitable material for the production permselectivity to water in the pervaporation of water/
of hollow fibers. Another polymer tested for this purpose methanol mixtures, as well as in acetic acid aqueous
is called Tedur (polyphenyle sulfide, PPS, manufactured solutions.
1294 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Table 10. Afforded Methods for the Synthesis of Porous Infiltrated Composite Membranes
method applications
chemical vapor deposition/infiltration synthesis of dense silica/γAl2O3 composite membranes highly selective to H2
(CVD/CVI) (supplied by MPT)82
direct impregnation of a porous support synthesis of VMgO/ZrO2/RAl2O383 (contactor for ODHP)
with salt solutions synthesis of perovskites/RAl2O384 (VOC combustion)
synthesis of meso- and microporous inert85 or catalytically active86 membranes
sol-gel/infiltration
synthesis of mixed oxides composite membranes (VMgO/RAl2O3, VPO/RAl2O377)
solvothermal (hydrothermal/infiltration) synthesis of supported zeolite membranes (silicalite-1, ZSM-5, A-type, mordenite,
zeolite Y, ferrierite, AlPO4-5, zeolite L, SAPO, etc.) with insertion of catalytically
active sites87

PEEK-WC modified by the introduction of NO2 thickness of the separating layer and, to a lesser extent,
groups or by sulfunation are also studied for gas changes in the material composition of the separating
separation applications.71,72 layer and optimization of the fiber size.
The use of PEEK-WC membranes functionalized The good H2 permselectivity and permeability of the
with o-octyloxycarbonyl β-cyclodextrin derivatives to recently developed dense (Pd-based) and almost dense
carry out the hydrolysis reaction of p-nitrophenyl ace- SiO2 membranes were successfully exploited for a
tate to p-nitrophenol in phosphate buffer enhances the number of H2-consuming or -generating reactions. For
reaction rate with an enzyme-like behavior, improving some applications, the thermochemical instability of Pd
productivity and stability and decreasing costs.73 membranes and the hydrothermal instability of silica
Much research on the synthesis of more selective, are the main problems to solve. Concerning O2-generat-
permeable, and stable membrane materials for gas ing or -consuming reactions, the development of O2
separation has been done and is still ongoing all over permselective membranes with good fluxes in the range
the world. For this purpose, some interesting results of 400-700 °C is still needed. Promising Brownmillerite
have been presented in the recent literature. dense membranes were recently developed by Eltron
Novel silicone-coated hollow-fiber membrane modules Research Inc.77 Most of the membrane research for
for the removal of toluene and methanol from N2 have membrane reactors aims at the development of thin
been tested.74 This novel membrane offers lower per- films on porous supports for obtaining high fluxes.
meation resistance than other silicone-based mem- Because of a strict synthesis protocol, large-scale pro-
branes because the selective barrier is ultrathin (1 µm) duction of such membranes with consistent quality
and the porosity of the polypropylene substrate is high. induces high-cost membranes and limits the range of
The bond between the substrate and the coating layer industrial applications. Porous infiltrated composite
has been obtained by plasma polymerization. High membranes (in which the membrane material is depos-
separation factors have been obtained (toluene/nitrogen ited in the pores of the support) are attractive candi-
)10-55; methanol/nitrogen )15-125; more than 96% dates, with good thermochemical resistance (barrier
of VOCs removed from a feed stream of 60 cm3/min effect) and easy reproducibility (see Table 10). Further-
when the permeate side was subjected to a high more, in the case of catalytic membranes, a high
vacuum).74 quantity of catalyst can be deposited in such a mem-
New 6FDA-DAF polyimide membranes have been brane configuration, which provides for easy diffusion
obtained by simultaneous suppression of intersegmental of the reactants to the catalyst.78,79 In particular, zeolite
packing and inhibition of intrasegmental motion with membranes,80 mainly used for gas and vapor separa-
a significant increase in both permeability and selectiv- tions, have scarcely been used as O2 distributors in
ity.75 These membranes have been tested with mixtures membrane reactors81 or for their catalytic properties.
of He-CH4 and CO2-CH4. Permselectivities of helium
The insertion (postsynthesis or in situ) of catalytically
and carbon dioxide over methane are improved with
active sites (e.g., Pd, Pt, V, etc.) might extend the
respect to the other polymers: the permeability of He/
possibilities of these membranes for membrane reactor
CH4 is 2.6 times higher in these membranes than in
applications.82,83
polysulfone.
Roman76 recently presented new fiber spinning and Recent studies on membranes made with perfluori-
processing technology and streamlined/automated nated polymers show the possibility of their application
bundle-forming processes to reduce manufacturing costs in the field of separation processes performed in hostile
and enable greatly increased production volumes. An environments, i.e., high temperatures or aggressive
important innovation has been the development of a nonaqueous media, such as chemicals and solvents.
proprietary co-extruded sheath/core fiber construction, Perfluoropolymers are polymers designed for high de-
effectively a thin asymmetric layer coated on a rugged manding applications in hostile environments. The
porous support. The mechanical support function is presence of fluorine in the polymer backbone imparts
uncoupled from the permeation function, so both func- to the structure an ability to withstand very high
tions can be optimized and a large fraction of the fiber temperatures and a very high resistance to chemical
wall, the core in this case, can be made of an inexpensive attack. Copolymers of tetrafluoroethylene (TFE) and
polymer to save on material costs. An additional ad- 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole (TTD), com-
vantage of the sheath/core construction is that it helps mercially known as HYFLON AD, are amorphous
form a thinner skin in the sheath layer by allowing the perfluoropolymers with glass transition temperatures
use of sheath spinning solution with low polymer (Tg) higher than room temperature. They show a
content and low viscosity (lower than could be used for thermal decomposition temperature exceeding 400 °C.
a self-supporting monolithic membrane). The O2 and N2 An important peculiarity of these polymer systems is
flow rates in Air Liquide’s N2 membrane have been that they are highly soluble in fluorinated solvents, with
increased 2-fold since 1990,77 via reduction of the low solution viscosities. This aspect allows for the
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1295

Table 11. New Modules and Strategies for Concentration Polarization and Fouling Control
module/strategy for fouling reduction effect applicationsa
countercurrent transverse flow mass-transfer coefficient increase RO
hollow-fiber module with baffles
spirally wound feed flow channels Dean vortex formation RO, UF, MF
coiled modules (tubular/hollow fiber) Dean vortex formation UF, MF, PV, MC
gas sparging secondary flow and local mixing generation near membrane UF, MF, MBR
surface
fluidized bed turbulence, continuous mechanical erosion of particle deposits MF
at wall of membrane
negative TMP pulsing (back-pulsing) periodic removal of particle cakes from membrane surface UF, MF
(with ceramic
membranes)
dynamic filtration generation of high shear rates in fluid near membrane UF, MF
rotary disk modules
vortex flow filtration
vibratory shear-enhanced processor
immersed membrane with aeration system contaminants not forced into membrane pores under high UF, MF, RO
pressure, aeration minimizes settling of solids and both
agitates and scrubs the membrane surface
a UF ) ultrafiltration; MF ) microfiltration; PV ) pervaporation; MC ) membrane contactor; MBR ) membrane bioreactor; TMP )

transmembrane pressure.

preparation of self-supported and composite membranes purification of biological materials for hemodialysis and
with desired membrane thicknesses.84,85 virus filtration.
During the 1990s Techsep (Orelis) initiated an ambi- In the meantime, Praxair, Inc. and the University of
tious R&D project to design inorganic nanofiltration New Mexico are studying a new gas separation technol-
membranes. These membranes were first developed in ogy consisting of porous membranes containing special
collaboration with the nuclear industry (Commissariat sites designed to temporarily bind to particular gas
à l’Energie Atomique and its subsidiary SFEC, France). molecules, promoting their transport through the mem-
The membrane is a pure inorganic ZrO2 layer obtained brane (facilitated transport membranes). In particular,
by sol-gel technology and deposited on a Kerasep TM polymeric systems, compatible with current manufac-
ceramic support. New possibilities have been opened by turing methods, and mixed inorganic-polymer coatings,
nanofiltration ceramic membranes now available on the offering better pore-size control, are being studied.
market for several years: they can be used in a very
broad range of operating conditions (pHs from 0 to 14, New Module Design and Strategies for
severe oxidizing or reducing conditions, thermal resis- Concentration Polarization and Fouling
tance from 0 to 350 °C, high-pressure resistance, inert- Control
ness toward radiation, etc.), which means that new
membrane applications can be examined. Although involving less novel scientific principles,
Recently, engineers at the TNO Institute of Applied module technology is also absolutely crucial to the
Physics, Materials Research and Technology Division, successful implementation of membrane technology.
in Eindhoven, The Netherlands, believe they have Seals, assembly methods, flow distribution, and pres-
solved several of the common problems with ceramic sure-drop minimization require careful attention, and
membranes by developing and commercializing them in this trend will intensify as the field matures and
the shape of hollow fibers instead of tubes. These competition intensifies.
patented hollow-fiber ceramic membranes have a high In the past few years, additional innovations in
surface-to-volume ratio (more than 1000 m2/m3) and are module design and new strategies and techniques have
easy to scale-up. TNO also combines this technology been explored, particularly in the reduction of concen-
with highly selective top layers. Compared to existing tration polarization and fouling problems in pressure-
flat and tubular membranes, ceramic hollow-fiber mem- driven membrane operations. Some examples are listed
branes have the advantage that they are compact and in Table 11.
up to 10 times less expensive to produce. These mem- A countercurrent transverse-flow hollow-fiber RO
branes are now being used in slurry reactors. There are module with baffles has been designed for low feed flow
also applications in wastewater treatment to selectively velocities transverse to the hollow fibers to achieve high
remove pollutants and in gas separation. One ceramic mass transfer coefficients in an overall countercurrent
membrane nearing commercialization is being devel- flow (on the module scale) to the permeate flow through
oped by Pall Corp., East Hills, NY, based on DOE the tube side.87
classified technology through a Cooperative Research Spirally wound feed flow channels with membrane
and Development Agreement (CRADA). Pall also re- walls will allow the formation of Dean vortices, which
cently commercialized a stainless steel membrane with will mix the bulk with the wall layers and reduce
this technology.86 concentration polarization without moving the mem-
Recently (October 1998), in the U.S., a research brane or the module or having flow reversal in the feed
project has been partially funded by the DOE to develop stream via inserts or otherwise.88 Such a concept is
a new fabrication process for ultrafiltration membranes useful for UF and MF as well (see Figure 19). Although
based on thermally induced phase separation (TIPS) to Dean flows satisfy the exigencies of an efficient mem-
produce membranes with more uniform microscopic brane process, such as high permeate flux by increased
pore sizes in an appropriate range (down to the 10-50 wall shearing, radial mixing, and low concentration
nm size range), enabling more efficient separation and polarization, the presently employed modules still have
1296 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 19. Schematic representation of a spiral tubular membrane module.

the problem of low packing density and increased The fluidized solids ensure a significant reduction in
pressure drop, which renders the process operating costs concentration polarization as well as a continuous
relatively higher than conventional processes.89-91 In mechanical erosion of the particles deposited at the wall
laminar conditions, the limiting flux obtained in ultra- of the membrane. The improved permeate flux that is
and microfiltration coiled modules is higher than that achieved is due to the combined action of turbulence and
obtained in straight ones. The enhancement can reach particle motion.97
a factor of up to 5 depending on module characteristics, Negative rapid transmembrane pressure (TMP) puls-
hydrodynamic conditions, and suspension properties. ing has been increasingly adopted to control fouling in
The energy analysis shows that, for the same energy conventional and ceramic membranes to restore mem-
dissipation, the limiting flow reached in a helical module brane productivity and increase solvant flux.98
is still far greater than that reached in a straight An other strategy explored to enhance filtration
module. performances in UF and MF is so-called “dynamic
There are also potential advantages of the Dean flow filtration”, which consists of creating high shear rates
in some other membrane operations, e.g., membrane in the fluid near the membrane by relative motion
oxygenators or pervaporation. between a fixed membrane and a moving wall or vice
In the laminar flow regime, the mass transfer coef- versa. The main advantages of this technique are that
ficients obtained in gas-liquid contactors (water oxy- these high shear rates can be generated independently
genation and VOC removal) are higher than those of the feed flow and that, because of the small head loss
obtained using modules with straight fibers.92,93 in the system, transmembrane pressure can be kept
It is known that, in ultrafiltration, concentration lower than in the classical cross-flow filtration. It is,
polarization affects the permeate flux (the productivity) therefore, advantageous for filtrating highly charged
and membrane rejection characteristics (the separation fluids or for some biotechnological applications99 when
efficiency). Injection of gas bubbles to generate second- it is necessary to use low TMPs for solute recovery. The
ary flow and to promote local mixing near the mem- system is very efficient in terms of permeate flux, for
brane surface proves effective in overcoming concentra- example, with highly concentrated mineral suspensions.
tion polarization. When applied to protein fractionation, A rotary disk module was developed based on the
gas sparging can also improve the selectivity signifi- patent of NIMIC and Hitachi Plant Engineering and
cantly. One application of such a process might be in Construction Co. for the low-power separation of highly
enzyme membrane bioreactors. For vertical membrane concentrated liquids. A conventional membrane module
systems, the observed enhancement, in terms of per- circulates the treated liquid at a high flow rate so as to
centage increase in permeate flux, depends on the obtain a rapid flow at membrane surface and a high flux
severity of the concentration polarization and membrane through the surface. On the other hand, rotating the
surface shear. When concentration polarization is se- membrane would allow a high flow rate at the mem-
vere, for example, at low cross-flow velocities, at high brane surface to be maintained without having to
transmembrane pressures, and at high feed concentra- maintain high pressure. Therefore, relatively low power
tions, the observed flux enhancement is higher (up to would be required to run the system.100
320%). With high shear systems, including hollow-fiber An alternative widely commercialized technique de-
module and spiral-wound membranes, or even for highly veloped by Membrex Inc. is called the Vortex Flow
turbulent flow, injecting gas at low flow can only achieve Filtration (VFF) system wherein the feed is introduced
a marginal flux enhancement (20-36%).94,95 into the annular gap between two cylinders, one of
Two-phase flow in ultrafiltration hollow fibers is very which is rotating. The membrane can be placed on either
efficient in enhancing mass transfer when it is limited the inner or the outer cylinder. Taylor vortices are
by particle deposition. Air sparging seems to expand the generated between the two curved surfaces, creating
particle cake, as it increases both cake porosity and high shear at the membrane surface, but the feed
thickness, thus allowing higher water fluxes. This effect pumping is low. The VFF technique is employed for
can be explained by the mixing and turbulence created smaller systems.
by the slug flow. In some cases, intermittence also For feed streams having high solids fractions, new UF
affects the cake structure.96 techniques are used commercially. The VSEP system
The use of a fluidized bed during the microfiltration employs membrane leaf elements as parallel disks
of suspensions on ceramic membranes results in a separated by gaskets in a disk stack, which is spun in
significant increase in permeate flux in comparison with a torsional oscillation like the agitator in a washing
results that can be obtained with an empty-tube system. machine at a fast rate to produce shear rates as high
This phenomenon is especially pronounced during the as 15000 s-1 and, therefore, a much higher flux. The
microfiltration of oil emulsions when the permeate flux cost per square meter is high compared to that of
in a fluidized-bed system is almost three times higher. commercial cross-flow systems. A second high solid
Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1297

commercialized UF system called Discover achieves sociated with water production and membrane fouling
high fluid shear at a flat membrane plate surface by (the contaminants are not forced into the membrane
spinning a grooved disk between adjacent membrane pores under high pressure). An aeration system permits
plates; fluxes are 5-6 times larger than those in a consistent flux to be maintained because of the
competing units with sludges containing oil and sus- generation of a recirculation pattern in the process tank
pended solids. that minimizes the settling of solids and both agitates
The PallSep VMF system101 is another vibrating and scrubs the membrane fiber surface to prevent
membrane system commercialized by Pall Co. used as plugging and fouling.
an efficacious and economical alternative to rotary
vacuum filters, centrifuges, and cross-flow systems for New Areas of Interest for Membrane
the treatment of a wide variety of difficult-to-filter Engineering
process streams in pharmaceutical and bioprocess ap-
plications. The significant results already reached in the devel-
opment of membrane operations as discussed in the
A characteristic of these UF techniques is the decou- previous pages suggest other areas in which the overall
pling of the wall shear from the bulk liquid flow rate possibilities of membrane engineering might be of
(and sometimes pressure). This is radically different importance.
from fluid management techniques used in conventional The case of transportation technologies is of particular
membrane devices for controlling polarization, fouling, interest.
gel layer formation, etc.102 Transportation technologies, for example, will go
Drinking water and industrial water on Hokkaido through an important revolution in the next few years,
island (Japan) are produced with conventional water mainly because of concerns about the poor air quality
production technology from natural river water that in many of the cities of industrialized countries, increas-
contains organic components such as humic substances, ing levels of greenhouses gases, and problems with the
but the conventional membrane separation system (UF) oil supply.
is not suitable for treating river water in the summer Various interesting projects are in progress worldwide
when turbidity and color become high. To solve the trying to accelerate the solutions to these problems.
problem mentioned above, vibratory shear-enhanced The Exploratory Technology Research Program in the
processing is used. The system has a unique vibration U.S., which seeks to identify new batteries and fuel-
mechanism that generates shear rates on the surface cell systems with higher performance and lower life-
of the membrane so that it is resistant to fouling caused cycle costs than those available today, is an important
by the PAC [poly(aluminum chloride] used to facilitate example of these actions. Membrane systems represent
coagulation of such natural organic matters for easy a significant aspect of these efforts.
removal. The commercial production facility achieves a For example, proton-exchange-membrane (PEM) fuel
fairly high permeate flux compared with that of con- cells are, in principle, capable of high power density and
ventional membrane operation technology and has been of changing their power output more quickly than other
able to produce the required water quality. The opera- fuel cell types, making them candidates for replacing
tion with vibration increases flux by about 1.5 times internal combustion engines in transportation applica-
when a relatively high pressure is applied.103 tions, particularly in the automotive industry. Methanol,
An inorganic membrane module of the external pres- ethanol, hydrogen, natural gas, and gasoline are being
sure type was developed by Kubota Corporation. The evaluated as fuels. The technical barriers that must be
main feature of the equipment is that some tubular overcome include size, weight, and cost reductions; fuel
membrane modules without casing are submerged in storage, conditioning and delivery; durability; reliability;
the anaerobic tank and row water is directly filtered etc.
through the membrane. The results obtained were At Argonne National Laboratory, a new 10-kW partial
succeeded by the Japanese national project Membrane oxidation methanol reformer with 50% H2, less than 4%
Aqua-Century 21 by the Ministry of Health and Welfare, CO, thermal efficiency of 88-95%, excellent dynamic
which was aimed at the development of membrane response, and rapid start-up (<100 s) has already been
technology for the purification of drinking water.104 The demonstrated.
equipment consists of a coagulation tank, an aeration Direct methanol fuel cells (DMFC), which eliminate
tank equipped with modules inside, an air blower, a the need for an external reformer, reducing the system
suction tank, and an air compressor for back-washing. weight and cost, are under investigation at Los Alamos
The driving force of filtration is hydraulic pressure and National Laboratories (LANL). Technical problems
the suction force of a pump to keep water flow constant. include methanol permeation through the membrane.
The system is now commercially available for water By NMR spectroscopy, the diffusion coefficient of metha-
purification. nol in Nafion membranes has been measured. It is only
Recently, ZENON Environmental Systems Inc.105 a factor of 2-3 smaller than the diffusion coefficient in
developed a new generation of membranes for water and aqueous solutions, and this is an important factor
wastewater treatment known as ZeeWeed. This new contributing to the sizable methanol crossover rates
membrane is of the immersed hollow-fiber type and is observed.
able to operate in high solids environments (10 000- Solid polymer electrolyte membranes play a vital role
15 000 ppm). Unlike conventional membranes that are in these fuel cell systems. Unfortunately, costs (U.S. $
housed in pressure vessels and require a positive 70-150/ft2) appear to be still too high.106
pressure, the immersed membrane operates in an open In the U.S., an interesting coordinated national
tank environment under a slight vacuum (-2 to -8 psi). program was launched in 1998 for the promotion of
The lower operating pressure, which provides increased industrial research in this area.
membrane life and reduced replacement costs, also The goal is to develop a totally new fuel cell system
permits the reduction of the energy requirements as- with improved CO tolerance (raising permissible levels
1298 Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

by 50 ppm to 3000 ppm), by using a high-temperature, In fact, as already evidenced, the most interesting
ion-conductive solid polymer membrane electrode as- developments for industrial membrane technologies are
sembly and new bipolar separator plates. Other impor- related to the possibility of integrating various of these
tant projects are in progress on fuel cell technologies membrane operations in the same industrial cycle, with
that are going to depend mainly on the membrane overall important benefits in terms of product quality,
concept design. plant compactness, environmental impact, and energetic
aspects.
Conclusions It is known that existing non-membrane-based equi-
librium-driven separation technologies (e.g., absorption,
Not many years have passed from the days when Loeb adsorption, distillation, extraction, ion exchange, strip-
and Sourirajan, with their preparation of asymmetric ping), which represent the core of the traditional chemi-
membranes, made the reverse osmosis process of in- cal and petrochemical industry, have significant short-
dustrial interest. comings: inherent operational difficulties, lack of
The early membranologists have always been opti- flexibility and modularity, slower rates, need for haz-
mistic about the possibilities of membrane operations, ardous chemicals, high capital costs, higher energy
but the scientific and technical results reached today requirements, and need for large equipment volume.
are even superior to the expectations. These shortcomings are exacerbated by new separation
The intrinsic multidisciplinary character of mem- demands (for example, environmental pollution control
brane science has been and is still today one of the major laws). New membrane-based separation concepts and
obstacles to the further exploitation of its possibilities. technologies (e.g., vapor permeation, osmotic distillation,
The new logic of membrane engineering based on a facilitated transport, supported liquid membranes, mem-
drastic rationalization of the existing process design and brane-based extractors, membrane-based absorption,
not on the more traditional approach of adding one and stripping in contactors) do not suffer from many
more, eventually innovative, unit at the end of the such deficiencies and are poised to invade more and
existing pipe, which has been another obstacle to the more the domain of traditional separation technologies.
growth of membrane units, will also contribute to the It is, then, realistic to affirm that new wide perspec-
exploitation of these technologies. tives of membrane technologies and integrated mem-
A variety of technical challenges must be overcome brane solutions for sustainable industrial growth are
to permit the successful industrial application of new possible.
membrane solutions. For example, the development of It is also important to recall that the most recent
catalytic membranes will depend on material advances legislation and standardization are finally starting to
and increases in module reliability under extreme- identify the role of membrane operations in various
temperature cycling. The development of affinity mem- areas (production of pure water for pharmaceutical uses,
branes will require research on electron-beam grafting production of wine, of drinkable water or of ultrapure
and other approaches to the modification of membrane water for electronic industry, etc.). In Japan and in the
chemistry. The development of tunable membranes will U.S., the introduction of official standards for character-
require extensive research on materials (e.g., conducting izing the membranes used in various processes is
polymers) and assembly processes (e.g., chemical vapor already in progress.
deposition). In general, advanced membrane and module
materials need to be matched with appropriate, eco-
nomical manufacturing processes. Acknowledgment
The limitations still existing today to the large-scale We have to acknowledge various colleagues from the
industrial applicability of some membrane operations IRMERC-CNR for their data and information on the
can be attributed only in part to inadequate intrinsic various processes of their specific interest and, in
membrane properties (low permeability and selectivity, particular, Dr. L. Giorno, Dr. G. Clarizia, Ms. A.
low thermal and chemical resistance, etc.) but probably Gordano, and Mr. A. Cassano.
more to inadequate module design, hydrodynamic stud-
ies, and, in general, engineering analysis.
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