Membranr Separation Technologies

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MEMBRANE SEPARATION TECHNOLOGIES: CURRENT DEVELOPMENTS

KAMALESH K. SIRKAR
a a
Department of Chemical Engineering, Chemistry and Environmental Science, New Jersey Institute of Technology, University Heights, Newark, NJ, 07102 Available online: 06 Apr 2007
To cite this article: KAMALESH K. SIRKAR (1997): MEMBRANE SEPARATION TECHNOLOGIES: CURRENT DEVELOPMENTS, Chemical Engineering Communications, 157:1, 145-184 To link to this article: http://dx.doi.org/10.1080/00986449708936687
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1997 OPA (Overseas Publishers Association) Amsterdam B.V. Published in The Netherlands under license by Gordon and Breach Science Publishers Printed in Malaysia
MEMBRANE SEPARATION TECHNOLOGIES: CURRENT DEVELOPMENTS

KAMALESH K. SIRKAR
Downloaded by [Midlands State University] at 01:49 21 May 2012
Department of Chemical Engineering. Chemistry and Environmental Science. New Jersey Institute of Technology. University Heights. Newark. NJ 07102 (Received 22 December 1995; In final form 26 June 1996)
This article provides a brief overview of major developments in membrane separation technologies over the last six years until 1995. Progress in membrane separation processes, membrane separation techniques and membranes for given separation problems are of primary interest. The order of importance for membrane separation technologies is: already commercialized, being commercialized 'and having great potential based on laboratory performance. Separations involving liquid solutions, gaseous mixtures and particle removals have been covered, Notable recent developments in eight commercialized technologies namely, reverse osmosis, ultrafiltration, microfiltration, electrodialysis, dialysis, pervaporation, gas permeation, emulsion liquid membrane are illustrated first. New membrane-based equilibrium separation processes involving gas-liquid and liquid-liquid contacting, distillation and adsorption are then considered. The progress in new membrane-based rate-governed separation processes of vapor permeation and continuous deionization are treated next followed by a number of developing techniques, e.g., perstraction, facilitated transport, osmotic distillation, contained liquid mernbrane, supported liquid membrane and supported polymeric liquid membrane. Developments in hybrid separation processes where one of the techniques employs membranes are identified. The potential and current reality of membrane reactors is provided at the end.
Keywords: Membrane separation technologies; commercialized processes; new membrane processes; hybrid processes; membrane reactors
l. INTRODUCTION
Established commercialized membrane separation technologies are being increasingly incorporated in industrial processes, large or small. New membrane separation technologies are overcoming the commercialization barrier. Research and development in membrane separation technologies are rapidly expanding all over the world. The objective of this article is to provide a brief overview of such membrane separation technologies as they
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have evolved over the last five to six years until 1995. References to publications and/or presentations in 1996 will be very limited. The emphasis will be on processes, technologies/techniques, and membranes capable of solving separation problems rather than analysis, membrane transport mechanisms, process models, etc. This will facilitate an understanding of the driving forces and dynamics of this rapidly evolving sector of separation technologies. For a comprehensive introduction to a variety of membrane separations processes, consult Ho and Sirkar (1992). Chapter one of this reference also lists major texts which treat different aspects of a variety of membrane separation processes. Recent notable texts not mentioned in Chapter one of Ho and Sirkar (1992) include Huang (1991), Mulder (1991), Matsuura (1993) and Noble and Stern (1995). Conventional separation processes like distillation, absorption, adsorption, stripping, extraction, etc. are employed to solve particular types or classes of separation problems. For example, distillation is employed to separate a liquid solution of two or more volatile substances. Membranes and membrane separation techniques have been employed, however, to separate a wide variety of types or classes of separation problems. The breadth of such applications is briefly illustrated in Table I for separations involving liquid solutions and suspensions. A similar table may be prepared for separation of gas mixtures, gas-vapor mixtures and vapor-vapor mixlures. Table I is illustrative of capabilities of membrane processes; many have been realized in commerical practice. Table I does not suggest that membrane separation processes are the most efficient, practical or economic way to solve all problems identified. In fact, many traditional separation processes, e.g., distillation, optimized through many years of research and develTABLE I Types of liquid separations' achieved by membrane separation technologies
A.
B.
C.
D. E. F. G.
H. I.
Dissolved Gases from Solution Minor Volatile Liquid AQ TORG Component from Bulk ORG TAQ Solvent ORG TORG Bulk Volatile Liquid Mixture Low and Medium (M.W. 200-700) Organic Fractionation Electrolyte In Aqueous Solution: Divalent-Monovalent;
Heavy Metal Separation from Water
Protein/Macromolecules in Solution:
Separation/Fractionation
Oil-Water-Emulsion/Particulates Separation
Isomer Separation Various Combinations of above
"'Feed conditions/requirements: slurry feed: fermentation broth; mono-
valem salt presence does not marter; hazardous waste stream; process stream.
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opment, are highly successful and versatile. Yet membrane processes are slowly but steadily solving problems considered traditionally the preserve of other separation processes. From their inception in the late fifties and early sixties, synthetic membranebased rate-governed separation technologies were developed to solve practical separation problems in chemical and biochemical processes and biomedical devices. Recent developments continue that tradition. The developments in membrane-based solution of practical separation problems in chemical and biochemical processes and water/air treatment during the last five to six years are being achieved primarily in three ways. First, established commercialized membrane separation technologies [Ho and Sirkar, 1992] may have had limitations of chemical stability, compactness, flux, fouling, pressure capability, scalability, selectivity, separation schemes, temperature, etc. in general or in particular applications. These technologies are reverse osmosis (RO), ultrafiltration (UF), microtiltration (MF), electrodialysis (ED), dialysis, pervaporation (PV), gas permeation and emulsion liquid membrane (ELM). Current generations of membranes and membrane devices for such processes have overcome a number of earlier shortcomings and/or perform substantially better. The progress in a given membrane separation process may be of an evolutionary nature or may involve a radical departure in terms of module design or membrane design or membrane material (e.g., ceramic vs. polymer). Second, existing non-membrane-based equilibrium-driven separation technologies (e.g., absorption, adsorption, distillation, extraction, ion exchange, stripping) may have significant shortcomings: inherent operational difficulties (emulsification, foaming, entrainment, weeping, etc.), lack of flexibility (flooding, loading, need for density difference, etc.), slower rates, need for hazardous chemicals, lack of modularity, high capital costs, higher energy requirements and the need for large equipment volume. These shortcomings are exacerbated by new separation demands (for example, environmental pollution control laws, etc.). New membrane-based separation concepts and technologies (e.g., continuous electrodeionization, vapor permeation, facilitated transport, osmotic distillation, contained liquid membranes, membrane-based absorption and stripping in contactors, membranes-based extractors, membrane adsorbers, etc.) do not suffer from many such deficiencies and are poised to enter the domain of traditional separation technologies like absorption, stripping, extraction, adsorption, ion exchange and distillation. Sometimes, these new techniques are even better than the more established membrane separation technologies. Third, a variety of hybrid processes are emerging where a traditional separation process and a membrane separation process are used in an integrated fashion to achieve what cannot be attained economically by
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either separation technique alone. Alternately, a hybrid process is needed since the individual technique may have a severe deficiency (e.g., a species present in some feeds at small concentrations will reduce the membrane performance drastically). The hybrid processes of the first kind employ process schematics where the inputs/outputs of two different processes in two different devices are coupled together in a variety of ways. Separation concepts have also emerged wherein two separation mechanisms are simultaneously operative within one device; such a hybrid process may be called a composite separation process. In chemical and biochemical processing, separation processes are usually employed to purify products (and recover unconverted reactants) from streams leaving the reactor. The reactor conversion and the subsequent separation steps are often facilitated by incorporating a membrane or two inside the reactor. Considerable research is being done to incorporate membranes within a reactor and some progress towards commercialization has been made. The excitement in the research community working in this area coupled with the material challenges and pote~tial rewards for the right membrane and the right reaction system suggest membrane reactors as the fourth vehicle for illustrating current developments in membrane separation technologies. This overview will briefly identify/illustrate many of the current developments in many (but not all) of the membrane separation technologies via the four categories described above. Concurrently, there will be occasional glimpses of future opportunities in each category. For a comprehensive listing of opportunities in established membrane processes, see DOE (1990). Current developments in established commercialized membrane separation technologies will be treated first (section 2), followed by those in new membrane-based separation technologies/concepts (section 3), hybrid processes (section 4) and membrane reactors (section 5) in that order. Given the extraordinary bustle in and the breadth of current membrane separation research and development activities, it is inevitable that some recent developments will not be mentioned here or receive inadequate attention. Such omissions/underemphasis are not by design.
2. ESTABLISHED COMMERCIALIZED MEMBRANE SEPARATION TECHNOLOGIES Notable recent development in eight established commericalized membrane separation technologies will now be considered in the following order: RO,
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UF, MF, ED, dialysis, PV, gas permeation and emulsion liquid membranes. Nanofiltration (NF) is considered in the section on reverse osmosis.
2.1. Reverse Osmosis (RO)

It is appropriate to consider RO first since the earliest boost to membranes for nonmedical applications was provided primarily by RO. Further, RO is often considered to be a "plateau" technology. Yet many significant innovations have been made to decrease the operating pressure to the ultralow value of 70 psig (0.58 MPa), increase the upper limit of operating pressure to 3000 psig (20.78 MPa) and above, handle highly fouling feeds, improve the membrane productivity, purify hazardous liquids, etc. The operating pressure in conventional RO with high NaCI-rejection capability varies from a high of around 800-1000 psig (5.61-8.37 MPa) for seawater desalination to around 200-400 psig (1.48-2.86 MPa) for brackish water desalination or water/wastewater treatment (Bhattacharyya et al. 1992). Improved membranes have now been developed so that high flux and high salt rejection are achieved even though the operating pressures are much lower. Such membranes are commercially marketed by Hydranautics, Inc. (San Diego, CAl under the brand name ESPA" (energy saving polyamide membrane) and Fluid Systems, Inc. (San Diego, CAl under the brand name Ultralow Pressure Thin Film Composites TFC"-ULP. It is useful to illustrate one such development. Ultralow pressure RO membranes and spiral-wound modules operate at pressures lower than 100 psig (0.79 MPa) and produce potable water via reduction in hardness and total dissolved solids (TDS), effective reduction in total organic carbon (TOC) as well as disinfection by-product precursors (humic acid, fulvic acid, etc.). Even at such low pressures (net driving pressures of 100 psi (0.68 MPa)), these membranes (TFe"-ULP) have 25-30 gfd (galjft2-day) water flux, >98% MgS0 4 rejection and >96% NaCI rejection for a feed having 2 giL NaCI and 5g1L MgS0 4 [Takigawa et aI., 1995]. It would be of interest to know the basis for this improved performance: whether these thin film composite (TFC") membranes have a thinner saltrejecting layer (on a porous support) than conventional TFC" membranes of arylalkyl polyetherurea and/or whether the thin polymer layer is supposedly more hydrophilic and less prone to fouling. The spiral-wound module and system design have been improved to reduced feed channel pressure loss. For a broad overview of thin film composite RO membranes, see Petersen (1993). For feed waters having high levels of suspended solids which would rapidly foul a spiral-wound RO module, tubular RO membrane devices,
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normally empolyed, have high energy comsumption 'and low membrane surface area packing density. An innovative membrane module, Rochem Disc Tube", has been developed and commercialized extensively to minimize membrane fouling, scaling and concentration polarization from high fouling feeds (Rochem Separations, Torrance, CAl. This is achieved in a stack of discs and membranes by providing an open channel feed flow path in a spacer disc over a circular membrane cushion built like the membrane leaf used in spiral-wound modules. The leaf edges are ultrasonically welded. In the center of the circular membrane cushion of 7 inch diameter, a hole is cut to create a permeate exit. The flow channel gap is 1 mm; the flow channel length is around 7.50 cm before the flow turns around a membrane cushion. The flow is turbulent. There is higher membrane surface packing density (150 m 2/m 3 ) than tubular modules, water fluxes as much as 40 gfd and standard operating pressures around 1000 psig [Stanford and Vail, 1992; Stanford, 1995]. Specialty versions are available for pressures as high as 2000 psig (13.89 MPa) and 3000 psig (20.78 MPa) to treat solutions having very high osmotic pressure. Many large systems up to 200,000 gpd (gallons per day) have been employed to treat contaminated pond waters, landfill leachates, cooling tower blowdowns, etc. System cleaning is easy. Feed pretreatment required is much less than that in conventional systems; in one case of pond water treatment, only 100 micron bag filters were needed. No modeling or analysis of this system is available in literature. Additional innovations in module design are being explored. A countercurrent transverse flow hollow fiber module with baffles has been designed for low feed flow velocities transverse to the hollow fibers to achieve high mass transfer coefficient in an overall countercurrent flow (on the module scale) to the permeate flow through the tube side [Futselaar et al., 1992]. Spirally-wound feed flow channels with membrane walls will allow the formation of Dean vortices which will mix the bulk with the wall layers and reduce concentration polarization without moving 'the membrane or the module or having flow reversal in the feed stream via inserts or otherwise [Brewster et al., 1993]. Such a concept is useful for UF and MF as well [Chung et al., 1993]. New applications of RO are being explored in water and wastewater treatements [Bhattacharyya et al., 1992] which continue to attract a major share of the membrane separation technology market. A most interesting one involves ultrapurification of multicomponent hydrofluoric acid (HF) etching solutions in semiconductor processing. A variety of commercially available RO membranes were found to allow highly selective permeation of HF and water through the membrane while strongly rejecting f1uosilicic
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acid and other trace metallic impurities in the HF etching solutions [Mukherjee et al., 1994a]. This research group has also serendipitously achieved a novel method of increasing the water flux of a Filmtec (SW30HR) TFC" RO membrane by an order of magnitude by chemically modifying the aromatic polyamide membrane surface via treatment with HF and fluosilicic acid; this resulted in partial fluorination and surface etching without any decrease in ionic rejection properties [Mukherjee et al., 1994b]. Some of the membranes have successfully performed for a period of 16 months with a 15 wt% HF solution [Kulkarni et al., 1994]. This is an interesting development and is being pursued further. Kulkarni et al. (1996) employed hydrofluoric, hydrochloric, sulfuric, phosphoric and nitric acids at various concentrations with or without alcohols to hydrophilize the surfaces of TFC membranes HR95PP and HR98PP (DDS membranes). Such exposure led to an increase in water flux from 2 to 10 times without any loss in ion-rejection. In all cases the membrane surfaces underwent an increase in hydrophilicity on exposure to protic acids. Many of the research opportunities and directions for RO membranes and processes identified in the DOE Report (1990), e.g., oxidation-resistant membrane, high-temperature capability, etc., have not yet been fully realized. The status of research efforts on understanding membrane-chlorine interaction for polymeric membranes and the failure modes of new generations of polyamide type membranes has been reviewed by Glater et al. (1994). Improved spacer design, spacer surface modification via surface charge, etc. to prevent fouling, lower limits of skin thickness in TFC" membranes for non-seawater type applications, reverse osmosis with organic liquids, etc. are additional areas of research opportunities in RO. Membranes in nanojiltration (NF) or "loose RO" introduced in the middle 80s have low rejections (10%-50%) of monovalent salts (e.g., NaCI) but high rejections (> 95%) of divalent ions (e.g., SO;) as well as organic. compounds of molecular weight 200 or greater. Such low rejections of monovalent salts like NaCI and high rejections of divalent salts and higher molecular weight organics allow low operating pressures to be used in high NaCI-containing feed solutions to achieve, for example, removal of BaS0 4 from seawater, organics from discharged water in offshore oil platforms, etc. Often the membranes are negatively charged. The operating pressure is usually around 200 psig (1.48 MPa). In terms of hypothetical pore sizes, NF membrane pores are larger than those in traditional RO membranes but are significantly smaller than those in UF membranes considered next. Rapidly emerging large-scale applications of the commercialized technology of NF are in the removal of hardness, color, TOC, and trihalomethane precursors
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in water treatement, water recovery from heavy metal-contaminated rinse waters, concentration of sugars etc. in the processing of streams in food and pharmaceutical industries and separating them from smaller molecular weight acids (e.g., acetic acid) which go through the membrane easily at low pHs [Bhattacharyya et al., 1992; Raman et al., 1994; Kramer and Al-Sarnadi, 1995]. There are a number of NF membrane/module suppliers, see Bhattacharyya et al. (1992). Improved NF thin film composite membranes having a better performance as well as resistance to caustic cleaning have been made [Kim, 1991]. Lin et al. (1992) have made a microporous y-alumina based NF membrane with a silica surface layer. A review of the progress in NF membranes has been provided by Petersen (1993). Membrane Products Kiryat Weizmann, Ltd. (Rehovot, Israel) has developed a series of SelRO NF membranes having molecular weight cut-off in the range of 200-700 and possessing excellent solvent resistance. These membranes are particularly useful for recovering, purifying or concentrating pep tides, homogeneous catalysts, etc. present in strong organic solvents, e.g., ketones, acetonitrile, toluene, tetrahydrofuran (THF), etc. Particular examples of these membranes are hydrophilic MPF-44, hydrophobic MPF-50, hydrophobic MPF60. The above membranes are available in flat form; hydrophilic MPS-44 (Type B) and TFC MPS-50 (Type B) (hydrophobic) are available in spiralwound form. Fractionation of organics, sugars (e.g., glucose from sucrose), etc. via a sharp pore-size distribution NF membrane is an attractive future opportunity [Li, 1993]. So far nanofiltration has been treated often as an adjunct of reverse osmosis (RO). As more and more novel applications are commercialized and more selective NF membrane are developed, the status of NF as a unique separation technology straddling the gap between RO and UF will be increasingly established. 2.2. Ultrafiltration (UF) Ultrafiltration has been commercialized since 1971 via the first whey-processing UF units in New Zealand. This pressure-driven process uses membranes having pore sizes between 10 to 1000 A ([Kulkarni et aI., 1992]; 10 to 200 A according to Cheryan (1986)). It has become a familiar unit operation in many industries as well as in laboratory operations, Progress is being made. in four different fronts: novel/improved membranes, fouling control in tangential flow devices, new module designs for high solids UF, improved permselectivity for viral retention. At least two new types of UF
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membranes have been introduced commercially for conventional UF processes: ceramic honeycomb monoliths (multichannel units) of alumina with Zr0 2 layers having pore sizes between 40 A and 500 A called Membralox" (U.S Filter, Warrendale, PAl [Bhave, 1991]; modified polyacrylonitrile flat membranes called UltraFilic (Membrex, Fairfield, NJ]. For ultrafiltration from nonaqueous solutions of solvents like ethyl acetate, polyimide membranes (Lenzing AG, Austria) have been successfully studied in a laboratory [Beerlage et al., 1996]. Brief details on inorganic UF membranes commercially available from different sources are provided in Bhave (1991). The most important problem in conventional tangential flow devices continues to be membrane fouling and consequent loss of productivity and solute fractionation capability. Negative rapid transmembrane pressure pulsing has been increasingly adopted to control fouling in conventional and ceramic membranes [Bhave, 1991], restore membrane productivity and increase solute flux [Rodgers and Sparks, 1991]. This technique employing a high backflush frequency is called "backflushing", In feed streams having high solids fraction, three new UF techniques are being used commerically. The VSEP system employs membrane leaf elements as parallel discs separated by gaskets in a disc stack which is spun in a torsional oscillation like the agitator in a washing machine at a fast rate to produce shear rates as high as 150,000 sec-I [Culkin and Armando, 1992] and, therefore, a much higher flux. Results on latex recovery from a waste stream with retentate total solids as high as 50% are good [Lodaya, 1995]; cost/m? is high comparable to commerical cross flow systems. A . second high solids commercialized UF system called Discover (Membrex) achieves high fluid shear at a flat membrane plate surface by spinning a grooved disc between adjacent membrane plates; fluxes are five to six times larger than competing units with sludges containing oil and suspended solids. An alternate widely commercialized technique developed by Membrex, Inc. is called Vortex Flow Filtration (VFF) system wherein the feed is introduced into the annular gap betwen two cylinders one of which is rotating; the membrane may be placed on either the inner or the outer cylinder. Taylor vortices are generated between the two curved surfaces creating high shear at the membrane surface but the feed pumping rate is low. VFF technique is employed for smaller systems. A theoretical analysis of such a system below the critical Taylor number has been made by Dolecek et al. (1995). A semi-empirical analysis and performance data are provided by Mateus and Cabral (1995) for VFF of a steroid solution containing albumin
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and/or whole cells. (The other two systems are likely to benefit from detailed models and analysis of the performance under actual operating conditions.) A characteristic of these three UF techniques is the decoupling of the wall shear rate from the bulk liquid flow rate (and, therefore, sometimes pressure). This is radically different from fluid management techniques used in conventional membrane devices for controlling polarization, fouling, gel layer, etc. Therapeutic proteins obtained from recombinant cell-based biotechnology suffer from potential contamination by virus or virus-like particles. Conventional polymeric UF membranes that are asymmetric often have "finger voids" in the substructure below the skin; further, they have a broad pore size distribution; a few large pores will allow a significant amount of virus to pass through the skin and, therefore, through the substructure and the membrane. The novel Yiresolve" membrane has a composite structure consisting of a thin polyvinylidene fluoride (PVDF) UF membrane cast on a preformed microporous substrate, a Durapore" PVDF membrane. The final composite is treated to be hydrophilic and low protein binding [DiLeo et al., 1992]. The structure allows maximum passage of product protein but retains > 99.9% of a 28 nm diameter virus. As the virus particle size increases, particle retention increases monotonically. Colloid-enhanced ultrafiltration (CEUF) techniques have been studied for removal of multivalent metals and organics from polluted waters; polyelectrolyte-enhanced ultrafiltration (PEUF) has been investigated for removing hardness ions (Ca ++, Mg+ +) from water. In such techniques, .micelle-forming surfactant or polyelectrolyte, added to the polluted water, binds or solubilizes the species to be removed; UF of such a solution produces purified water. The retentate is taken to a separate processing scheme for recovering the surfactants/polyelectrolytes for recycle to the process and to produce a concentrated waste stream. Economic feasibility, competitiveness and shortcomings of such UF-based separation techniques and other references are provided in Tabatabai et al. (1995).
2.3. Microfiltration (MF) To separate fine particles and colloidal materials from gas streams and liquid suspensions, dead end and crossflow MF techniques are employed using membranes having pore diameters 0.1-10 urn. Eykamp [in DOE (1990)] had rightly placed considerable hope on progress in crossflow MF on three initiatives: ceramic membranes by CeraMem, Inc. (Waltham, MA)
MEMBRANE SEPARATION. TECHNOLOGIES
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and Ceraver (U.S. Filter, Warrendale, PAl and back pulsing-based liquid MF. The ceramic high temperature (up to 900C) crossflow gas filter of CeraMem is prepared by coating a thin (- 50 11m) ceramic MF membrane of 0.2-0.5 11m pore size on a porous cordierite honeycomb monolith (used in automobile catalytic converters), It is then modified by plugging the channels on both ends in an alternate-adjacent pattern to form a deadended flow-through filter. The particulate matter collected on the membrane surface from hot gases is removed periodically by backpulsing (for 50-100 milliseconds) into a dust hopper. Pilot tests for particle filtration from a feed gas at high temperature have been successfully completed [Bishop et at., 1995]. Commercialization has begun; two units are operational, one being located in the MIT Biological Waste Incinerator (Cambridge, MA). Particle stickiness on the filter surface usually requires development of optimum operating conditions on a system-by-system basis. The potential for industrial success of these regenerable compact filters is high since the efficiency of filtration/capture of particles (especially submicron ones) from hot gases by ceramic MF membranes is much higher than those of other techniques including electrostatic precipitation [Eggerstedt et al., 1993]. Ceramic crossflow MF membranes in multichannel configuration and having a selective layer of a-alumina or zirconia have been commercialized extensively on a large-scale for a variety of MF applications. In one variety of such multichannel monoliths (CeraMem), some of the passageways have been converted to filtrate conduits to eliminate the resistance of the porous support encountered in normal monoliths. Backpulsing is successfully employed to prevent particle buildup and provide high fluxes [Bhave, 1991] justifying the costlier ceramic membranes. Memtek (Billerica, MA) has installed a large number of MF units of crossflow tubular membranes employing periodic gas-driven filtrate-based backwash. Direct gas-based backpulsing has been employed for removal of particle buildup on polypropylene-based hydrophobic hollow fiber membrane surface (Memcor, Timonium, MD). Every 15-18 minutes of operation, compressed air at 90-100 psig is introduced into the filtrate side of the system and released through the hollow fiber wall. Accummulated solids are dislodged from the membrane surface and are simultaneously flushed from the membrane surface using feed water. Filtrate is not used for backpulsing. Polymeric membranes of polyvinylidene fluoride or polytetrafluoroethylene are now routinely used in MF of organic solutions [Goel et al., 1992]. Large scale protein harvesting (rt-PA) from mammalian cell culture by tangential flow filtration over MF hollow fibers (0.2 11m AKZO Microdyn) is a reality [Van Reis et at., 1991], Success in such use requires control of
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filtration rates (especially initial filtration rates) since the MF membranes have very high water permeability which leads to high initial filtration rates and rapid membrane fouling due to a deadend type of filtration. Such filtration rates may be controlled by having a backpressure on the filtrate line. The scale-up range achieved in this .application is 0.1 m 2-180m 2 . Microfiltration with uniform transmembrane pressure has been carried out for filtration of milk and dairy products using a dynamic counterpressure recirculation pump placed in the permeate-side loop (the Bactocatch process referred to in Bhave (1991)). A model has been developed to describe the performance of crossflow MF with high frequency backpulsing for yeast cell separation using a 0.2 urn cellulose acetate flat sheet membrane [Redkar and Davis, 1995]. 2.4. Electrodialysis (ED) One of the rapidly growing but perhaps the oldest of commercialized membrane separation technologies, electrodialysis (ED), is primarily used to remove salts or acids (organic included) from aqueous solutions [Strathmann, 1992J and concentrate them. In recent years, a form of ED requiring electrodialytic water dissociation has gathered momentum due to the availability of good bipolar membranes from Allied-Signal [Chlanda et al., 1988]. In such a process employing a bipolar as well as a cation-exchange and an anion-exchange membrane in each unit cell, salts like NaX are converted into the corresponding acid HX and the base NaOH each available in a separate stream. (It is not a traditional separation process; it is primarily a reaction-separation process). Three examples are illustrative. The first example to be described considers a process used in a plant at Washington Steel in Washington, PA; although installed in 1986, this process is included here for a wider perspective. In the steel industry, the steel pickling liquor of HF and HN0 3 is reduced to a hazardous waste after pickling due to dissolved Fe+ 3 , Ni+ 2 , and Cr+ 3 nitrates and fluorides. By reacting the liquor with KOH and precipitating the heavy metals as hydroxides, a clear solution of KF/KN0 3 is obtained. The latter is converted via bipolar and monopolar membranes to KOH for recycle to the neutralization vessel and HF/HN0 3 for recycling to the pickling operation [Chlanda et al., 1988]. For the second commercialized example, consider HF vapor from alkylation processes in petroleum industry; it is converted into aqueous KF by caustic scrubbing and sent to the plant waste in conventional processing. By electrodialytic water-splitting, the aqueous KF waste IS converted into a KOH base product recycled to the caustic
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scrubber and an HF acid product salable in the market after upgrading [Byszewski and Piccari, 1995]. The third example concerns recovery of fermentation-based organic acids produced in the form of a salt (e.g., sodium lactate or sodium succinate) [Datta and Tsai, 1995]. The crude organic acid salt (NaX) is first concentrated by conventional ED. Water-splitting ED is next employed to regenerate the alkali needed for pH control in fermentation and the organic acid to be further concentrated and purified. Conventionally such a process would have produced a large volume of salt or gypsum byproduct or waste depending on the alkali employed in fermentation and the acid employed for converting the salt. This trend of converting what would conventionally be a waste stream into chemicals to be used upstream via ED will continue to gather momentum. An additional ion exchange membrane-based process extensively commercialized is diffusion dialysis employing a single ion exchange membrane without any applied electrical gradient. In such a process, the membranes are usually permselective to H + ion but not to other cations. Thus, acids may be recovered form metal-contaminated solutions; this process has been already commercialized by Tokuyama, Tokyo, Japan. A variation of this process employs Tokuyama's cation exchange membranes in a San Diego plant to remove sodium ions from a spent etching solution containing aluminum ion which is rejected. The product chambers produce 17-20% caustic product for reuse while the spent etching solution depleted in caustic is sent to a crystallizer to remove aluminum trihydroxide prior to recycling to the etching bath [Byszewski and Jaffari, 1993]. Tokuyama Co. in Japan has also developed ion-exchange membranes having different properties to solve a variety of separation problems in electrodialysis. Each membrane of the. NEOSEPTA" brand (available in standard and special grades) has special capabilities, e.g., anion-exchange membrane permeable to acid diffusion; anion-exchange membrane that retards acid diffusion; cation-exchange membrane permeable to base diffusion; loosely crosslinked to pass large ions; mono-cation permselective; mono-anion permselective, etc. According to Thomas A. Davis, this company develops ED membranes tailored to customer needs which is somewhat unusual in the membrane industry. 2.5. Dialysis Although dialysis membranes have a lion's share of the total membrane sales, it is primarily due to hemodialysis. A detailed treatment is omitted here due to the focus on process industries. The primary innovations are in
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the development of asymmetric membranes [Kessler and Klein, 1992] as well as those membrances sterilizable by y-radiation (e.g., polyamidimide hollow fiber membrane by Toyo Boseki Kaisha, Osaka, Japan). The process of diffusion dialysis, sometimes considered under dialysis, has already been mentioned under electrodialysis. 2.6. Pervaporation (PV) Pervaporation separation is being increasingly employed to selectively remove one or more volatile species from a mixture of volatile liquids through a permselective nonporous membrane. Pervaporation is being applied to three types of separation problems: water removal from liquid organics; removal of volatile organics from water; organic/organic separation. In all cases, the technique involves feed liquid mixture flow on the feed side and a vacuum pulled on the permeate side of the membrane and the permeate condensed in a condenser. A comprehensive treatment of such separation processes is available in Rautenbach and Albrecht (1989), Huang (1991), Mulder (1991), Fleming and Slater (1992), Matsuura (1993), and Noble and Stern (1995). Removal of water from liquid organics has been commercialized on a large scale. There are three types of applications in this category. Dehydration of ethanol from 'streams containing 80-95.5% by weight of ethanol obtained in distillation processes applied to fermentation products is carried out in PV units' to yield a 99.5-99.95% ethanol containing stream as the concentrate by removing water (usually through a GFT (Deutsche Carbone AG, Germany) composite hydrophilic pervaporation membrane of polyvinyl alcohol (substantially selective for water over alcohol) on polyacrylonitrile support). There are many plants overseas, none in the USA. The second type of application generally involves dehydration of any organic stream (e.g., THF, methylethyl ketone, xylene, etc.) to the level of 10-20 ppm water from feed water levels of 0.1-10 wt%. There are many new pervaporation plants achieving this type of separation [Fleming and Slater, 1992]. A third type of application involves water removal from an organic reaction mixture, e.g., an esterification reaction mixture, as the reaction is going on in a separate reaction vessel'to increase the equilibrium conversion [Briischke et al., 1995]. Future prospects in this successful area include development/marketing of hollow-fiber-based or other systems that are substantially cheaper than the flat membrane polymeric systems currently used. A radical change will be achieved if the high flux and very high selectivity of water over ethanol demonstrated by a zeolite NaA membrane hydrothermally
t59
grown on a porous cylindrical substrate of o-alumina can be scaled up [Kita et al., 1995]. The second type of separation problem, namely, removal of volatile organic compounds (VOCs) from water, is largely driven by environmental laws apart from needs of resource recovery (e.g., recovery of aromas and flavors in the food industry). The membranes are primarily organophilic, sometimes of silicone on a micro porous solvent-resistant substrate. This technique is being slowly commercialized [Athayde et al., 1995]. Membrane modules are generally spiral (MTR, Inc., Menlo Park, CA; Hoechst Celanese, Charlotte, NC) 2 to 8 inches in diameter and can handle aqueous streams containing aggressive solvents like methylene chloride, toluene, etc. at saturation concentrations and high temperatures. Typical VOC separation factors vary from 1-10 for compounds like acetic acid, methanol, ethanol, etc. to 1000 + for benzene, toluene, xylene, etc. Hollow fiber units have also been developed (Zenon Environmental, Burlington, ON, Canada). The boundary layer mass transfer coefficient in the aqueous feed is quite important. As a result, transverse flow of feed liquid over the fiber practiced in the Zenon device is likely to be quite efficient. The third type of separation problem, namely organic/organic mixture, is of interest to chemical, petroleum and petrochemical industry. Systems frequently studied include methanol/methyl t-butyl ether (MTBE), aromatics/paraffins (toluene, n-heptane), chlorinated hydrocarbons/paraffins, etc. No process has been commercialized yet. A process being developed at Exxon by Ho et al. (1995) and described below is likely to be commercialized soon. Heavy catalytically cracked naptha containing aromatics/saturates in the same boiling range (therefore, distillation is not suitable) are separated by pervaporation at 170-200C into an aromatics-lean retentate which is useful for diesel fuel and an aromatics-rich permeate needed for high octane number gasoline. The membrane is a copolymer of polyirnide/aliphatic polyester where polyimide provides a solvent-resistant high Tg (~350C) glassy structure and the aliphatic polyester having a rubbery structure provides a selectivity of as much as 20 for toluene over isooctane with a high permeability. The membrane performance stability has been verified in plant tests using large spiral-wound modules prior to larger scale commercialization. This is an important development for polymeric membranes since the membrane was stable at high temperatures and in a solvent environment. Exxon researchers [Schucker, 1995b] have also studied the same pervaporation-based separation with hollow fiber membranes. A copolymer membrane of polyurea/urethane was applied on a variety of microporous hollow fiber supports, symmetric or asymmetric, and the seperation studied.
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2.7. Gas Permeation Membrane gas-separation [Koros and Fleming, 1993; Stern, 1994] has truly taken off in the last ten years. If one excludes the capacity for air separation (see Prasad et al. (1994) for an overview on membrane-based commercial air separation), every year anywhere between 250-450 MMSCFD of membrane processing capacity is being added worldwide [Backhouse et al., 1995]. As a result there are, for example, 230 worldwide membrane installations for produced natural gas treatment [Cooley et al., 1995]. Although exact details are not available, the following list of polymers are illustrative for particular separations; N 2 separation from air: ethyl cellulose, polycarbonate, polyolefins, polysulfone, polydimethylsiloxane, polyimides;. CO 2/CH 4 separation: cellulose acetate, polysulfone, polyamides, polyimides; H 2 separation: same as in CO 2/CH 4 separation. Progress in membrane-based N 2 generation technologies merits special attention since they are growing at a high rate of around 20%. State-of-theart effective membrane thickness (based on the total membrane transport resistance which includes membrane skin plus support layer resistances) has been reduced to less than 500 A in l ' Air Liquide's 2 membranes. At 25C, 02IN 2 selectively of around 7 is achieved by a separating layer of a skin of a high-selectivily aromatic polyimide and a coating of an ultrahigh selectivity aromatic polyamide. To develop high performance. modules, the non uniformity of fiber dimensions in a fiber bundle is reduced; tube-side feed flow and shell-side permeate flow occur in a bundle designed such that true countercurrent flow is achieved. Coextruded sheath (dense skinj/core fiber (rugged porous support layer) structure developed by new fiber spinning and processing technology has reduced the cost of l' Air Liquide's mainstream N 2 membranes to close to $1/ft 2. Few membrane devices are sold at such low prices (notable exception: dialyzers). These and other details are available in Roman (1996). General considerations on economics of gas separation membrane processes are provided in Spillman (1995). Recent developments have focused on polymeric materials [Stern, 1994] that are more selective and more permeable, operate over more demanding conditions and can handle toxic and/or corrosive gases. MTR, Inc. (Menlo Park, CAl has developed rubbery polymeric/elastorneric membranes and modules to 1) separate and recover Cl 2 from Chlor-alkali plant tail gases containing 10-45 mol% CI2 having Cl 2IN2 selectivity> 20,2) separate H 2S from natural gases containing 0.1-5 mol% H 2S using a membrane module having a module H 2S/CH 4 selectivity of > 30 and a flux twice that of cellulose acetate and, 3) recover S02 from streams cotaining 30-65% S02
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produced in sulfuric acid plants [Lokhandwala, 1995]. Such separations are now being tested on site. For elevated temperature operations, Costello et al. (1994) have found a rigid polypyrrolone material to be much better than conventional polymers both in terms of selectivity as well as permeability for 02IN 2 and He/CH 4 systems at temperatures of up to 125-200C. Ideal separation factor for gas separation through a polymeric membrane is known to be a product of solubility selectivity and mobility selectivity [Zolandz and Fleming, 1992]. In rubbery polymers, solubility selectivity (determined by the relative condensibility of the gases as well as by specific interactions between the gases and the polymeric groups) dominates. This will explain the H 2S/CH4 separation behavior mentioned in the last paragraph. In glassy polymers, mobility selectivity dominates for supercritical gas pairs like O 2 and N 2 which will have low solubility selectivity. A great deal of new glassy polymeric membrane development has been directed, therefore, to enhancing mobility selectivity without affecting the permeance itself since traditionally it is thought that increased selectivity leads to reduced permeance and vice versa along an upper bound (Robeson, 1991). Koros and Fleming (1993) have summarized the heart of this effort thus: "When changing the structure within a family of polymers, inhibiting intersegmental packing, while simultaneously hindering the backbone mobility tends to produce a desirable trade off between productivity and perrnselectivity changes." It has been successfully demonstrated for membranes made of polycarbonates, polysulfones, polyimides, etc. In the same spirit of developing membrane performance beyond the upper bound, cryogenic membrane separations are being investigated. Hsu et al. (1993) have found that the surface treatment of a polytrimethylsilylpropyne (PTMSP) by UV radiation enhances the 02IN2 selectivity to 4 from 1.4; subambient temperature (-Ioloq operation of this membrane was found to yield a 02IN2 selectivity of 12 although the permeance of oxygen showed considerable decrease. Researchers at Dow have found similarly that the-0 2 IN2 selectivity of chlorinated polycarbonate membranes were improved from five to six at room temperature to over 20 at - 80C [Moll et al., 1994] but the O 2 permeance decreased considerably. They have suggested the following: there is enhanced solubility as well as solubility selectivity at low temperatures in such "cyrogenic membranes"; further, lower temperature causes 11 decrease in diffusivity and an increase in diffusivity selectivity. However, performance beyond an upper bound is likely to result from solubility and solubility selectivity only. Almost all commercial gas separation systems employ polymeric membrances. However, considerable research is being conducted to develop
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ceramic, metallic (primarily palladium) and ceramic-polymer composite membranes with an eye towards' higher temperature separations and membrane reactors. Research in ceramic membranes invariably focuses on depositing on a microporous ceramic substrate a thin selective layer of silica, titania, etc. for H 2-selective membranes [Wu et al., 1994] or zirconia for Oj-selective membranes by a variety of techniques including CVD (chemical vapor deposition), sol-gel methods, etc. Usually H 2 permeances are low and selectivity quite high. Temperature of operation is in the range of 200 to 750C. For highly selective oxygen transport, ceramic membranes of mixed conductors (displaying electronic conductivity as well) have been used. The mechanism of O 2 permeation through thin ionic-electronic mixed-conducting solid oxide membranes has been elucidated [Lin et al., 1994]. Balachandran et al. (1994) have employed ceramic powders of La-Sr-Fe-Co-O along with Zr0 2, formed a dense membrane tube by slipcasting and sintering, and transferred O 2 from air on the outside of the tube to the inside where partial oxidation of methane was achieved at 850C. Brief surveys of inorganic membranes for gas separation, their strengths and potential have been provided in Hsieh (1988), Saracco et al. (1994) and Keizer et al. (1995). Inorganic membranes still suffer from the following deficiencies: high capital and repair costs; brittleness; poisoning of Pd membranes by many gases, CO, H 2S, S02' etc.; low permeance and not high enough selectivity except in a few cases; sealing problems; low surface area to-volume ratio. An additional approach proposes to develop molecular sieve-like structures having controlled pore size < lOA in the membrane for gas and vapor separation and, therefore, molecular sieve-like selectivity. Two routes are being followed. The first is to take polymeric membranes and pyrolyze them to produce carbon molecular sieve membranes [Koresh and Soffer, 1987]. Such membranes tend to be fragile even though their separation performance is very good; often, however, water vapor adversely affects their performance (see, however, Jones, and Koros (1995) and their hydrophobic polymer-carbon composite). The second route involves direct hydrothermal synthesis of different zeolites (e.g., silicalite) on a porous substrate [Jia et al., 1993; Bakker et al., 1993; Jia et al., 1994; Van et aI., 1995]. Results are highly encouraging; the presence of non-zeoli tic pores,' the thickness of the zeolite layer, etc., however, require considerable attention before such membranes can be harnessed for practical use. Pyrolysis of a larger hydrocarbon molecule introduced into the defects of a zeolite membrane as a post-treatment was
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recently found to be highly effective in raising the n-butane: isobutane selectivity from 9 to 108 CYan et al., 1996] at O.OI-latm. and 185C. Carbon molecular sieve membranes may be utilized to achieve separation by a mechanism other than molecular sieving. Rao and Sircar (1993) have prepared a nanoporous carbon membrane by pyrolyzing a PVC-acrylate latex on a macroporous graphite substrate at 1000C under N z atmosphere to produce 5-6 A pores which will allow selective adsorption and surface diffusion of more strongly adsorbed hydrocarbons vis-a-vis Hz. These selective surface flow (SSF) membranes show a C 4H IO/H z selectivity of almost 100 and allow recovery of Hz available in low pressure refinery streams. No commercial system has been built. Research and development opportunities and needs for carbon molecular sieve membranes for gas separation have been identified by Ho and Ying (1995). A totally different route for gas separation membranes has also been suggested for utilizing ceramic materials [Ho and Ying, 1995]: tunable synthesis of polymer-inorganic hybrid membranes where the polymer is bonded chemically to the inorganic; the inorganic governs the temperature stability of the membrane and controls/restricts polymer swelling for improved selectivity while the polymer provides high selectivity and permeability up to 300C. Such a membrane may be used for natural gases containing high CO, (;:;, 50%) without much plasticization. In so far as metals are concerned, palladium membranes are known and used for producing virtually pure hydrogen. Palladium-coated tubular membranes of niobium and tantalum have been made for extracting 100% pure hydrogen at high temperatures, e.g., 420C [Buxbaum, 1992; Buxbaum and Kinney,1996]; Hz permeance as high as 0.00147 rnol/mv-s-Pa vtz was obtained in long term tests suggesting good economics for Hz recovery in petrochemical plants and membrane reactors. Platinum-coated composite ceramic-metal membrane has been used to remove Hz also from a reaction mixture for thermolysis of HzS at 700C [Edlund and Plegar, 1993]. A significant effort was made in the early eighties to develop separation schemes (e.g., continuous membrane column, permeate recycle, etc.) employing gas permeation modules to enhance the composition of particular streams (see Zolandz and Fleming, 1992). Work is continuing. A notable example is the work by Xu and Agarwal (1996) on one-compressor cascades and Agrawal and Xu (1996) on two-compressor cascades amongst others. Xu and Agrawal (1996) have shown that cascades with minimal exergy loss due to mixing are often more efficient than a "series type two unit separation cell".
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2.8. Emulsion Liquid Membrane (ELM) A comprehensive introduction to the ELM technique is available in Ho and Li (1992). Commercialized operation is practiced in three plants: zinc removal from wastewater in the viscose fiber industry at Lenzing AG, Austria, phenol removal from wastewater in Guangzhou, China [Marr and Draxler, 1992], cyanide removal (130 to 0.5 mg(L) from waste liquors in gold processing in Chashe City, China [Ho and Ying, 1995]. Additional process development information is limited. Research is continuing; specific examples include removal of arsenic from wastewater, removal of copper from wastewater, removal of selenium from agricultural drainage water [Gleason et al., 1995] etc. 3. NEW MEMBRANE-BASED SEPARATION PROCESSES There are two categories of such processes: 1) membrane-based equilibrium separation processes; 2) membrane-based rate-governed separation processes. 3.1. Equilibrium Separation Processes By means of porous(microporous membranes, the first category of new membrane-based separation processes achieve traditional equilibriumbased separation processes of absorption, stripping, extraction, distillation (specific types only) and adsorption (see Ho and Sirkar (1992) except for adsorption). In such processes the membrane does not generally function as a species-selective barrier (except in membrane adsorption where the pore surfaces have adsorption sites). Instead for gas-liquid, vapor-liquid and liquid-liquid systems, the phase interfaces are located in the membrane pores or at the pore mouths and stabilized by appropriate operating phase pressures for given membrane wetting characteristics, interfacial tensions and pore diameters: the membrane device functions as a dispersion-free phase contactor with two phases flowing on two sides of the membrane. In such phase-contacting processes, the membrane prevents dispersion; there is no flooding or loading in the membrane-based contactor. Consequently, the operation is much more flexible. The interfacial contact area is essentially known. There is no need for the two phases to have different densities. Further, with hollow fiber devices, the interfacial area per unit equipment volume can be an order of magnitude larger than that in conventional contactors.
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3.1.1. Gas-Liquid Contacting

For gas-liquid contacting, current applications [studies initiated by Qi and Cussler, 1985] are a take-off of blood oxygenation studies initiated in 1975 using gas-filled hydrophobic hollow fibers [Sirkar, 1992]. Gas absorption and gas stripping [Sirkar, 1992] have been successfully commercialized on a large scale using hydrophobic fibers and gas-filled pores. Stripping of CO 2 to extend anion bed life, adding CO 2 to carbonate beverages [Sirkar, 1995], deoxygenation of water to prevent corrosion [Sengupta et al., 1995] are being implemented in commercialized hydrophobic microporous membrane-based contacting devices (Hoechst Celanese, Charlotte, NC) having continuous flow rates of sevetal thousand liters per minute. Volatile organic compound (VOC) removal is targeted for future markets. Application to CO 2 removal by amine-based scrubbing solutions (e.g., monoethanolamine solutions) have faced problems due to long term wetting out of the pores by the volatile organic amines. The latest generation hydrophobic hollow fiber devices of Hoechst Celanese, Charlotte, NC (Liqui-Cel" Extra-Flow) have two distinct features: the shell-side fluid has transverse flow vis-a-vis the fibers locally resulting in high mass transfer coefficient and overall countercurrent flow vis-a-vis the tube-side fluid by means of shell-side baffles; fibers are potted in a solvent-resistant polyolefin tube-sheet to handle a variety of solvents. Further, the fibers are present in a fabric form wrapped around the central tube feeder for the shell-side fluid [Sengupta et al., 1994]. Current hydrophobic microporous membrane-based gas absorption and stripping processes and devices employ operating conditions where the pores are gas-filled. For highly reactive absorption processes, liquid-filled pores may not increase the resistance much since gas-side resistance becomes important [Karoor, 1992]. Karoor and Sirkar (1993) have shown that for slower reactions, the resistance increases considerably if the pores are absorbent-filled. They had employed hydrophobic fibers and a special wetting procedure. Tsou et al. (1994) have employed hydrophilic fibers with aqueous AgNO) solution in pores as well as on the other side to selectively absorb ethylene from ethane. The pores were spontaneously wetted by the solution and the gas pressrue (0-200 psig) was equal to or higher than that of the liquid. For organic absorbents in VOC absorption from N 2/air, pores in a hydrophobic fiber will be wetted and the gas phase pressure should be higher than that of the organic absorbent in pore to prevent dispersion unless the membrane is a hydrogel. The additional resistance of the organic liquid-filled pores will be less than that of a highly VOC-permeable but absorbent-blocking nonporous ultrathin silicone skin on the porous fiber [Poddar et aI., 1996].
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For nondispersive operation with porous fibers having a nonporous silicone skin, the gas pressure should be lower than that of the liquid absorbent to prevent gas dispersion in the liquid [Poddar et al., 1996]. Gas-liquid contacting processes where there is a thin nonporous coating (highly selective and permeable to the species desired to be transferred) on a porous membrane are also being studied for transfer of other species, e.g., CO 2 Matsumoto et al. (1992) have compared the performances of coated hollow fibers with noncoated fibers for CO 2 removal from flue gas. Coated fibers have significantly higher resistance. Although it is not a separation application, it is worth noting that for complete dissolution of any gas or gas mixture in water. or any other liquid without bubbles, one can use similar/rnicroporous fibers with one end sealed and floating [Ahmed and Semmens, 1992] in the module. Such an arrangement is being used commercially (Membran, Mineapolis, MN) in large scale to achieve direct dissolution of 02' CH 4 , H 2 etc. for in situ remediation of groundwater. For the separation of gas mixtures, membrane-based absorption processes mimicking pressure swing adsorption in a fixed bed are being studied [Bhaumik et al., 1996]. Such a cyclic process can purify the feed gas stream to a very high degree characteristic of traditional pressure swing adsorption processes but not of traditional membrane processes; yet, they have their own advantages based on high-surface area low-pressure drop membrane systems. However, the part of the cycle dealing with the regeneration of the absorbent bed has to be improved. 3.1.2. Liquid-liquid Contacting Nondispersive liquid-liquid contacting (initiated by Kiani et al. (1984)) has been reviewed by Prasad and Sirkar (1992); it can employ hydrophobic, hydrophilic and hydrophobic-hydrophilic membranes. Additional treatment and design guidance are provided by Reed et al. (1995). This technique is being commercialized using Liqui-Cel@ Extra-Flow devices having considerable solvent resistance. Sengupta et al. (1994) have evaluated microporous membrane-based solvent extraction of n-hexanol from water into the solvent n-octanol using two 4" diameter 28" long semi-commercial scale hollow fiber Liquicel" Extra-Flow modules (having polyolefin tube sheets) in series. Octanol was recovered from the extract as bottoms in a distillation column present in a large-scale distillation/extraction setup and recycled back to the extractor. The mass transfer performance of the hollow fiber extractor was very good; a height equivalent to a theoretical stage (HETS) of 5 feet was obtained compared
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with 50 feet for a packed extractor employing commerical-scale type 2 structured packing for the same system at the same facility (University of Texas at Austin, TX). Further, there was a deterioration in the efficiency of the packed extractor with increasing continuous phase flow suggesting the onset of flooding condition. Reed et al. (1994) successfully carried out pilot-scale evaluation of microporous membrane-based solvent extraction of a wide range of organic contaminants from industrial wastewaters at two industrial plant sites in the Netherlands. They employed 3 Liquicel" hollow fiber extractors, each having 2-3 m 2 contactor area, in series to extract 8 chlorinated compounds from a wastewater flowing at 75 L/hr at an Akzo-Delfzil facility; at the DSM-Gellen facility these modules extracted 6 aromatics from wastewater flowing at the same rate. These experiments were run over extended periods (~3 months at DSM-Gellen) and treated water concentrations of individual pollutants were reduced to less than 10 J.1g!L. Process economics appeared quite competitive with other conventional technologies. Kathios et al. (1994) have demonstrated the utility of the membrane-based solvent extraction modules for the extraction of actinides via surrogate species like neody. mium (a surrogate for americium). They used earlier generation of parallelflow modules; the current generation of transverse-flow Liquicel" ExtraFlow extractors have much better mass transfer characteristics. Currently available hydrophobic microporous membrane-based modules are quite effective for extraction of a solute from an aqueous solution into an organic extractant having a strong affinity for the solute. For the back extraction of this solute into an aqueous phase, hydrophilic microporous membranes are desirable if the solute prefers the aqueous back extraction solution. Efficient solvent-resistant hydrophilic membrane-based modules are needed for rapid commercialization of membrane-based solvent extraction technology.
3.1.3. Membrane Distillation

No major developments have benefited membrane-based distillation of solutions (primarily aqueous) via hydrophobic microporous membranes nonwetted by the solution; for a brief introduction, see Sirkar (1992).
3.1.4. Membrane Adsorption

Among gas-liquid adsorption and liquid-solid adsorption, the latter is considered first. In membrane adsorption processes for adsorption from liquids, the membrane pore surface area provides adsorption sites as the liquid flows through the pore; generally the rates of transfer are much higher than
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those with adsorbent beads where pore diffusion is the slow step [Thomrnes and Kula, 1995]. Pore diffusion is absent in membrane adsorption. After the membrane pore surface sites are exhausted, they are regenerated by a stripping liquid. Membrane-based adsorption processes have been commercialized for the separation/recovery of proteins as a replacement for a packed column of adsorbent beads. Often such processes are called membrane chromatography [Thomrnes and Kula, 1995] or adsorptive membrane chromatography [Roper and Lightfoot, 1995]. The adsorbing membrane may be in the form of a hollow fiber [Brandt et aI., 1988] or a stack of flat microporous membranes with active ligands grafted. on the surfaces of pores (0.5-1 11m diameter) of a microfiltration membrane. Since the liquid flows through the membrane pore, the adsorption bed length is equal to the membrane thickness which is quite small. Due to MF membranes used, the pressure drop for this flow is very low, 1-2 psi, as much as 100 times lower than a comparable packed bed at the same flow rate. Since the ligand utilization in membrane adsorption is very high, the ligand loading capacity can be 2-3 orders of magnitude smaller. Purification cycle times are short; bed capacities are a few times higher, especially at higher flow rates [Klein, 1995]. A number of different mem- . branes and modules are available commercially; while affinity ligands are much more common, hydrophobic interaction and reversed-phase technology are also being introduced along with heavy metal recovering chelating iminodiacetate group [Le et al., 1994] or ion exchange groups (see Hori et al. (1995) for ultrapure water production). An entirely different approach has been adopted by Pan and McMinis (1992) for membrane-based gas-solid adsorption. Since mass transfer characteristics are considerably improved in adsorbent particles of very small size, these particles are either put in the lumen of porous hollow fibers or on the shell side of a hollow fiber module. The gas mixture flows correspondingly on the shell side or through the lumen of the fibers. This reduces drastically the gas flow pressure drop encountered in a packed bed of very small particles. The hollow fiber membrane device then allows the potential of smaller adsorbent particles to be realized without paying the penalty of a large bed pressure drop. However, Gilleskie et al. (1995) have concluded that such an advantage is not enough to overcome the disadvantage of a small void fraction available for gas flow. Uneven spacing of fibers is an added concern in hollow fiber adsorbent devices. These problems are avoided in liquid-liquid systems in hollow fiber liquid chromatography [Ding et al., 1989] where the stationary phase (e.g., an organic liquid) is immobilized in the pores of a rnicroporous/porous hollow fiber. The aqueous
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mobile phase flows through the fiber bore. Smaller molecules as well as protein mixtures have been separated effectively.
3.2. New Rate-Governed Membrane Separation Processes

The second category of new membrane-based separation processes are true membrane processes in that separation depends on different intrinsic rates of transport of different species through the selective membrane under comparable driving forces. Examples are: vapor permeation, continuous deionization, perstraction, facilitated transport, gas membrane, osmotic distillation, contained liquid membrane, supported liquid membrane (SLM), supported polymeric liquid membranes (SPLM), etc. Of these, the first two have been successfully commercialized. Others are undergoing differnt degrees of development. 3.2.1. Vapor Permeation In vapor permeation processes applied to removal/recovery of VOCs from airfN2' a partial pressure driving force across a thin rubbery membrane supported on a porous substrate allows a highly VOC-enriched permeate stream to be produced from the feed stream which is purified of the VOCs. A significant number of commercial vapor permeation units are in operation recovering gasoline vapors, VOCs including CFCs, etc. (MTR, Inc.; GKSS). The modules of MTR, Inc. (Palo Alto, CAl are spirally wound. The modules of GKSS (Geesthacht, Germany) consist of round flat-sheet membranes welded at the outer edge to form a membrane envelope; these envelopes are placed around a central permeate tube; the whole assembly is kept inside a pressure vessel [Ohlrogge et al., 1995]. For atmospheric pressure feed streams, permeate side is maintained under vacuum via a condenser and a vacuum pump [Baker, 1985]. In an alternate arrangement, the VOCcontaminated feed gas is compressed, passed through a condenser and then fed to the vapor-permeation unit to get rid of the VOC. The permeate at atmospheric pressure is recycled to the contaminated feed gas at atmospheric pressure [Wijmans, 1992]. Highly VOC-permeable membranes possessing high VOC-N 2/air selectivity preferably in the form of hollow fibers are likely to be preferred in the future. Friesen et al. (1994) have described VOC-separation from nitrogen using countercurrent sweep vapor/gas stream in a hollow fiber device; the microporous hollow fibers based on crosslinked polyimide have very high chemical resistance. The selective layer is a rubbery nonporous coating on
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the fiber internal diameter; the feed gas flows through the fiber lumen. Short modules of plasma polymerized silicone-coated micro porous polypropylene hollow fibers have also been used to purify nitrogen of VOCs with very high efficiency [Cha et al., 1996]; the high efficiency resulted form tube-side feed being imposed on the silicone skin from the microporous substrate side while the shell side was subjected to vacuum. This mode of operation is quite unusual. Vapor permeation from saturated vapor streams is being studied [Cen and Lichtenthaler, 1995]. A recent comparative perspective for pervaporative dehydration vs. dehydration by vapor permeation for ethanol-water mixtures is provided by Ellinghorst et al. (1995). Downloaded by [Midlands State University] at 01:49 21 May 2012 3.2.2. Continuous Deionization In the continous deionization (CDI) process, sometimes called electrodeionization (ED I), each diluate compartment between an anion-exchange membrane and a cation-exchange membrane in ED is filled with a mixed bed of ion-exchange resin beads [Ganzi, 1988]. In normal electrodialysis, purification below a certain level will cause severe polarization, and water-splitting happens. Kedem and Maoz (1976) showed that polarization in ED can be suppressed by suitably shaped ion-conducting spacers. In the same manner, the presence of mixed ion-exchange resins in COl prevents severe polarization without any need for bed regeneration. Almost completely deionized water is obtained [Auerswald, 1994]. Further, COl devices are capable of removing dissolved CO 2 without pH adjustement, reduce TOC levels if there is a RO-based pretreatment to remove higher molecular weight organics, and can reduce bacteria and bacterial endotoxin to acceptable levels provided there is a RO pretreatment since the elctropositive anion-exchange beads having the greatest degree of water spliting will be batericidal for bacteria having electronegative surfaces [Ganzi and Parise, 1990]. First introduced in 1987, the COl technique is used in 700 systems worldwide and has an equally bright future due to the absence of any hazardous chemicals needed in ion-exchange bed regeneration in traditional processes. 3.2.3. Other Processes The processes included here are as follows: perstraction, facilitated transport, osmotic distillation, gas membrane processes, hollow fiber contained liquid membranes, supported liquid membrane, supported polymeric liquid membrane. They will now be considered in the same sequence starting with perstraction. Perstraction with polymeric membranes has been reviewed in Sirkar (1992). Developments of perstraction separation for hydrocarbon liquid mixtures, e.g., aromatic-aliphatic separation by hollow fiber membrances using
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n-heptane as a sweep liquid have been described by Schucker (1995a). The membranes were a series of copolymers of polyurea/urethane. For perstraction with aqueous contained liquid membranes, Papadopoulos and Sirkar (1993) achieved a very high separation factor for 2-propanol/n-heptane system using dodecane as the sweep liquid stream. For the process ofjacilitated transport where the flux of a species through a liquid or polymeric membrane can be increased considerably by reversible complexation of the species with a carrier species in the membrane, consult Way and Noble (1992). Facilitated O 2 transport with high selectivity and flux vis-a-vis N 2 in liquid as well as fixed carrier solid membrane (especially the Japanese work), facilitated CO 2 transport, facilitated olefin transport vis-a-vis paraffins, facilitated NH 3 transport and facilitated S02 transport have been reviewed by Way and Noble (1992) and briefly reviewed in Ho and Ying (1995). Long term performance deterioration continues to be a problem for fixed carrier solid membranes, e.g. Oj-selective membranes. Crown ethers, e.g., dicyclohexano-18-crown-6, have been successfully incorported into a cellulose triacetate membrane during film casting to facilitate cation transport through the polymeric membrane form an aqueous solution [Schow et al., .1996]. Osmotic distillation and gas membrane processes are described in Sirkar (1992). In osmotic distillation-based fruit juice concentration, the fruit juice flows on one side of a hydrophobic micro porous hollow fiber; on the other side flows a concentrated brine solution with a very high osmotic pressure to provide a partial pressure driving force for moisture from the juice to the brine through the gas-filled pores. The diluted brine is taken to a concentrator for regeneration and reuse. For larger scale and semi-commercial studies in osmotic distillation-based fruit juice concentration, see Sirkar (1995) which gives details of fruit juice concentration in a pilot system in Australia containing 22 4" x 28" (surface area 425 m 2) Liqui-Cel" modules (Vineland Concentrates and Hoechst Celanese). Commercialization prospects for osmotic distillation-based fruit juice concentration look good; module cleaning after each batch concentration is a concern. Hollow fiber contained liquid membrane-based permeation and separation have been shown to be highly stable and efficient; details for gas and liquid separations are available in Majumdar et al. (1992). Successful laboratoryscale applications to facilitated and selective transport of particular cationic metals (radioactive, alkali, or otherwise) over others using crown ethers or other agents have been carried out [Lamb et al., 1990; Izatt et al., 1993; Guha et al., 1994]. Recent innovations are higher pressure operation for gas separation with modified fibers [Papadopoulos and Sirkar, 1994],
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pervaporation removal of VOCs from water [Yang et al., 1995] and isomer separation with aqueous cyclodextrin-containing membranes from organic feed solutions. Modules of up to 2" diameter have been built and tested. Fabrication of large modules with low values of effective membrane thickness is a concern (see the latest review by Sirkar (1996)). No important development has benefitted the supported liquid membrane (SLM) technique. The hollow fiber contained liquid membrane technique as well as the not-verystable SLM technique use lower molecular weight liquids as the membrane. Ho et aJ. (1996) have demonstrated that supported polymeric liquid membranes (SPLM) prepared by crosslinking lower molecular weight polypropylene glycols (PPG-4000 for example) in the pores of hydrophobic microporous membranes can be an elffective membrane for removing organics from aqueous solutions containing high levels of salt. Pilot tests using large hollow fiber modules (19 m 2 ) have been carried out successfully [Ho, 1996].
4. HYBRID PROCESSES
Of the many membrane-based hybrid processes possible, those that are commercially practiced or have reached the pilot plant stage or are being worked on otherwise are of interest. A common commercialized example is that of pervaporation downstream of a distillation column for ethanol production. Pervaporation breaks up the ethanol-water azeotrope and produces ethanol of various degrees of purity (99.5% to 99.95%) [Fleming and Slater, 1992]. The membrane employed is usually an asymmetric composite polyvinyl alcohol (GFT) flat membrane. Attractive savings in such a process compared to entrainer distillation are identified in a case study [Humphrey and Seibert, 1992]. Other possible membrane-based hybrids containing distillation column include distillation-vapor permeation and reverse osmosisdistillation. Conversely, there are other hybrids proposed with pervaporation: RO-pervaporation, absorption-pervaporation, etc. For the hybrid of absorption-membrane permeation of gases, there exist a number of well known processes for CO 2 separations: SACROC unit for enhanced oil recovery via CO 2 injection employs membrane permeation of CO 2 followed by K 2C0 3 absorption prior to reinjection; these and others including amine absorption-membrane permeation are discussed in Zolandz and Fleming (1992). The regions of optimum performance for CO 2 removal from natural gas by a hybrid process vs. a gas permeation membrane process or an amine scrubbing process have been delineated in a recent study by Kellogg/GRI and briefly illustrated in Koros and Fleming (1993).
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Additional hybrid processes of cryogenic-membrane permeation, membrane-PSA [Choe et aI., 1987; Doshi, 1987], PSA-membrane-cryogenic [MacLean et al., 1987] have been patented some time back. In CO 2 removal from natural gas, small amounts of C 6 + hydrocarbons or some vapor phase aromatic hydrocarbons severely damage the CO 2-selective membrane and are, therefore, to be removed by adsorption, absorption or condensation-based pretreatment [Cooley et al., 1995]. Nanofiltration has been employed to premeate and separate acetic acid (and/or formic acid) from higher molecular weight soluble organics (molecular weight cut off in the range of 150-300) etc. in biomass wastewater streams using Zenon nanofiltration technology. The permeate was then subjected first to reverse osmosis to increase the 1-2% acetic acid concentration in the NF permeate to a RO retentate concentration of 8-10%. The concentrated RO retentate was subjected to solvent extraction using a proprietary (Glitsch Technology Corp., Houston, TX) complexing solvent to achieve acetic acid extraction and recovery of up of 99.5%. Recovery includes additional steps of solvent dehydration, acid stripping and purification [Kramer and Al-Samadi, 1995]. This hybrid of NF-RO-solvent extraction results in a very high performance for the solvent extraction step not achieved otherwise (high molecular weight soluble organics would have been extracted without NF); large systems are available for this process being commercialized. There are other hybrids with NF, e.g., NF-ion exchange [Rautenbach and Groschl, 1990]. Commercialized or near-commercialized hybrids employing new membrane-based separation processes are also of interest. A hybrid of RO and continous electrodeionization (COl) produces commercially USP-grade purified water [Ganzi and Parise, 1990]; RO achieves bulk deionization, removes bacteria, particles and TDS as COl technology polishes the water next without using any hazardous chemicals required in ion exchange column regeneration (U.S. Filter, Lowell, MA). In nearly all applications for high purity water in pharmaceutical, microelectronic and chemical industry, COl equipment is used as part of a sequential combination of technologies such as filtration, adsorption and RO; this is unlike a classical hybrid where there is integration. RO treatment for extractable species like phenol may be combined with membrane solvent extraction for phenol (Ray et al., 1991). The new membrane technique of vapor permeation (VP) is often commercially employed with an inlet gas or vapor stream whose vapor concentration fluctuates; therefore, the treated stream vapor concentration fluctuates which is not desired. If a condenser is put upstream of the VP unit, the feed stream entering the vapor permeation module is very likely to have a near-constant
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vapor composition; the treated gas stream concentration will then fluctuate much less. The VOC permeation rate is also increased significantly due to compression and increased VOC partial pressure [Wijmans, 1992]. Energy requirements and capital costs for compression of larger volume streams do, however, increase the cost of .such a hybrid. An additional hybrid of VP employs pressure swing adsorption and condensation for gasoline vapor recovery [Ludtke and Behling, 1995] A hybrid of distillation, membrane contacting [Tsou et al., 1994] and flash separation has been tested successfully in a pilot plant and is now operational at 220 psi and 40C in a demonstration plant at a BP oil refinery, Toledo Ohio [OIT, 1993] for the recovery of propylene from cracking purge gases. For the same system of propylene/propane separation, Gottschlich and Roberts (1990) have simulated a hybrid of distillation and a facilitated transport membrane and concluded that the hybrid is superior to either distillation or membrane process when high product purity is desired. Guidelines and general rules for optimal design of such hybrids have been considered by Stephan et al. (1995). These hybrid processes couple, in general, two different separation techniques externally. A composite separation process or an internally hybrid separation process achieves such coupling internally within a given device. For example, CDI achieves conventional electrodialysis and continuously regenerated mixed bed ion-exchange within one device albeit at different axial locations along the feed flow path [Ganzi and Parise, 1990]. On the other hand, in the pervaporation process based on contained liquid membrane mentioned earlier [Yang et al., 1995], there is locally solvent extraction and then pervaporation from the solvent phase at every axial location in the hollow fiber module.
5. MEMBRANE REACTORS
Membrane reactors may employ polymeric, ceramic, metallic or liquid membranes for separation as a reaction (or reactions) goes on in the reactor containing a membrane or two. In a multiphase membrane reactor containing a polymeric microporous water-filled hydrophilic hollow fiber membrane used to immobilize an enzyme catalyst, steroselective enzymatic hydrolysis of the undesired isomer from a racemic mixture or glycidic esters and its removal in methanol buffer has been carried out in a large scale in a nondispersive aqueous-organic system [Lopez, 1993; Dodds and Lopez, 1993]. In this commercialized process, the microporous membrane acts as a phase-contactor (with appropriate allowances for differences in phase
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pressures), a phase separator (as in micro porous membrane-based solvent extraction) and as an interfacial catalyst [Matson and Quinn, 1992]. There are a large number of possible membrane reactor configurations involving membranes, catalysts, reactions, separations [Govind and Itoh, 1989; Noble and Armor, 1993; Saracco et al., 1994; Falconer et al., 1995] oriented towards production of a variety of chemicals, biochemicals, etc. Most research is directed towards equilibrium shift whereby one of the products is selectively removed from the reaction zone by the membrane to increase conversion. Often this product is H 2 as in dehydrogenation reactions. Many membranes capable of withstanding higher temperature are quite selective to H 2: metallic membranes of Pd, silica-based membranes, etc. No process has been commercialized yet although the potential is high. Having a membrane of appropriate selectivity and (permeability/membrane thickness) at the higher temperature of operation is a difficult task. The success of membrane reactors at higher temperatures is intimately linked with the successful development of highly selective ceramic/metallic membranes having acceptable permeance levels. There are a number of other hurdles as well already pointed out in section 2.7 for gas permeation [Saracco et aI., 1994]. Porous, microporous or nonporous membranes that are catalytically active have also been employed in what are called catalytic membrane reactors. These have significant potential [Falconer et al., 1995]. However, none have been commercialized. A joint effort of Argonne National Lab, Amoco Chemical Company and DOE at PETC has led to the developement of Oy-specific dense ceramic membranes made of certain perovskite-type oxides containing cationic dopants. Such a membrane allows oxygen to permeate through the membrane from air on the outside of a ceramic tube through the bore of which a flowing methane stream is converted to H 2 and CO via partial oxidation of CH 4 at 850C [Balachandran et aI., 1994]. A pilot scale demonstration is under active study [DOE, 1995]. Modified porous a-alumina membrane is being used in a tube-and-shell type inorganic reactor to distribute O 2 feed along the length of the reactor for oxidative dehydrogenation of ethane to ethylene or propane to propylene using a magnesium oxide catalyst doped with samarium oxide. This configuration controls overoxidation yet achieves high hydrocarbon conversion [Tonkovich et al., 1995]; it needs pure O 2 the production cost of which is reduced in Balachandran et al. (1994) via 02-selective densse membrane. The above examples deal with production of chemicals via a membrane reactor. The destruction of hazardous organic chemicals (present in wastewater) in a membrane reactor via ozonation has been demonstrated. In single-phase ozonation, a simple silicone capillary-based reactor allowed a much higher k.a to be achieved for ozonation of wastewater compared to
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conventional bubble-based dispersive ozonation devices [Shanbhag et aI., 1995]. (Here k,a is the product of the mass transfer coefficient based on the liquid phase (k,) and the interfacial area per unit reactor volume (a)). In two-phase ozonation employing a 2-fiber-set membrane ozonator, a silicone capillary was used to supply ozone to an inert high-boiling perfluorocarbon liquid on the shell side having an 0 3 solubility 16 times that of water. A second porous Teflon capillary allowed extraction of pollutants from water flowing through the capillary into the perfluorocarbon reaction medium on the shell side. The Teflon capillary pores were wetted by the perfluorocarbon and pollutants were partitioned into it on the capillary outer diameter. The oxidative degradation products were removed by partitioning into the two flowing streams through the two membrane sets [Guha et aI., 1995]. Both types of reactors have been tested for few hundreds of hours. Material stability for longer periods are unknown at this time. Of these two techniques, single-phase ozonation using one set of capillaries or hollow fibers as in Shanbhag et al. (1995) has considerable commercialization potential; it may employ microporous/porous capillaries/hollow fibers of Teflon with or without a coating of an ozone-selective material. Combination of reactors with external membrane devices in the recycle mode has been practiced commercially for some time especially in the bioprocessing industry. A successfully commercialized system in biological treatment of wastewater is the ZenoGem process of Zenon Environmental (Burlington, ON, Canda). It consists of a biological reactor integrated with an UF membrane system which filters the reactor-treated water prior to discharge and recycles the biological solids to the bioreactor. The UF system also recovers higher molecular weight soluble materials and returns them to the bioreactor for further biodegradation prior to ultimate discharge. In conventional processing, these higher molecular weight soluble materials would have passed through conventional clarifiers and filters. ZenoGem technology has also been used along with RO to treat a highly saline wastewater stream successfully in' a 4 month on-site pilot test [Mourato et al., 1995]. Dilution of wastewater was employed to render the organics biodegradable; the required water for dilution was recovered from the biologically treated effluent by RO. Combination of a bioreactor with an internal membrane device for treatment of process wastewaters having extreme pHs or high salt concentrations etc. that preclude microbial growth has been studied via an extractive membrane bioreactor [Brookes and Livingston, 1994]. Toxic organics from wastewater are extracted through a nonporous dense phase silicone rubber capillary membrane into a biological medium for biodegradation. Pilot
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plant studies have been made in a plant containing 10 m 2 surfa~e area membrane module [Livingston et aI., 1995]. Instead of a solid silicone membrane, a hollow fiber contained liquid membrane has also been studied to extract aromatics from a salt-containing waste stream to a bioreactor feed stream [Tompkins et al., 1994].
Acknowledgements
The author wishes to acknowledge the generous help and comments of many individuals. The inputs by A. Allegrezza, Jr., D. Bhattacharyya, B. Bishop, T. Davis, S. Matson and W. S. Winston Ho were particularly helpful.
References
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Chemical Engineering Communications

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MEMBRANE SEPARATION TECHNOLOGIES: CURRENT DEVELOPMENTS

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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MEMBRANE SEPARATION TECHNOLOGIES

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Preparation, characterization and gas permeation. J. Membrane Sci., 82, 15.

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