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  • Journal of Membrane Science 281 (2006) 7087

    Review

    Forward osmosis: Principles, applications, and recent developmentsTzahi Y. Cath a,, Amy E. Childress b, Menachem Elimelech c

    a

    Abstract

    Osmosiresearchersyntheticin engineeseparationresearch idrug relealimitation 2006 E

    Keywords:

    Content

    1. Int2. Os

    2.12.2

    3. Co3.13.2

    3.34. Me

    4.14.2

    Abbreviatinational pototal Kjeld

    CorrespE-mail

    0376-7388doi:10.101. Membranes for forward osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

    . Membrane modules and devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 764.2.1. Plate-and-frame . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774.2.2. Spiral-wound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774.2.3. Tubular . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774.2.4. Hydration bags . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

    ons: CP, concentration polarization; DOC, direct osmotic concentration; DS, draw solution; FO, forward osmosis; MD, membrane distillation; NPDES,llutant discharge elimination system; OD, osmotic distillation; PRO, pressure-retarded osmosis; RO, reverse osmosis; TDS, total dissolved solids; TKN,ahl nitrogen (sum of organic nitrogen and ammonia); TMDL, total maximum daily loadonding author. Tel.: +1 303 273 3402; fax: +1 303 273 3413.address: [email protected] (T.Y. Cath).

    /$ see front matter 2006 Elsevier B.V. All rights reserved.6/j.memsci.2006.05.048s

    roduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71motic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71. Classification of osmotic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71. Draw solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72ncentration polarization in osmotic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73. External concentration polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73. Internal concentration polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

    3.2.1. Modeling concentrative internal concentration polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743.2.2. Modeling dilutive internal concentration polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

    . Influence of internal concentration polarization on water flux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75mbranes and modules for forward osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75Colorado School of Mines, Division of Environmental Science and Engineering, Golden, CO 80401-1887, United Statesb University of Nevada, Department of Civil and Environmental Engineering, Reno, NV 89557-0152, United States

    c Yale University, Department of Chemical Engineering, Environmental Engineering Program, New Haven, CT 06520-8286, United StatesReceived 30 December 2005; received in revised form 30 May 2006; accepted 31 May 2006

    Available online 6 June 2006

    s is a physical phenomenon that has been extensively studied by scientists in various disciplines of science and engineering. Earlys studied the mechanism of osmosis through natural materials, and from the 1960s, special attention has been given to osmosis throughmaterials. Following the progress in membrane science in the last few decades, especially for reverse osmosis applications, the interestsred applications of osmosis has been spurred. Osmosis, or as it is currently referred to as forward osmosis, has new applications inprocesses for wastewater treatment, food processing, and seawater/brackish water desalination. Other unique areas of forward osmosis

    nclude pressure-retarded osmosis for generation of electricity from saline and fresh water and implantable osmotic pumps for controlledse. This paper provides the state-of-the-art of the physical principles and applications of forward osmosis as well as their strengths ands.lsevier B.V. All rights reserved.

    Osmosis; Forward osmosis; Direct osmosis; Desalination; Reverse osmosis; Pressure-retarded osmosis

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 71

    5. Modern applications of forward osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 785.1. Wastewater treatment and water purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

    5.1.1. Concentration of dilute industrial wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78.

    .

    . .

    s5.2. . .5.3. . .5.4. .5.5. . .

    6. Conc .Ackn . .Refer . .

    1. Introdu

    Osmosiby human brealized thapreservatioother potendie or becoventionallyacross a se

    ence in osmpermeablemolecules oof the applPresent-dayfrom waterand novel mfocus on othe field ofapplicationunderstand

    In the fia more famdescriptionof osmosisthe osmotipurified waforce for mosmotic prNumerouswastewater

    Fewerosmosisment/engtheless, Fbench-scfull-scale(at benching wastdemonstrand forRecent d

    f-rer

    eppse

    o

    c

    et

    re

    nblFre

    tatva

    pae

    o

    sotrros

    d.5.1.2. Concentration of landfill leachate . . . . . . . . . . . . . . . . . . . . . . . . . .5.1.3. Direct potable reuse for advanced life support systems . . . . . . .5.1.4. Concentration of digested sludge liquids . . . . . . . . . . . . . . . . . . .5.1.5. Forward osmosis for source water purificationhydration bagSeawater desalination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Food processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .The pharmaceutical industryosmotic pumps . . . . . . . . . . . . . . . . . . . . . .Osmotic powerpressure-retarded osmosis . . . . . . . . . . . . . . . . . . . . . . . .

    luding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .owledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    ction

    s is a physical phenomenon that has been exploitedeings since the early days of mankind. Early culturest salt could be used to desiccate foods for long-termn. In saline environments, most bacteria, fungi, andtially pathogenic organisms become dehydrated andme temporarily inactivated because of osmosis. Con-, osmosis is defined as the net movement of waterlectively permeable membrane driven by a differ-otic pressure across the membrane. A selectively

    membrane allows passage of water, but rejects soluter ions. Osmotic pressure is the driving force for many

    ications that will be reviewed and discussed herein.applications of the osmosis phenomenon extend

    treatment and food processing to power generationethods for controlled drug release. This review will

    smosis through polymeric membranes, primarily inwater treatment and desalination. References to others of osmosis will be made when necessary to furthertheoretical and applied aspects of osmosis.eld of water treatment, reverse osmosis is generallyiliar process than osmosis. Because of this, a briefof the RO process is given prior to further discussion

    . RO uses hydraulic pressure to oppose, and exceed,c pressure of an aqueous feed solution to produceter [1]. In RO, the applied pressure is the drivingass transport through the membrane; in osmosis, theessure itself is the driving force for mass transport.publications on the use of RO for water treatment and

    the use oPressurebeen testfor powedifferencwater toosmoticcan be u

    The mlow or nrange ofing propBecauseto flowequipmeof a processing,withoutdetrimencan assisoral bioa[25].

    Thisrelated mductioncompariof massfor the pFO procediscussereclamation appear in the literature.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

    FO in controlled drug release in the body [2427].etarded osmosis (PRO), a closely related process, hasd and evaluated since the 1960s as a potential processgeneration [2839]. PRO uses the osmotic pressurebetween seawater, or concentrated brine, and freshressurize the saline stream, thereby converting theressure of seawater into a hydrostatic pressure thatd to produce electricity.ain advantages of using FO are that it operates athydraulic pressures, it has high rejection of a wide

    ontaminants, and it may have a lower membrane foul-nsity than pressure-driven membrane processes [4].he only pressure involved in the FO process is duesistance in the membrane module (a few bars), thet used is very simple and membrane support is lessem. Furthermore, for food and pharmaceutical pro-O has the benefit of concentrating the feed streamquiring high pressures or temperatures that may bel to the feed solution. For medical applications, FO

    in the slow and accurate release of drugs that have lowilability due to their limited solubility or permeability

    per presents an extensive review of FO and closely-mbrane processes. The review begins with an intro-

    f the basic principles of the FO process, includingn to other closely related processes. Special aspectsansport in the process as well as the membranes usedcess are described. Strengths and limitations of the

    s in a broad spectrum of applications are reviewed andAnd last, the future of FO technology is considered.publications on the use of osmosis or forward(FO), or direct osmosis (DO) for water treat-ineering applications appear in the literature. Never-O has been used to treat industrial wastewaters (at

    ale) [24], to concentrate landfill leachate (at pilot- and) [57], and to treat liquid foods in the food industry-scale) [816]. FO is also being evaluated for reclaim-ewater for potable reuse in life support systems (atation-scale) [1720], for desalinating seawater [21,22],purifying water in emergency relief situations [23].evelopments in materials science have also allowed

    2. Osmotic processes

    2.1. Classication of osmotic processes

    Osmosis is the transport of water across a selectively perme-able membrane from a region of higher water chemical potentialto a region of lower water chemical potential. It is driven by adifference in solute concentrations across the membrane thatallows passage of water, but rejects most solute molecules orions. Osmotic pressure () is the pressure which, if applied tothe more concentrated solution, would prevent transport of water

  • 72 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    across the membrane. FO uses the osmotic pressure differential() across the membrane, rather than hydraulic pressure dif-ferential (as in RO), as the driving force for transport of waterthrough the membrane. The FO process results in concentrationof a feed stream and dilution of a highly concentrated stream(referred to as the draw solution).

    PRO can be viewed as an intermediate process between FOand RO, where hydraulic pressure is applied in the oppositedirection of the osmotic pressure gradient (similar to RO). How-ever, the net water flux is still in the direction of the concentrateddraw solution (similar to FO).

    The general equation describing water transport in FO, RO,and PRO is

    Jw = A( P) (1)where Jw is the water flux, A the water permeability constantof the membrane, the reflection coefficient, and P is theapplied prePRO, >FO, PRO,driving forearly 1980RO zone, aFig. 2.

    2.2. Draw

    The conbrane is thDifferent teincluding dsolution, osity, the termWhen seleca higher ospressures osolutions wSystems Inas a functimodeling bpropertiestemperatur

    irection and magnitude of water flux as a function of applied pressureRO, and RO. FO takes place when the hydraulic pressure difference ise PRO zone is where the applied pressure difference is between zero andreversal point, and the RO zone is where the applied pressure differencer than the osmotic pressure difference. Figure adapted from [30].

    smotic pressure as a function of solution concentration at 25 C for var-ential draw solutions. Data were calculated using OLI Stream Analyzer.

    Fig. 1. Solven uses to the more saline side of the membrane. For PRO, water diffusesto the more sa the less saline side due to hydraulic pressure (P > ).ssure. For FO, P is zero; for RO, P > ; and forP. The flux directions of the permeating water in

    and RO are illustrated in Fig. 1. Flux directions andces for the three processes were characterized in thes by Lee et al. [30]. The FO point, PRO zone, andlong with the flux reversal point, are illustrated in

    solutions

    centrated solution on the permeate side of the mem-e source of the driving force in the FO process.rms are used in the literature to name this solutionraw solution, osmotic agent, osmotic media, drivingmotic engine, sample solution, or just brine. For clar-draw solution is being used exclusively in this paper.ting a draw solution, the main criterion is that it hasmotic pressure than the feed solution. The osmoticf several solutions being considered for use as drawere calculated using OLI Stream Analyzer 2.0 (OLIc., Morris Plains, NJ) [40] and are presented in Fig. 3on of molarity. This software uses thermodynamicased on published experimental data to predict the

    of solutions over a wide range of concentrations andes.

    Fig. 2. Din FO, Pzero. Ththe fluxis greate

    Fig. 3. Oious pot2.0 [40]

    t flows in FO, PRO, and RO. For FO, P is approximately zero and water diffline liquid that is under positive pressure ( > P). For RO, water diffuses to

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 73

    Another important criterion in some applications of FO isthe selection of a suitable process for reconcentrating the drawsolution afan NaCl soatively simwithout rissolution thrcific applicion solutioin PRO, seaseawater [2have been utigations of

    Variousas solutes ftion applicasolution asGlew [42]of water analiphatic althe first tojunction wiKravath antion of seawof glucose[45] usedtious drinka two-stagedependent sgested solu(SO2) as drapplicationwas demongases in sptions of theproduced Fof 250 atmwater fromin brine dilogical apptested as aferritin canmagnetic fi

    3. Concen

    The wadescribed bpressure diIn such proactive layeference, wh[30,39,48,5attributed tena. Specifiphenomenaosmotic-dr

    3.1. External concentration polarization

    ressca

    . Reon r

    re the toraneranembr

    em

    ay bressolutis bermeatrati

    ve os

    osm

    easiby

    fluxredua inre-dr

    toind

    red teenmem

    than

    tern

    en aetely, theulk

    ranesena

    of aFO

    orienraneshedpropive iive eand ttionf theyer fhe d. Than

    iffereter it has been diluted in the FO process. Very oftenlution is used because it has high solubility and is rel-ple to reconcentrate to high concentration with ROk of scaling. Diffusion of the solute from the drawough the membrane must also be considered. In spe-ations where high rejection is desired, multivalentns may be preferable. In some applications such aswater may be used as the draw solution. In the past,8], Dead Sea water [33], and Salt Lake water [34]sed or considered for draw solutions in various inves-FO and PRO.

    other chemicals have also been suggested and testedor draw solutions, particularly in seawater desalina-tions. Batchelder [41] suggested using sulfur dioxidethe draw solution in FO desalination of seawater.

    expanded on this idea and suggested using mixturesd another gas (e.g., sulfur dioxide) or liquid (e.g.,

    cohols) as the draw solutions for FO. Glew was alsopropose the recycling of the draw solution in con-th FO. Frank [43] used an aluminum sulfate solution,d Davis [21] used a glucose solution in FO desalina-ater, Kessler and Moody [44] used a mixed solutionand fructose for seawater desalination, and Stachea concentrated fructose solution to create a nutri-during FO of seawater. McGinnis [46] suggestedFO process that takes advantage of the temperatureolubilities of the solutes. Specifically, McGinnis sug-tions of potassium nitrate (KNO3) and sulfur dioxideaw solutions for seawater desalination. In a later novel

    of FO by McGinnis and coworkers [22,47,48], itstrated that combining ammonia and carbon dioxideecific ratios created highly concentrated draw solu-rmally removable ammonium salts. This approachO draw solutions with osmotic pressures in excess

    , allowing unprecedented high recoveries of potableconcentrated saline feeds and substantial reductionsscharges from desalination. In a new nanotechno-roach, naturally non-toxic magnetoferritin is beingpotential solute for draw solutions [49]. Magneto-be rapidly separated from aqueous streams using a

    eld.

    tration polarization in osmotic processes

    ter flux in osmotic-driven membrane processes isy Eq. (1). In this equation, represents the osmoticfference across the active layer of the membrane.cesses, the osmotic pressure difference across the

    r is much lower than the bulk osmotic pressure dif-ich results in much lower water flux than expected0,51]. The lower-than-expected water flux is ofteno several membrane-associated transport phenom-cally, two types of concentration polarization (CP) external CP and internal CP can take place in

    iven membrane processes as discussed below.

    In pate flowsurfacenomen

    pressuCP dumembmembthe meof the mThis mCP in pdraw sbranethe peconcen

    effectiCP onby incrface orwaterCP bynomen

    pressuDue

    foulingcompaIt has bdrivenlower-

    3.2. In

    WhcomplFig. 4aof the bmembphenomsistingused inbranemembestablisolutecentratcentratlayer,applicalayer oport lalayer, tdiluted

    It csure dure-driven membrane processes, convective perme-uses a buildup of solute at the membrane active layerferred to as concentration polarization (CP), this phe-educes permeate water flux due to increased osmoticat must be overcome with hydraulic pressure [5254].water permeation is not limited to pressure-drivenprocesses and also occurs during osmotic-drivenprocesses, on both the feed and permeate sides of

    ane. When the feed solution flows on the active layerbrane (like in RO), solutes build up at the active layer.e called concentrative external CP and is similar toure-driven membrane processes. Simultaneously, theion in contact with the permeate side of the mem-ing diluted at the permeatemembrane interface byting water. This is called dilutive external CP. Bothve and dilutive external CP phenomena reduce themotic driving force. The adverse effect of externalotic-driven membrane processes can be minimizedng flow velocity and turbulence at the membrane sur-manipulating the water flux [55]. However, becausein FO is already low, the ability to diminish externalcing flux is limited. For modeling external CP phe-FO, equations similar to those developed for CP ofiven membranes can be used [53,54].the low hydraulic pressure used in FO, membraneuced by external CP has milder effects on water fluxo the effects in pressure-driven membrane processes.shown that external CP plays a minor role in osmotic-

    brane processes and is not the main cause for the-expected water flux in such processes [48].

    al concentration polarization

    n osmotic pressure gradient is established across arejecting dense symmetric membrane, as depicted indriving force is the difference in osmotic pressures

    solutions in the absence of external CP. However, FOare asymmetric, adding more complexity to the CP. When a composite or asymmetric membrane con-dense separating layer and a porous support layer is, two phenomena can occur depending on the mem-tation. If the porous support layer of an asymmetricfaces the feed solution, as in PRO, a polarized layer isalong the inside of the dense active layer as water andagate the porous layer (Fig. 4b). Referred to as con-nternal CP [48], this phenomenon is similar to con-xternal CP, except that it takes place within the porousherefore, cannot be minimized by cross-flow. In FOs for desalination and water treatment, the activemembrane faces the feed solution and the porous sup-aces the draw solution. As water permeates the activeraw solution within the porous substructure becomesis is referred to as dilutive internal CP (Fig. 4c) [48].be clearly seen in Fig. 5 that the osmotic pres-nce between the bulk feed and bulk draw solution

  • 74 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    Fig. 4. Illustr osmosymmetric de cing(c) An asymm le illurepresented b this

    (bulk) isthe membrtive osmotto internalexchangersration (feedbrane but ithe membr[56].

    3.2.1. Modpolarizatio

    Unlike Ris mostly amembrane

    lso srane.sitein Find dtionsces (cen

    ptinet alter flations of driving force profiles, expressed as water chemical potential, w, fornse membrane. (b) An asymmetric membrane with the porous support layer faetric membrane with the dense active layer facing the feed solution; the profi

    y w. External CP effects on the driving force are assumed to be negligible in

    higher than the osmotic pressure difference acrossane (m) due to external CP and that the effec-ic pressure driving force (eff) is even lower dueCP. Furthermore, similar to the operation of heat, operation of FO in a counter-current flow configu-

    and draw solution flowing tangential to the mem-n opposite directions) provides constant alongane module and makes the process more efficient

    eling concentrative internal concentration

    layer amembcompotratedfeed acentrainterfathe con

    AdoLoebthe wanO, for which water transport through the membraneffected by the hydraulic resistance created by thestructure, in FO, internal CP in the porous support

    orientation

    Jw = 1K

    ln

    Fig. 5. (a) Concentrative internal CP and (b) dilutive internal CP across a csis through several membrane types and orientations [48]. (a) Athe feed solution; the profile illustrates concentrative internal CP.strates dilutive internal CP. The actual (effective) driving force isdiagram.

    ubstantially affects mass transfer of water across theThe concentration profile across an asymmetric or

    FO membrane for concentrative internal CP is illus-g. 5a. C1 and C5 are the concentrations of the bulkraw solution, respectively; C2 and C4 are the con-of the feed-membrane and draw solution-membraneresulting from external CP), respectively; and C3 istration at the active layersupport layer interface.g the models that were developed by Lee et al. [30],. [50] introduced a simplified equation to describeux during FO without consideration for membrane:

    HiLow

    (2)

    omposite or asymmetric membrane in FO.

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 75

    whereK is the resistance to solute diffusion within the membraneporous support layer, and Hi and Low are the osmotic pressuresof the bulktively, negl

    K = tDs

    where t, ,porosity, resolute. Howvalid only fthis equatiofor concent

    K =(

    1Jw

    )

    where B isof the memexperiment

    B = (1 R

    where R isseverity ofmore sever

    3.2.2. Modpolarizatio

    The conFO membrLoeb et al.dilutive int

    K =(

    1Jw

    )

    Recent studequation assuccessfullan FO-desi

    3.3. Inuewater ux

    Mehta asupport laytion concethe membrfluids on ththe permea(Fig. 6).

    Experimfiber) Permout that A (not constanpressure (iThe declindehydratio

    O tesal CPto th

    declin

    dryitic drt. Rl CP

    mbr

    emb

    eralal ca,39,nfig

    mem

    raned fisaters196evelrane separation from a laboratory to an industrial pro-as the development of the LoebSourirajan process forg defect-free, high-flux, anisotropic RO membranes [61].nd co-workers [50,59] investigated the use of asymmetrictic polyamide membranes for FO and PRO.he 1970s, all studies involving osmosis (mostly PRO stud-ed RO membranes, either flat sheet or tubular, and ines, researchers observed much lower flux than expected.et al. [2] and Anderson [3] used several commerciallyle RO membranes and an in-house cellulose acetate mem-o treat dilute wastewater by FO using a simulated seawa-w solution. Kravath and Davis [21] used flat sheet ROranes from Eastman and cellulose acetate hollow fiberranes from Dow to desalinate seawater by FO using glu-s the draw solution. Goosens and Van-Haute [60] usedse acetate membranes reinforced with mineral fillers tote whether membrane performance under RO conditionspredicted through FO testing.draw solution (C5) and feed solution (C1), respec-ecting external polarization effects. K is defined as

    (3)

    and are the membrane thickness, tortuosity, andspectively, and Ds is the diffusion coefficient of theever, it has been recently demonstrated that Eq. (2) is

    or very low water fluxes [57]. Further development ofn [50] has led to a more general governing equationrative internal CP:

    ln(

    B + AHi JwB + ALow

    )(4)

    the solute permeability coefficient of the active layerbrane, which can be determined from an RO-type[50] using)A(P )

    R(5)

    the salt rejection. Eq. (4) can be used to quantify theinternal CP; larger values of K are associated withe internal CP.

    eling dilutive internal concentrationncentration profile across an asymmetric or compositeane for dilutive internal CP is illustrated in Fig. 5b.[50] presented a simplified governing equation for

    ernal CP in asymmetric membranes:

    ln(

    B + AHiB + Jw + ALow

    )(6)

    ies [48,57] have shown that this simplified governingwell as the equation for concentrative internal CP,

    y predict the results obtained during experiments withgned membrane.

    nce of internal concentration polarization on

    nd Loeb [39,58] studied the effect of the porouser on internal CP and the effect of high draw solu-ntrations on the overall permeability coefficient ofane. Results show that upon swapping the workinge two sides of the membrane, flux (as indicated bybility coefficient) sharply declines due to internal CP

    enting with DuPont B-9 (flat sheet) and B-10 (hollowasep RO membranes, Mehta and Loeb [58] pointedthe membrane permeability constant from Eq. (1)) ist in FO and PRO; it declines with increasing osmotic.e., increasing concentration) of the draw solution.e of A was explained by partial drying or osmoticn of the membrane at high osmotic pressures. Such

    Fig. 6. Fof internexposedsharply

    partialosmo

    transpointerna

    4. Me

    4.1. M

    Genmateri[2,3,21lary coEarlymembtle, angoldbe

    Bybeen dmembcess w

    makinLoeb aaroma

    In ties) usall casVottaavailabbrane tter dramembmembcose a

    celluloevaluacan bets with NaCl and MgSO4 solutions as draw solutions. The effectcan be seen after 2 h when the support side of the membrane is

    e draw solution instead of DI water. The water permeation ratees after dilutive internal CP starts. Figure adapted from [58].

    ng can be accompanied by pore contraction, known aseswelling, and hence increased resistance to wateresults from recent studies [48,57] confirmed thatis actually the cause of the substantial flux decline.

    anes and modules for forward osmosis

    ranes for forward osmosis

    ly, any dense, non-porous, selectively permeablen be used as a membrane for FO. Such membranes50,5860] have been tested (in flat sheet and capil-urations) in the past for various applications of FO.brane researchers experimented with every type ofmaterial available, including bladders of pigs, cat-

    h; collodion (nitrocellulose); rubber; porcelain; and skin [3].

    0, the elements of modern membrane science hadoped and the important discovery that transformed

  • 76 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    Fig. 7. A crosis embedded wthickness is le

    Also inwith DuPomasep ROFlux throug(approxima

    Duringoped by OTechnologia wide va[5,6,8,16,1applicationand recreatthe membrbrane is thobe seen thaand it is evquite differtypically coa thick porthick suppovides mech(see SectioHTI is supmajor contmembrane

    In summFO wouldrejection; aport layer fhydrophilicand high mused for PRmembranesMembraneminimal inport high hin current ations for FO

    4.2. Membrane modules and devices

    ferent module configurations can be used to hold orembranes for FO. Laboratory-scale modules have been

    ed for use with either flat sheet or tubular/capillary mem-. Larger-scale applications [5,6,18] have been designedilt with flat sheet membranes in plate-and-frame configu-. Each configuration has advantages and limitations thate taken into consideration when planning the research orping the application. Prior to discussing the advantagesitations of plate-and-frame, spiral-wound, tubular, and

    nfigurations, differences between continuous flow andperation must first be considered.

    continuous flow FO applications, the draw solution isedly reconcentrated/refreshed and reused. In this mode,d solution is recirculated on the feed side of the membranee reconcentrated/refreshed draw solution is recirculatedpermeate side (Fig. 8). For this reason, modules that use

    eet membranes are more complicated to build and oper-the FO process compared to pressure-driven processes.

    ample, the spiral-wound module, one of the most com-acking configurations in the membrane industry, cannotd in its current design for FO because a liquid stream can-forcepplicolutwer

    ted aat thpplicwere

    of datchrecon

    ice uations-sectional SEM image of HTIs FO membrane. A polyester meshithin the polymer material for mechanical support. The membraness than 50m. Figure taken from [22].

    the 1970s, Mehta and Loeb [39,58] experimentednt B-9 (flat sheet) and B-10 (hollow fiber) Per-

    membranes made of an aromatic polyamide polymer.h the B-10 Permasep membrane was relatively lowtely 8 l/m2 h at a driving force of 80 bar).the 1990s, a special membrane for FO was devel-smotek Inc. (Albany, Oregon) (currently Hydrationes Inc. (HTI)). This membrane has been tested inriety of applications by different research groups8,19,48]. It is also used successfully in commercials of water purification for military, emergency relief,ional purposes [62]. A cross-sectional SEM image ofane is shown in Fig. 7 [22]. This proprietary mem-ught to be made of cellulose triacetate (CTA). It cant the thickness of the membrane is less than 50mident that the structure of the CTA FO membrane isent from standard RO membranes. RO membranesnsist of a very thin active layer (less than 1m) andous support layer. The CTA FO membrane lacks art layer. Instead, the embedded polyester mesh pro-anical support. Results from various investigations

    Difpack mdesignbranesand burationsmust bdeveloand limbag cobatch o

    Inrepeatthe feeand thon theflat shate forFor exmon pbe usenot bePRO adraw sfor posupporand thscale atanks)supply

    In bis notthe devApplicn 5) indicate that the CTA FO membrane made byerior to RO membranes operated in FO mode. Theributing factors are likely the relative thinness of theand the lack of a fabric support layer.ary, the desired characteristics of membranes for

    be high density of the active layer for high solutethin membrane with minimum porosity of the sup-

    or low internal CP, and therefore, higher water flux;ity for enhanced flux and reduced membrane fouling;

    echanical strength to sustain hydraulic pressure whenO. The development of improved semi-permeablefor FO is critical for advancing the field of FO.

    s that can achieve high flux and salt rejection, haveternal CP, and have high mechanical strength to sup-ydraulic pressures will lead to improved performancepplications as well as development of new applica-.

    Fig. 8. Flowsof the membrof the membrturbine to prod to flow on the support side (inside the envelope). Inations, the pressure of the receiving stream (i.e., the

    ion) is elevated to achieve the high pressure neededgeneration. This requires that the membrane is wellnd able to withstand pressure on the permeate side,e flow channels are not blocked. In advanced large-ations of PRO, additional accessories (e.g., pressuresuggested by Loeb [33,34] to handle the continuous

    raw solution at elevated pressures.FO applications, the draw solution is diluted once andcentrated for further use. In this mode of operation,sed for FO is most often disposable and is not reused.s using this mode of operation include hydration

    in FO and PRO processes. Feed water flows on the active sideane and draw solution flows counter-currently on the support sideane. In PRO, the draw solution is pressurized and is released in aduce electricity.

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 77

    bags for water purification and osmotic pumps for drug delivery[26,63].

    Even coable semi-pbranes. Fosheet memfiguration o

    4.2.1. PlatThe sim

    plate-and-fstructed indevices thascale systedesign anders is well emembranetations of pare lack ofsity. Lack ohydraulic psides of thtrol). Lowhigher capibrane replaconfiguratiing, difficurange of osures) [18]

    4.2.2. SpirComme

    (e.g., spirastream (thevelocity tanvery slowlyand its comerties of thein its currebe operatedforced to fl

    Mehta [wound elemcan be usedflows throuthe same wfor RO. Hois blocked hto the otheof the meminside the efirst half ofthe envelopperforatedcan also beof the envein spiral-w

    low patterns in a spiral-wound module modified for FO. The feed solu-s through the central tube into the inner side of the membrane envelope

    draw solution flows in the space between the rolled envelopes. Figurefrom [36].

    of the main limitations in operating a spiral-woundrane element for RO is the inability to induce flow in theate channels (i.e., the inner side of the envelopes) of theraneue a

    embtopposi

    f thec baembn. As to(Figuld

    Tubuuse

    uous

    Effect of osmotic backwashing on the performance of a spiral woundbrane after desalination. The feed solution consisted of 0.5% NaCl andturated CaCO3. Figure adapted from [64].nsidering their limitations, the most readily avail-ermeable polymeric membranes are flat sheet mem-

    r continuous flow operation of an FO process, flatbranes can be used in either a plate-and-frame con-r in a unique spiral-wound configuration.

    e-and-frameplest device for packing flat sheet membranes is arame module. Plate-and-frame modules can be con-different sizes and shapes ranging from lab-scale

    t hold single, small-size membrane coupons to full-ms that hold more than 1700 membranes. While theconstruction of large plate-and-frame heat exchang-stablished, the construction of large plate-and-framemodules is more complicated. Two of the main limi-late-and-frame elements for membrane applicationsadequate membrane support and low packing den-f adequate membrane support limits operation to lowressure and/or operation at similar pressures on bothe membrane (requiring relatively high process con-packing density leads to a larger system footprint,tal costs, and higher operating costs (labor for mem-cement). Other limitations of the plate-and-frame

    on include problems with internal and external seal-lty in monitoring membrane integrity, and a limitedperating conditions (e.g., flow velocities and pres-.

    al-woundrcially marketed spiral-wound membrane elementsl-wound RO elements) are operated with only onefeed stream) flowing under direct control of its flowgential to the membrane. The permeate stream flowsin the channel formed by the two glued membranes

    position and flow velocity are controlled by the prop-membrane and the operating conditions. Therefore,

    nt design, spiral-wound membrane elements cannotin FO mode because the draw solution cannot be

    ow inside the envelope formed by the membranes.36] designed and successfully tested a unique spiral-

    ent for FO. Both outside-in and inside-out operation. In Fig. 9 (inside-out operation), the draw solution

    gh the spacers and between the rolled membranes, inay that a feed stream flows in a spiral-wound elementwever, unlike RO elements, the central collecting tubealfway through so that the feed solution cannot flow

    r side. Instead, an additional glue line at the centerbrane envelope provides a path for the feed to flownvelope. In this configuration, the feed flows into thethe perforated central pipe, is then forced to flow intoe, and then flows out through the second half of the

    central pipe. It is worth noting that this configurationefficiently used for PRO. The draw solution outside

    lope can be pressurized similar to the way it is doneound membrane elements for RO.

    Fig. 9. Ftion flowand theadapted

    OnemembpermemembA uniqRO mUpon sby osmside oosmotiRO msolutiofor 20resultsflux co

    4.2.3.The

    contin

    Fig. 10.RO memsuper-saelement for the purpose of cleaning or backwashing.pplication of FO for backwashing of spiral-wound

    ranes was investigated by Sagiv and Semiat [64].ing the RO process after desalination, water diffused

    s from the permeate channels back into the feedmembrane, thus cleaning the membrane through

    ckwashing. In their investigation, a spiral-woundrane was purposely scaled with saturated CaCO3t predetermined intervals, the system was stoppedallow osmotic backwashing to occur. Preliminary. 10) indicate that almost complete recovery of waterbe achieved.

    larof tubular membranes (tubes or hollow fibers) for

    ly operated FO processes is more practical for three

  • 78 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    main reasons. First, tubular membranes are self-supported. Thismeans they can support high hydraulic pressure without defor-mation anda holding vlar modulemodules amembraneit is the aumost suitablayer as ininternal CP

    The maibranes is thhollow fibebe achievelimited. Uning can redmembranesachieved an

    That saibranes (ROsemi-permmarket as fldue to theRO membrexcessive ffiber RO mspecially dhave to takhydraulic cbranes for

    4.2.4. HydThe hyd

    membrane.an FO memsucrose) anthe FO baghydration b

    5. Modern

    Forwardtions. Coming in the wthe pharmaing sectionwastewatertion, foodgeneration.

    5.1. Waste

    Severaltreatment han early stu[2,3], an in

    study on direct potable reuse of wastewater in advanced life sup-port systems for space applications [5,18,19], and an investiga-

    con

    mest in mte prmate

    Conof t

    for w3].dustmetay thembrs conrnalrang

    thanr eqin Rgateaw sulat

    potene ofon oed a

    Naon. Dgateolyv

    ersin. Won, tcreas

    to tcalededed f

    Condfillts ahightings, did to

    te iste isaste

    cs, hfor Tse TDo co

    efficthey can be easily packed in bundles directly insideessel. Second, it is much simpler to fabricate tubu-

    s and packing density is relatively high. Third, thesellow liquids to flow freely on both sides of the

    a flow pattern necessary for FO [65]. Furthermore,thors opinion that hollow fiber membranes may bele for FO because there is no need for a thick supportflat sheet RO membranes. This will result in reducedand enhanced performance.

    n difference between hollow fiber and tubular mem-e flow regime that can be achieved on the bore side. Inrs (internal diameter

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 79

    Table 1Raw leachate and final effluent water quality characteristics [6]Contaminant m lea

    AluminumArsenicBariumCadmiumCalciumChromiumCopperIronLeadMagnesiumManganeseNickelPhosphorusPotassiumSeleniumSiliconSilverSodiumStrontiumTitaniumVanadiumZinc

    Contaminant achat

    AlkalinityBOD-5Chloride-wateCODFluoride-freeN-AmmoniaTKNpHTDSTSSSpecific cond

    ND = not dete

    evaporationhorizontalprocesses.mechanicavery effecticonstructedof landfillOregon [6,receives mo20,00040,to meet the(NPDES) tbe treated tcation.

    An FO pCTA membWater recoinant rejeccessing of robserved dcomplete fl(metals or salts) Untreated leachate (g/l) Recovered water fro1320 ND39 ND305 14 0.03691600 150146 ND18 ND8670 2412 ND73700 331480 ND81 ND5740 ND56000 543ND ND35500 ND7 ND1620000 39902370 ND468 ND132 ND531 ND

    Untreated leachate (mg/l) Recovered water from le

    5000 4

    472 2r 1580 23

    3190 ND1 ND

    1110 1.6780 ND

    8 5.62380 48

    100 NDuctance 9940S/cm 25S/cm

    cted.

    (e.g., vapor compression, vertical tube falling film,tube spray film, forced circulation) and membraneA comprehensive evaluation of vapor recompressionl evaporation, RO, and FO revealed that FO can beve in treating landfill leachate [6]. In 1998, Osmotek

    a pilot-scale FO system to test the concentrationleachate at the Coffin Butte Landfill in Corvallis,7]. Because this landfill is located in an area thatre than 1400 mm per year of rainfall, approximately000 m3 of leachate is generated annually. In order

    National Pollutant Discharge Elimination Systemotal maximum daily load (TMDL), the leachate musto a TDS level lower than 100 mg/l prior to land appli-

    ilot system was tested for 3 months using Osmoteksrane (Section 4.1) and NaCl as the draw solution.

    veries of 9496% were achieved with high contam-tion. Flux decline was not apparent during the pro-aw leachate; however, a flux decline of 3050% wasuring processing of concentrated leachate. Almostux restoration was achieved after cleaning.

    The succonstructiosystem, theis extractedstaged) ROapplicationapproximafied before

    Betweentreated overecovery of35S/cm [feed and efTable 1. Mfinal efflueNPDES TM

    5.1.3. Diresystems

    Long-teself-sufficiechate (g/l) Rejection (%) NPDES TMDL (g/l)100100

    99.6799.10 1.899.84

    100 16100 18

    99.72100 5.399.96

    100100100

    99.0310010010099.75

    100100100100 120

    e (mg/l) Rejection (%) NPDES TMDL (mg/l)

    99.9299.58 4598.54 378

    10010099.86 2.8

    10030.0097.98

    10099.75

    cess of the pilot-scale system led to the design andn of a full-scale system (Fig. 11). In the full-scaleraw leachate is collected and pretreated before waterin six stages of FO cells. A three-pass (permeate-system produces a stream of purified water for landand a reconcentrated stream of draw solution at

    tely 75 g/l NaCl. The concentrated leachate is solidi-disposal [6].

    June 1998 and March 1999, the treatment plantr 18,500 m3 of leachate, achieving an average water91.9% and an average RO permeate conductivity of

    6]. The concentrations of major contaminants in thefluent of the full-scale FO system are summarized inost contaminants had greater than 99% rejection andnt concentrations were substantially lower than the

    DL levels.

    ct potable reuse for advanced life support

    rm human missions in space require a continuous andnt supply of fresh water for consumption, hygiene,

  • 80 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    Fig. 11. A flofrom [6].

    and maintemissions owater treatmater generaThe threeand reusedter, urine, awastewaterhigh perceally, the synance, min[66].

    A pilot-centration (reuse in spare being e

    Table 2Water flux through one FO membrane and four RO membranes in FO mode [18]Membrane used Water flux (l/m2 h)CTAOsmotek 17.4OsmonicsCE 1.90OsmonicsCD 1.97HydranauticsLFC1 0.54HydranauticsLFC3 0.66

    100 g/l NaCl solution was used as the draw solution and DI water as the feed.

    Administration (NASA) for water reuse in space. The NASADOC test unit originally consisted of a permeate-staged ROcascade and two pretreatment subsystems. The first subsystem(DOC#1) utilized an FO process only and the second (DOC#2)utilized a unique combination of FO and osmotic distillation(OD). The OD process targeted the rejection of small com-pounds, like urea, that easily diffuse through semi-permeablemembranes [17,19]. A schematic drawing of the original DOCtest unit is shown in Fig. 12.

    he fiuctioccom

    ase (iverzatioain gce,r a mer p

    rren

    desigstemO wiwit

    o of

    Fig. 12. Flowdrinking watew diagram of the full-scale FO leachate treatment process. Adapted

    nance. Long-range/long-duration missions, like lunarr a human Mars exploration mission, depend on a

    ent system that recovers potable water from wastew-ted on board a spacecraft or in the planetary habitat.main sources of wastewater that can be reclaimedin long-term space missions are hygiene wastewa-nd humidity condensate. The system to treat theses must be reliable, durable, capable of recovering antage of the wastewater, and lightweight. Addition-stem should operate autonomously with low mainte-imal power consumption, and minimal consumables

    In tconstrwere a

    ond phthe UnoptimiThe mformandata foand othIn a cubeingthis sy(i.e., Fsystem

    Tw

    scale FO system, referred to as the direct osmotic con-DOC) system, was developed for direct potable waterace [5,17]. DOC is one of several technologies thatvaluated by the U.S. National Aeronautics and Space

    relate to meprocesses.brane usedRO membr

    diagram of the original NASA DOC test unit. Three waste streams are pretreatedr is produced by the RO subsystem [18].rst phase of the DOC study (19941999), design,n, and testing of the basic functions of the DOC unitplished by NASA and Osmotek [17,20]. In the sec-

    20022004), the NASA DOC unit was transferred tosity of Nevada, Reno for thorough investigation andn of the operating conditions of the system [18,19].oals of this phase were to study the long-term per-

    advantages, and limitations of DOC, and to validateass metrics comparison between the DOC system

    otential advanced wastewater reclamation processes.t third phase (20042007), a new prototype system isned and fabricated for delivery to NASA. Althoughwill have similarities to the original DOC system

    ll be used as pretreatment for RO), it will be a uniqueh a separate process for urine treatment [67].the important findings in Phase 2 of this researchmbrane performance and energy consumption in FOResults in Table 2 indicate that the FO CTA mem-in this study outperformed commercially availableanes. This is likely due to the lower internal CP inin DOC#1 and DOC#2. The draw solution is reconcentrated and

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 81

    Fig. 13. Specific energy consumption as a function of draw solution flow rate,salt loading, a

    the CTA mspecific memeasured dThe paramof the procand the amvaried. Thevariable opalmost alwproduced. Finvestigatio

    5.1.4. ConSludges

    often treatethe recalcitAfter digecentrifugestream (i.e.

    of nutrients (e.g., ammonia, ortho-phosphate, organic nitrogen),heavy metals, TOC, TDS, color, and TSS. In some agriculturalcommunities the centrate is used as a soil fertilizer [68]; how-ever, the common practice for centrate treatment is to return itback to the headworks of the wastewater treatment facility forre-treatment. When these species are returned to the head of thetreatment facility, they increase the facility loading and operat-ing cost, and it is suspected that some of these constituents arerecalcitrant and end up in the effluent as nitrogen and phospho-rous species.

    In a current study [4], FO is being investigated as a potentialprocess for concentration of centrate at the Truckee MeadowsWater Reclamation Facility (TMWRF) in Reno, Nevada. Themain objectives of this study are to determine the advantagesand limitations of using FO to concentrate centrate; to designa hybrid system consisting of FO as pretreatment for RO forconcentration of centrate; to develop an economic model anddetermine the cost effectiveness of the FO process; and to eval-uate the potential agricultural use of the concentrated stream as

    izer.r to

    esh (cen

    l drtrati

    ch tras w

    12 hThuew, 71 thrd ann foa) wind

    te thranetude

    Fig. 14. Watedecline betwend RO pump capacity for the DOC system [18].

    embrane stemming from the unique structure of thismbrane (see Section 4.1). Power consumption wasuring operation under variable operating conditions.

    eters that were found to be important in the operationess (e.g., draw solution flow rate, RO pump capacity,ount of NaCl loaded in the draw solution loop) were

    results summarized in Fig. 13 indicate that undererating conditions, specific power consumption is

    ays less than 30 kWh for every 1 m3 of purified waterurther optimization of the process is currently undern.

    centration of digested sludge liquidsproduced in wastewater treatment facilities are mostd in anaerobic digesters for further degradation of

    rant organic solids and for stabilization of the sludge.stion, the sludge is commonly dewatered using a

    a fertilPrio

    150 mtreatedan NaCconcen

    For eaNaCl;matelyNaCl.with n(trial #stoppesolutioFig. 14a curve

    illustramembmagniwhich produces concentrated biosolids and a liquid, centrate). The centrate contains high concentrations

    membranetrial, flux d

    r flux as a function of draw solution (DS) concentration during FO concentration of (en trials is due to organic and suspended solids fouling. Flux was markedly restoredFO, the centrate is pretreated by filtering it through a

  • 82 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    decline between each trial (for trials #1 through #4) is the resultof membrane fouling over time. After the short cleaning cycle(between trials #4 and #5), the flux was completely restored to itsinitial level. A similar performance was observed when raw (notpretreated) centrate was used as the feed solution (Fig. 14b).However, the extent of flux decline between trials was muchmore apparent and was attributed to greater fouling caused byhigh concentrations of suspended solids (Fig. 14). Some fluxrestoration after cleaning was achieved; however, complete fluxrecovery was not obtained. Phosphorous rejection exceeded 99%and ammonia and total Kjeldahl nitrogen (TKN) rejections wereapproximately 87% and 92%, respectively. Color and odor com-pounds were almost completely rejected. It is expected that acombination of FO and RO (for draw solution reconcentration)will result in even higher rejections of pollutants from the finaleffluent.

    5.1.5. Forward osmosis for source waterpurication

    The usein Sectionmilitary, reable drinkibags are onslower thanrequire nomuddy watthat in mosmeating waand most io

    In the hor beveragsemi-permbag in an athe osmotisolid drawdraw solutnutrients anan ultimatFor small,34 h to co

    Fig.

    bags can be placed directly in the source water or they canbe suspended in another sealed plastic bag that holds thesource watuser. In recemergencyis debate atreatment psweet drink

    5.2. Seawa

    Severalsystems fohowever, mVery few pbe found. KAtlantic Ocand hollow

    n. Ked anbjec

    encyr seaecen

    en uanddio

    O. Tniumtionsonatesis ofrce (trati

    withe am

    highe frory.chemcess

    andmodto amt wa

    eral sdistilrodun avch-s

    e FOreat

    ed wce oux, m

    fore pehydration bagsof FO for water purification was briefly introduced

    4. The concept of hydration bags was developed forcreational, and emergency relief situations when reli-ng water is scarce or not available [63,69]. Hydratione of the few commercial applications of FO. Althoughother water purification devices, FO hydration bags

    power and only foul minimally, even when used wither. The high selectivity of an FO membrane ensurest situations and for most sources of water, the per-ter is free of microorganisms, most macromolecules,ns.

    ydration bags, an edible draw solution (e.g., a sugare powder) is packed in a sealed bag made of aeable FO membrane [63]. Upon immersion of thequeous solution, water diffuses into the bag due to

    c pressure difference and slowly dilutes the initiallysolution. At the end of the process the diluted

    ion can be consumed as a sweet drink containingd minerals. In this regard, hydration bags represent

    e treatment process; not a pretreatment process.personal devices (Fig. 15), the process can takempletely hydrate a 12 oz beverage. The extraction

    15. Illustration of water purification hydration bag [69].

    solutiomodelTheir oemergcess fo

    In rthat whbrane)carbonwith Fammo

    proporbicarbAnalying foconcen

    waterwith thratherto brinrecove

    A sFO prowaterUponposesproducby sevbranepure psolutio

    Bendioxidtions gachieving forhigh fldrivingthat therproviding better mobility and autonomy to theent years, the military procured hydration bags forand relief efforts around the world [23]. Yet, there

    mong experts whether hydration bags provide waterer se because the product is not pure water but athat can only be used for specific applications.

    ter desalination

    patents have been awarded for different methods andr water desalination by FO [4143,4547,7073];ost of them have not matured or proven feasible.

    eer-reviewed publications on FO desalination couldravath and Davis [21] investigated desalination of

    ean seawater by FO using cellulose acetate flat sheetfiber membranes and glucose solution as a draw

    essler and Moody [44] and Moody and Kessler [74]d tested similar applications of FO for desalination.tive was to develop a batch desalination process forwater supply on lifeboats, not as a continuous pro-water desalination.t bench-scale studies [22,47,48], it was demonstratedsing a suitable FO membrane (e.g., the FO CTA mem-a strong draw solution (highly soluble ammonia andxide gases), seawater can be efficiently desalinatedhe draw solution was formed by mixing togethercarbonate and ammonium hydroxide in specific[48]. The salt species formed include ammonium

    , ammonium carbonate, and ammonium carbamate.the process has shown that an osmotic pressure driv-

    ) as high as 238 bar for a feed water with a salton of 0.05 M NaCl, and as high as 127 bar for a feeda salt concentration of 2 M NaCl, can be achievedmonia/carbon dioxide draw solution [48]. This is a

    driving force considering that 2 M NaCl is equivalentm seawater desalination at approximately 70% water

    atic drawing of the novel ammoniacarbon dioxideis illustrated in Fig. 16. Water is extracted from sea-

    dilutes the ammoniacarbon dioxide draw solution.erate heating (near 60 C), the draw solution decom-

    monia and carbon dioxide. Separation of the freshter from the diluted draw solution can be achievedeparation methods (e.g., column distillation or mem-lation (MD)). The degasified solution left behind isct water and the distillate is a reconcentrated drawailable for reuse in the FO desalination process.cale FO data demonstrates that the ammoniacarbonprocess is a viable desalination process. Salt rejec-

    er than 95% and fluxes as high as 25 l/m2 h wereith the FO CTA membrane with a calculated driv-

    f more than 200 bar [22]. Although this is a relativelyuch greater flux is actually expected for such a high

    ce. Further analysis of the results [48] has indicatedrformance ratio (defined as experimental water flux

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 83

    Fig. 16. Sche[22].

    divided bywas at moslower-than

    All of thdesalinatioFOlack oan easily seseawater deis desired, Fa high osm

    5.3. Food

    Althougfruits andFO treatmehas been shas severaages and liand low prtaste, aromrejection, apressure-dr

    Severaldevices an[76,77]. Shin chronolo

    Two detof FO in th[14] reviewMD forvided a mo(including

    Popper efirst generajuices. Themembranesusing saturfruit juicesthe membr

    Based on the development of a new plate-and-frame mem-brane module for FO [77] by Osmotek Inc., Beaudry and Lampi

    lishtrati

    solutwardcentd waffee,the hma

    508olstapber

    eva

    n. Dncel diftratecos

    s theptin

    ] furtd intrate-ma

    ranesalciuhylenhickllingr mewat

    ition, espocessodeleterison ppolyam thantagmatic drawing of the novel ammoniacarbon dioxide FO process

    theoretical water flux) of the FO CTA membrane usedt 20%, and on average between 5% and 10%. This

    -expected flux is attributed to internal CP.e previous, yet limited, work on FO as an alternativen process has exposed the two major limitations off high-performance membranes and the necessity forparable draw solution. Moreover, when consideringsalination, and especially when high water recoveryO can be utilized only if the draw solution can induce

    otic pressure.

    processing

    h osmotic treatment of food products (e.g., preservedmeats) is very common in the food industry [75],nt for concentration of beverages and liquid foodstudied at laboratory-scale only [8,1114,16]. FO

    l advantages as a process for concentrating bever-quid foods, including operation at low temperaturesessures that promote high retention of sensory (e.g.,a, color) and nutritional (e.g., vitamin) value, highnd potentially low membrane fouling compared toiven membrane processes.patents have been awarded for inventions of FOd methods for the concentration of liquid foods

    [8] pubconcen

    sugarwere a

    to conshoweand codue tothe sumuse of

    Wrred rasvacuum

    solutiodifferesitionaconcen

    capitaladdres

    Ado[12,13be useconcen

    custommembride, cpolyetbrane tcontroThinnehigherIn addtrationFO prand mcharacrates)matic

    Froof advort summaries of the main studies are provided belowgical order.ailed summaries were published on the potential usee processing of liquid foods. Petrotos and Lazaridesed low pressure membrane processes FO, OD, andconcentration of liquid foods. Jiao et al. [11] pro-re comprehensive summary on membrane processesFO (DOC)) for concentration of fruit juices.t al. [15] were the first to use modern techniques andtion polymeric RO membranes to concentrate fruity used both tubular and flat sheet cellulose acetateand achieved an average water flux of 2.5 kg/m2 h

    ated NaCl as the draw solution. Highly concentratedwere produced but salt was found to diffuse throughane into the grape concentrate.

    processes flow operaticentrationsindustries,recovery prto transform

    5.4. The ph

    The oraadministratachieving drelease, targedy in theillnesses. Aed a short summary on the use of the DOC process foron of fruit juices. They recommended that 72Brixion be used as the draw solution. Herron et al. [77]ed a patent on a membrane module and a method

    rate fruit juices and wines. Laboratory test resultster fluxes as high as 4 and 6 l/m2 h for orange juicerespectively. These relatively high fluxes are partiallyigh turbulence achieved in their FO module [77]. Inry of the invention, the inventors recommended the5 wt.% sugar solution as the draw solution.

    d et al. [16] compared the sensory characteristics ofry juice concentrated by FO with that concentrated byporation. High fructose corn syrup was used as drawescriptive sensory analysis revealed no significant

    between the products of the two processes. Compo-ferences between the two types of processed juice

    were minor. No comparison of other aspects (e.g.,t or energy requirements) was provided to furtherbenefits or limitations of the FO process.g the methods of Herron et al. [77], Petrotos et al.her explored the optimal conditions by which FO canthe concentration of tomato juiceone of the mostd vegetable juices. Petrotos and co-workers usedde tubular thin-film composite aromatic polyamideand different draw solutions including sodium chlo-m chloride, calcium nitrate, glucose, sucrose, ande glycol 400 (PEG400). Results showed that mem-

    ness and draw solution viscosity are the main factorswater flux in the FO concentration of tomato juice.mbranes and lower viscosity draw solutions yielded

    er fluxes, and therefore, faster juice concentration., it was shown that pretreatment in the form of fil-ecially ultrafiltration, enhances the efficiency of the. In further studies, Dova et al. [9,10] investigatedd the impact of process parameters (e.g., membrane

    tics, feed and draw solution concentrations, and flowrocess performance using thin-film composite aro-mide RO membranes.

    ese studies, the FO process appears to have a numberes over evaporation and pressure-driven membraneor concentration of liquid foods. Low energy use,ng temperatures and pressures, and high product con-are the main advantages. However, similar to otherthe lack of optimized membranes and an effectiveocess for the draw solution are the main limitationsing FO into a full-scale process in the food industry.

    armaceutical industryosmotic pumps

    l route, which is still the most acceptable mode ofion of prescription drugs, may have limitations inesired outcomes. In special circumstances, extendedeted delivery, or especially accurate dosage of a rem-body is requiredparticularly in cases of chronicdditional benefits of the controlled release of drugs

  • 84 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

    include decreased dosing frequency, more regular drug concen-tration in the bloodstream, enhanced bioavailability, improvedpatient compliance, and reduced side effects [25]. For example,delivering therapies to specific cells can be an obstacle in treat-ing neurodegenerative diseases, such as Parkinsons disease andHuntingtons disease. Targeting treatment to the brain is diffi-cult because the bloodbrain barrier blocks many drugs [78]. Inother cases, a drug can have low oral bioavailability (e.g., it canhave low solubility or limited permeability) in the gastrointesti-nal tract [25].

    Controlled- or modified-release of drugs is possible throughthe use of osmotic pumps. Osmosis offers several advantagesas a driving force for constant pumping of drugs, includingaccurate mass transfer. For example, when considering targetedtreatment, osmotic pumps can deliver medicine directly to thecerebrospin

    The devcommerciastudies in thhave beenment of druOROS Purelease drupumps havtion, metersamples [7

    The prinsystem arein a titaniumand 40 mmfrom enzymight deacbrane covemembranesimpermeabtion) occupThe draw spharmaceuton separatdrug reservsion and eitbe stable atime, usualsmall orific

    Fig. 17. Crosmembrane cosolution) occtomeric pistonreservoir. Upoand the drug i

    der. Exit ports can range from simple, straight channels to morecomplicated design configurations [27].

    When taqueous sothe membrbuilds up,the piston,consequentfice. The raspect of athe drug wthe principmethodicalrate.

    The volnt oKa

    is plcan

    DS

    DSresse

    P

    Pdelivefor tnt wide o

    botmbr

    P

    can

    ic puic prion chumtartiing aed thic prluesllingn beo, w

    n,

    smo

    ewant saal fluid, where it is ultimately taken up into neurons.elopment of osmotic pumps was pioneered with thelization of the ALZET osmotic pump for animale mid-1970s [26]. More recently, osmotic principles

    applied to human therapy, resulting in the develop-g delivery systems such as the DUROS system [27],sh-PullTM, L-OROSTM, and EnSoTrol [25] that cangs continuously for up to 1 year. Recently, osmotice been studied as regulated systems for the acquisi-ing, buffering, delivery, and assay of fluid biological9].cipal components of a typical osmotic drug-deliveryillustrated in Fig. 17. The osmotic pump is contained

    alloy cylindrical reservoir that is 4 mm in diameterin length. This reservoir protects the drug molecules

    mes, body moisture, and cellular components thattivate the drug prior to release. A polyurethane mem-rs one end of the reservoir. Like other semi-permeable, it is permeable to water but almost completelyle to ions. The osmotic engine (i.e., the draw solu-ies a portion of the cylinder behind the membrane.olution is most often NaCl and a small amount oftical excipients in a tablet form. An elastomeric pis-es the draw solution from the drug formulation in theoir. The drug may either be a solution or a suspen-her aqueous or non-aqueous in nature. The drug mustt body temperature (37 C) for extended periods ofly from 3 months to 1 year. The drug exit port is ae located at the opposite end of the titanium cylin-

    s-section of the implanted DUROS System [27]. A polyurethanevers one end of the reservoir. The osmotic engine (i.e., the drawupies a portion of the cylinder behind the membrane. An elas-

    separates the draw solution from the drug formulation in the drugn diffusion of water into the osmotic engine, the piston is pusheds released through the drug outlet orifice.

    partmeKedempumpe,

    =wherebe exp

    P =wheredrug dessaryconstahand sonly ifthe me

    (DSand

    Pd Eq. (9)osmotosmotreflectin the[26]. Sassum

    saturatosmotThe vacontropartitioEven ssolutio

    5.5. O

    Rendifferehe osmotic pump is brought into contact with anlution or wet environment, water diffuses through

    ane into the draw solution compartment. As pressureit expands the draw solution compartment, pushesincreases the pressure in the drug compartment, andly induces the release of the drug through the ori-ate of water diffusion is the most important designn osmotic pump because it dictates the rate at whichill be released. Theeuwes and Yum [26] summarizedles of design and operation of osmotic pumps andly described the design criteria for constant delivery

    umetric flux of water into the draw solution com-f osmotic pumps can be described by the simplifiedtchalsky equation (Eq. (1) in Section 2). When theaced in an environment with an osmotic pressure of

    be expressed as

    e (7)is the osmotic pressure of the draw solution. P cand as

    d Pe (8)is the internal pressure difference associated with thery through the orifice and Pe is the pressure nec-he piston to compress the drug reservoir. To achieveater flux, and hence constant delivery rate, the right-f Eq. (1) must be constant. This condition can be meth terms, and P, are constant (assuming thatane permeability coefficient is constant)e) = constant (9)

    e = constant (10)be satisfied if (1) the amount of draw solution in the

    mp can ensure saturation in the water solution, (2) theessure of the environment is negligible, and (3) theoefficient is constant. Implantable osmotic pumpsan body can easily meet these three requirements

    ng from solid or very concentrated draw solution, andsmall drug reservoir, the draw solution can be keptroughout the delivery time period and at much higher

    essure than the osmotic pressure in the human body.of P in Eq. (10) can be reduced to almost zero bythe orifice size and by selecting a highly deformabletween the draw solution and drug compartments [26].hen a low molecular weight salt is used as a draw will generally always be much greater than P.

    tic powerpressure-retarded osmosis

    ble energy can be extracted wherever two streams oflinity or different chemical potential meet. Consid-

  • T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087 85

    Fig. 1

    ering that tapproximawater is recan be usedSection 2 abe used to

    A schemtrated in Fitaining meFO membrside of thethe pressurdiluted andone is deprond passesthe incominity are the[33,80] sugdiffer in ththe permeation of thepressurizatble of with[33,80].

    Power gthat make iit is renewacompared tdensity (i.eEstimates ssalinity gra

    For the leration has[3135,39,generatedpared PROfrom saliniPRO for pUnion andof NorwayForschungsTechnologymembranesequivalent

    The deveration wil

    for water treatment and desalination. Both processes depend onthe same semi-permeable membranes that at this time do not

    ercially exist.

    ncluding remarks

    increased attention to FO from various disciplines ariseshe fact that FO can be employed in many fields of sci-nd engineering including water and wastewater treat-seawater/brackish water desalination, food processing,elivery, and electric power production. Despite the lackust membranes and membrane modules for FO, basich on FO and the development of new applications of FOadily growing. Currently, the most important measure ton in order to advance the field of FO is the developmentmembranes in both flat-sheet and hollow fiber configura-he membranes need to provide high water permeability,

    jection of solutes, substantially reduced internal CP, highal stability, and high mechanical strength. For the future,

    ensity packing methods for well-performing flat-sheet FOranes (such as the modified spiral-wound module shown9) must be further developed. Development of draw solu-at can induce high osmotic pressure is another important

    wards further progress of the FO process. Most desirablew so

    entrathate wi

    wled

    authch,andAdm

    enc8. Simplified process layout for a PRO power plant [28].

    he salinity of seawater yields osmotic pressures oftely 2.7 MPa and that the osmotic pressure of riverlatively insignificant, a large portion of the 2.7 MPa

    for power generation. PRO (as briefly described innd illustrated in Figs. 1 and 2) is one method that canrealize this energy.atic drawing of power generation by PRO is illus-

    g. 18. Fresh water is pumped into a PRO module con-mbranes, in principle, similar to the semi-permeableanes described earlier. The fresh water flows on onemembrane and diffuses through the membrane intoized side of the membrane filled with seawater. Thepressurized seawater is then split into two streams;

    essurized in a turbine to generate power and the sec-through a pressure exchanger to assist in pressurizingg seawater. The two key components of a PRO facil-pressure exchanger and the membrane. Loeb et al.gested two possible steady-state flow systems that

    eir means of pressurizing the draw solution enteringte-receiver side of the membrane: pump pressuriza-draw solution (as depicted in Fig. 18) and permeateion of the draw solution using at least two tanks capa-standing the pressure of the permeate-receiver side

    enerated by PRO from seawater has certain featurest very attractive. It is a large and unexploited resource;ble; its use has minimal environmental impact; ando other potential sources of energy from the ocean, its., power capacity per physical size) is high [38,81].uggest that global power production potential fromdients is on the order of 2000 TWh per year [28].ast several decades, the PRO process for power gen-been continuously studied by Loeb and co-workers

    50,58,59,82]. Additionally, Jellinek and Masuda [29]power from PRO pilot testing. Wick [38] com-

    and reverse-electrodialysis for power generationty gradient sources. Currently, an intensive study of

    comm

    6. Co

    Thefrom tence a

    ment,drug dof robresearc

    are stebe takeof newtions. Thigh rechemichigh-dmembin Fig.tions thstep toare drareconc

    water,reactiv

    Ackno

    TheResear0801,Space

    Nom

    ABCDJwK

    Ptower generation is being funded by the Europeanbeing conducted by a joint effort of Statkraft SF

    , ICTPOL of Portugal, SINTEF of Norway, GKSS-zentrum of Germany, and Helsinki University ofof Finland with the main objective being to developfor PRO power that have a production capacity

    to at least 4 W/m2 [28].elopment and future success of PRO for power gen-l, in turn, have great influence on the success of FO

    Greek le

    lutions that require low energy for regeneration ortion, that are easily separable from the product fresh

    have low or no toxicity, and that are chemically non-th polymeric membranes.

    gments

    ors acknowledge the support of the Office of NavalAward Nos. N00014-03-1-1004 and N00014-05-1-the support of the U.S. National Aeronautics andinistration (NASA), Award No. NNA04-CL12A.

    lature

    water permeability coefficient (m3/m2 s Pa)solute permeability coefficient (m/s)concentration (mol/l)diffusivity (m2/s)water flux (m3/m2 s)resistance to salt transport in the porous support(s/m)hydraulic pressure (Pa)membrane thickness (m)

    ttersdifference operatormembrane porositychemical potentialosmotic pressure (Pa)reflection coefficientpore tortuosity

  • 86 T.Y. Cath et al. / Journal of Membrane Science 281 (2006) 7087

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