LIGAND BASED FORWARD OSMOSIS

Abstract

Forward osmosis methods and apparatus using a supported osmotic agent to establish or enhance an osmotic forward bias are disclosed. A supported osmotic agent may be assisted by osmotic agents not attached to a support and/or a pressure differential between an influent and effluent chamber and/or a temperature gradient and/or other means to increase the osmotic pressure in an effluent chamber.

Claims

1. An apparatus for producing a purified effluent solution or concentrating influent solution, comprising: first and second fluid chambers; a first fluid solution comprising a first solvent; at least one semi-permeable and hydrophilic or at least one semi-permeable and hydrophobic membrane, separating a portion of the first and second fluid chambers, wherein the at least one semi-permeable membrane is permeable to first solvent in the first fluid chamber; and at least one supported osmotic agent attached to a solid surface within the interior space of the second fluid chamber, wherein the solid surface comprises a plurality of membrane layers attached to the at least one semi-permeable membrane; whereby upon exposure of the first fluid solution to the at least one semi-permeable membrane, the first solvent passes through the at least one semi-permeable membrane due to an increased osmotic potential generated by the at least one supported osmotic agent and establishes fluid communication with the at least one supported osmotic agent.

2. The apparatus of claim 1 wherein the first fluid chamber has at least one discharge port to facilitate continuous discharge of the first fluid solution during operation of the apparatus.

3. The apparatus of claim 1, wherein the second fluid chamber has at least one discharge port to facilitate continuous discharge of the first fluid solution solvent during operation of the apparatus.

4. The apparatus of claim 1 further comprising at least one unsupported osmotic agent in said second fluid chamber cooperating with said at least one supported osmotic agent.

5. The apparatus of claim 1 wherein said at least one supported osmotic agent comprises a modified chitosan.

6. The apparatus of claim 1 wherein the support of said at least one supported osmotic agent comprises a modified chitosan.

7. An apparatus for producing a purified effluent solution or concentrating an influent solution, comprising: first and second fluid chambers; a first fluid solution comprising a first solvent; at least one semi-permeable and hydrophilic or at least one semi-permeable and hydrophobic membrane, separating a portion of the first and second fluid chambers, wherein the at least one semi-permeable membrane is permeable to first solvent in the first fluid chamber; in a forward osmosis method, causing an osmotic forward bias by introducing at least one supported osmotic agent to the second effluent fluid solution to create an osmotic potential higher than exists in the first influent fluid solution such that diffusion of the first influent solution solvent to the second effluent fluid solution occurs through the at least one semi-permeable membrane; wherein the said supported osmotic agent is attached to a solid surface; in the forward osmosis method, assisting the supported osmotic agent, which assisting comprises: introducing a single or plurality of osmotic agents not attached to the solid surface; wherein the solid surface is at least one of a plurality of membrane layers, a mesoporous substrate, and a wall or surface of a container; and causing at least one of a pressure differential and a temperature gradient between an influent and effluent solution chamber; and wherein the purified effluent solution has a solute concentration less than that prior to the said diffusion.

8. The apparatus of claim 7 wherein the solid surface is at least one of a mesoporous substrate, and a wall or surface of a container.

9. The apparatus of claim 7 further comprising, in the forward osmosis method, a means for increasing the osmotic potential of said second effluent solution, wherein the said means comprises adding a second osmotic agent to said second effluent fluid solution wherein the second osmotic agent is caused to work in cooperation with said at least one supported osmotic agent to increase the said osmotic potential.

10. The apparatus of claim 7 wherein the causing at least one of a pressure differential and a temperature gradient between the influent and effluent solution chamber further comprises, on said first influent fluid solution, raising the pressure, increasing the temperature or both.

11. The apparatus of claim 7 wherein the said second solvent is the same as the said first solvent.

12. The apparatus of claim 7 wherein the said at least one supported osmotic agent comprises a modified chitosan.

13. The apparatus of claim 7 wherein the support of said at least one supported osmotic agent comprises a modified chitosan.

Description

BRIEF DESCRIPTION OF THE DRAWING(S)

[0021] FIG. 1 is a Forward Osmosis (FO) Desalination Process schematic diagram.

[0022] FIGS. 2a and 2b are reported and calculated energy requirements for desalination of sea water by distillation, Reverse Osmosis (RO) and Forward Osmosis (FO) processes by McGinnis.

[0023] FIG. 3 is a drawing of a membrane plus osmotic agent and support in a Forward Osmosis (FO) system.

[0024] FIG. 4 shows an embodiment with no draw water in a Forward Osmosis (FO) Desalination Process.

[0025] FIG. 5 is a schematic process flow diagram for a multi-filter process for the desalination of sea water or the purification of water using Forward Osmosis (FO).

[0026] FIG. 6 shows example ligand/osmotic agents.

[0027] FIGS. 7a, 7b and 7c show additional example ligand/osmotic agents.

[0028] FIG. 8 shows additional example ligand/osmotic agents.

DETAILED DESCRIPTION

[0029] The following discussion is presented to enable a person skilled in the art to make and use the invention. Various modifications to the described embodiment will be readily apparent to those skilled in the art, and the generic principles herein may be applied to other embodiments and applications without departing from the spirit and scope of the present invention as defined by the appended claims. Thus, the present invention is not intended to be limited to the embodiment shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.

[0030] In one embodiment a ligand comprising one or more active groups is attached to a mesoporous substrate such as boehmite, titania, or other synthetic or natural mineral. The substrate is placed in fluid contact with a semi-permeable membrane. A feed solution or influent is placed on the upside of a membrane. In one embodiment there is no fluid initially on the other side, or permeate side of a membrane. In some embodiments a feed solution is sea water; alternatively a feed solution may be non-potable water; alternatively it may be industrial waste water; alternatively it may be non-aqueous, such as an alcohol or hydrocarbon-based fluid or other organic fluid; optionally mixed with water or not.

[0031] In one embodiment a ligand comprising one or more active groups attached to a substrate is chosen to have a high surface charge, optionally positive or negative. One or more active groups may disassociate in a solvent to achieve a high surface charge density. In some embodiments a second compound is added to a chosen solvent to assist a selected active group disassociate while remaining bound to a substrate. In some embodiments a second compound, acting as a second osmotic agent is disassociated by an active group bound to a substrate. In some embodiments a first active group may bind to a surface of a membrane like material; in this case a second active group is attached through an intermediate linking group to the first active group; the second active group has high surface charge or other property giving it high osmotic pressure characteristic. In some embodiments an intermediate linking group may link to more than two active groups.

[0032] Optionally, active groups and ligands functioning as an osmotic agent to increase the osmotic potential of a solvent are similar to those described in U.S. application Ser. No. 11/350,202.

[0033] A membrane is, optionally, for example, a sheet of asymmetric hydrophilic cellulose acetate nano-filtration membrane similar to those available from Hydration Technologies, Inc. of Albany, Oreg.; optionally a membrane is similar to one described in U.S. 2006/0226067; alternatively a membrane may be part of a membrane unit as a SEPA cell from GE Osmonics of Trevose, Pa. In some embodiments a membrane is at least one semi-permeable hydrophilic or hydrophobic membrane; optionally a membrane may be spiral wound or hollow fiber membrane modules.

[0034] FIG. 3 shows an example embodiment. FIG. 3 is a drawing of a membrane plus osmotic agent and support in a Forward Osmosis (FO) system; forward osmosis system 300 has waste water 305 passing through semi-permeable membrane 310. Waste water 305 is acted upon by osmotic potential difference created by the osmotic potential of 305 versus the osmotic potential of osmotic agent ligand plus support 320, in fluid communication with waste water 305. Semi-permeable membrane 310 prevents solute components of 305 from passing into osmotic agent ligand plus support 320; effluent 330 is measurably improved water as compared to 305. In some embodiments a multi-step process may be needed to achieve an acceptable purity of water for various applications such as drinking water or an industrial application such as integrated circuit manufacture. In some embodiments the osmotic potential difference provided by 320 is sufficient to pull water 305 across membrane 310; in some embodiments additional forces may be added such as pressure or temperature differential.

[0035] In another embodiment a second osmotic agent is added to a effluent side; in one example carbon dioxide or a precursor is added to increase a osmotic potential. The key characteristic is that the added osmotic agent(s) are not bound to a support as a first osmotic agent(s) is.

[0036] Another embodiment is a continuous process, as shown schematically in FIG. 4. FIG. 4 shows an embodiment with no draw water in a Forward Osmosis (FO) Desalination Process. Sea water, contaminated water, or other forms of influent solutions to be purified are represented as influent water 410, which is supplied to an influent side of membrane 420; 420 may be one or more membranes and, optionally, comprise one or more osmotic agent ligands plus support in fluid communication with one or more semi-permeable membranes. Potable water 430 flows out of FO apparatus 400 under gravity in one embodiment; influent 410 flows or is pumped pass membrane 420. In another embodiment effluent 430 is pumped out of FO apparatus 400. In the instant invention there may be no actual draw solution; in one embodiment the influent or feed solution supplies the first liquid into the effluent side of a water purifier and the fluid is continuously replaced by additional fluid from the influent side.

[0037] Another embodiment is a continuous process FO apparatus 500, as shown schematically in FIG. 5. FIG. 5 is a schematic process flow diagram for a multi-filter process for the desalination of sea water or the purification of water using Forward Osmosis (FO). Sea water, contaminated water, or other forms of influent solutions to be purified are represented as feed solution 510, which is supplied to apparatus 500. Feed water 510 is optionally filtered (not shown), and enters forward osmosis (FO) unit 500. FO unit 500 preferably includes semi-permeable membranes 520. Supported osmotic agent 530 are located in chambers 540 or, optionally attached to membranes 520 as discussed in FIG. 3. Supported osmotic agent 530 are surface charged enough and/or at high enough concentration such that the osmotic potential of effluent solution 570 while in chambers 540 is higher than that of feed water 510. Feed solution 510 while in flow paths 560 has a lower osmotic potential than effluent solution 575 while 575 is in fluid communication with osmotic agent 530. Note that effluent solution entering 500 may be at some composition 570; while traversing FO 500 effluent is of composition 575 which varies as effluent makes its way through 500; upon exiting effluent is at some composition 580, representing a gradual dilution of effluent with permeate from 510. Optionally, effluent 570 may comprise one or more second osmotic agents upon entering or shortly after entering, not shown. As those persons skilled in the art will appreciate, FO unit 500 could be any one of a number of design configurations, including but not limited to, spiral wound, hollow fiber, or flat sheet.

[0038] Supported osmotic agents comprising active groups, linking groups and substrate may be used multiple times; in some embodiments additional ligand comprising active groups and linking groups may be added to a substrate already in place in a water purifier.

[0039] In one embodiment supported osmotic agents comprise an ammonia active group and a carboxyl active group; alternatively a carboxyl active group is added as a liquid or gas to an entering effluent solution and an ammonia active group is a supported osmotic agent ligand. As used herein, influent solution refers to one wherein the solvent is crossing a semi-permeable membrane to an effluent solution; in the prior art a feed solution is also an influent solution and a draw solution is also an effluent solution.

[0040] As the skilled practitioner will appreciate, concentration polarization becomes a limiting factor in either forward osmosis or in reverse osmosis. Essentially, the boundary layer adjacent to the semi-permeable membrane becomes too concentrated in solute on the influent side and too diluted with driving solvent on the effluent side, thereby adversely affecting the forward osmotic driving force. High fluid velocities and mixing are usually used to mitigate this inherent problem.

[0041] In one embodiment a supported osmotic agent active group may be placed in very close proximity to a membrane, thereby increasing the localized concentration of the supported osmotic agent active group adjacent to a membrane.

[0042] In one embodiment a second, unsupported osmotic agent is a carboxyl ion; in one embodiment a second, unsupported osmotic agent is carbon dioxide bubbled through an effluent solution.

[0043] A metal complex, also known as coordination compound, is a structure composed of a central metal atom or ion, generally a cation, surrounded by a number of negatively charged ions or neutral molecules possessing lone pairs. Counter ions often surround the metal complex ion, causing the compound to have no net charge. The ions or molecules surrounding the metal are called ligands. Ligands are generally bound to a metal ion by a coordinate covalent bond, and are thus said to be coordinated with the ion. The process of binding to the metal ion with more than one coordination site per ligand is called chelation. Compounds that bind avidly to form complexes are thus called chelating agents (for example, EDTA). Coordination numbers, or the number of bonds formed between the metal ions and ligands, may vary from 2 to 8. The number of bonds depends on the size, charge, and electron configuration of the metal ion. Some metal ions may have more than one coordination number. Different ligand structural arrangements result from the coordination number. A coordination number of two corresponds with a linear geometry; a coordination number of four corresponds with either a tetrahedral or square planar molecular geometry; and a coordination number of six corresponds with an octahedral geometry. Simple ligands like water or chlorine form only one link with the central atom and are said to be monodentate. More examples of monodentate ligands include hydroxide, nitrite, and thiocyanate. Some ligands are capable of forming multiple links to the same metal atom, and are described as bidentate, tridentate etc. Oxalate and ethylenediamine (en) are examples of bidentate ligands, while diethylenetriamine (dien) is a tridentate ligand. EDTA is hexadentate, which accounts for the great stability of many of its complexes. Herein the terms coordination site, attraction site, binding site, linking site and interaction site are used approximately equivalently.

[0044] Previous work with coated or surface-modified zeolites may be found in U.S. Pat. No. 6,080,319 and U.S. 2004/0108274; both disclose methods for adsorbing contaminants, including pathogens, onto a porous substrate such as zeolite. U.S. Pat. No. 6,838,005 teaches a nano-porous, synthetic substrate of aluminum hydroxide fibers for adsorption purposes. U.S. 2004/0108274 discloses HDTMA as a ligand with a charged active group for attracting charged molecules; HDTMA is a candidate osmotic agent ligand.

[0045] Ligands of interest in some embodiments are prepared by a method of Johnson and co-workers as described in ArsenicInteractions Stabilize a Self-assembled As.sub.2L.sub.3 Supramolecular Complex; Angew. Chem. Int. Ed. 2004, 43, 5831, incorporated by reference herein in its entirety. The trigonal-pyramidal coordination geometry of As(III) features a stereochemically active lone pair when coordinated by sulfur-based ligands and is predictable enough to be exploited as a target for specific ligand design. Treatment of N-(2-mercaptoethyl)-1, 8-naphthalimide (HL) with stoichiometric amounts of AsCl.sub.3 and base affords AsL.sub.2Cl and AsL.sub.3 complexes stabilized in part by secondary As . . . O bonding interactions. The use of these secondary bonding interactions (SBI's) between As(III) and heteroatoms of appropriate ligands offers a complementary tool for designing ligands specific for this ion. Secondary bonding interactions are observed between main group metals and heteroatoms such as O, N, S or halogens with interatomic distances less than the sum of the corresponding van der Waals radii. These interactions have only recently been systematically studied in the context of supramolecular chemistry and they offer a potentially useful method towards designing chelators optimized to bind main group metalloids. The -mercaptoimido ligand represents two examples of SBI's between an imido oxygen of a ligand and the central arsenic atom of the complex.

[0046] The characteristic coordination of As(III) by sulfur-containing biological molecules such as glutathione or cysteine has recently been reported in the context of developing a better understanding of arsenic toxicity. However, there are relatively few known structures of arsenic thiolate complexes: a search of the Cambridge Structure Database (CSD) reveals only 59 examples of an As(III) ion coordinated by one or more thiolate organic ligands. Of these examples, only three complexes demonstrate As . . . O SBI's within the range of 2.7 to 3.2 . The use of thiolate ligands optimized for the specific pyramidal coordination geometry of As(III) that possess additional functional groups capable of exhibiting secondary bonding interactions is relevant towards designing specific chelators and sensors for this toxic main group element. One class of ligands used for the instant invention is of the benzyldithiol family; alternatives are shown in FIG. 2. Initial data indicate that the ligands are not toxic to humans or animals.

[0047] Suitable substrates for an osmotic agent ligand based coating comprise titania, zeolites, surface-modified zeolites, carbon, natural minerals or synthetic resins, with a macro, micro or nano porous structure and other materials known to one knowledgeable in the art; alternatively plastic, glass, steel and other materials of filter construction may be used. In some embodiments, an osmotic agent's contribution to overall osmotic potential is a function of how many charges it manifests; each substrate material/osmotic agent ligand combination has a different capacity based on its surface structure and cumulative osmotic agent charges. Application of a ligand based coating to a substrate may be prepared by coating first with a compound which can functionalize a substrate's surface enabling a preferred osmotic agent ligand based layer to be coated on to a prepared substrate. Alternatively, a substrate may require no special pretreatment apart from cleaning to remove debris or other foreign material; in these cases a bi- or multi-functional osmotic agent ligand attaches directly to active sites on a substrate and has one or more coordination sites available. In one embodiment an article of manufacture for FO comprises a substrate comprising a porous structure and at least one interaction or attachment site in combination with at least one ligand comprising at least two coordination or attachment sites, wherein the at least one ligand binds to the at least one substrate attachment sites by one of the at least two ligand coordination sites.

[0048] Turner, in Molecular Containers: Design Approaches and Applications discusses numerous molecular containers, completely enclosed hollow species capable of holding one or more guest species inside, and their ability to form a covalent assembly of guest-encapsulating host species; the first examples of host species binding their guests within a three-dimensional array of interactions were the class of compounds known as cryptands, discussed in a 1969 article; typically cryptands are synthesized by the addition of a diacyl-chloride to an a zacrown ether. Turner describes other molecular shapes such as a cavitand, which can be likened to a deep bowl in which a guest can reside, shown in FIG. 7c. Turner describes carcerands and hemicarcerands wherein a guest specie is enclosed by a cage compound; in one embodiment a cavitand captures a specie suitable as an osmotic agent. A cavitand or other suitable molecule is bound to a substrate and holds a guest specie osmotic agent such that it is in fluid communication with an influent solution across a semi-permeable or other appropriate membrane.

[0049] In an alternative embodiment a first coordination site of a first ligand may attach directly to a substrate site and a first osmotic agent active group attach to at least a second coordination site of first ligand; optionally additional osmotic agent active group attach to a second or more coordination sites. Alternatively, a substrate may first be treated or coated with a material which functionalizes a surface in order to enhance attachment of a first osmotic agent active group. Examples of such materials for functionalizing are phosphonic acids, examples shown in FIG. 7a, silanes, examples shown in FIG. 7B, or other organic or inorganic compounds, such as a cavitand in FIG. 7c, which may coordinate simultaneously with a chosen substrate-ligand pair or substrate-osmotic agent active group pair; some examples are metallic thin films, carbon nano-tubes and nanospheres, metallic nano-tubes and nanospheres, ceramic nano-tubes and nanospheres, proteins and organic templates; others are known to one knowledgeable in the field.

[0050] FIG. 8 contains examples of ligand/osmotic agent active group candidates. These molecules may be used directly to attach to a substrate or in combination to attach to a substrate and then coordinate with a particular osmotic agent active group.

[0051] In some embodiments a support for an osmotic agent may comprise chitin or chitosan or a chitosan/cellulose mixture; a chitosan material may be cross linked, or not; additional ligands may be added to a chitosan or chitosan/cellulose structure to facilitate it acting as a support; cellulose addition and/or the cross linking and/or ligand addition serve to form a modified chitosan. Optionally, a modified chitosan may act either as a support or as a supported osmotic agent or both simultaneously; optionally a modified chitosan may be formed around a hard particle following examples taught by Boddu in U.S. Pat. No. 6,786,336 and others of her publications. In some embodiments a modified chitosan may be formed as a hollow fiber after Bai (2007) and an osmotic agent placed on the interior, optionally, exterior, of the hollow fiber. Optionally, one type of osmotic agent may be on the exterior and another type on the interior.

[0052] Examples of materials of utility in some embodiments are found in U.S.2008/0149561; specifically, polyalcohols such as polyvinyl alcohol, cationically modified polyvinylalcohol, anionically modified polyvinylalcohol; polysaccharides such as chitosan, hyaluronan, cellulose, regenerated cellulose, cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethyl cellulose, cellulose esters such as cellulose acetates (including mono-, di-, and tri-acetates); proteins such as collagen, gelatin, etc.; ionomers; polyalkylene oxides such as polyethylene oxide, polypropylene oxide, polyethylene glycols, crosslinkable polyethylene glycol, etc.; polyurethanes; polyureas; poly(urethane-urea); polyimines such as polyethylene imine; polyvinylpyrrolidone; polyacrylic acids; polymethacrylic acids; polysiloxanes such as polydimethylsiloxane; poly(ester-co-glycol) copolymers; poly(ether-co-amide) copolymers; and mixtures, derivatives, copolymers and crosslinked forms of any of the above. Derivatives include ethers, esters, amides, etc. formed by alkylation, acylation etc. of functional groups (e.g., hydroxyl or amine groups), or by hydrolysis of hydrolyzable functional groups (e.g., esters, amides, anhydrides, etc.) present in the polymer of which the nanofiber is comprised. In particular embodiments, the nanofibers of the fibrous supports comprise polyacrylonitrile (PAN), polyethersulfone (PES), polyvinylidenefluoride (PVDF), crosslinked water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, modified cellulose, modified chitosan, etc. Other possibilities for modifying chitosan include water soluble polymers such as polyvinyl alcohol, polysaccharides (e.g., chitosan and hyaluronan), polyalkylene oxides (e.g., polyethylene oxide), gelatin and derivatives can be cross-linked using methods known in the art. For example, polymers containing hydroxyl or amine groups (e.g., polyvinyl alcohols, polysaccharides, proteins, etc.) can be cross-linked using aldehydes (e.g., formaldehyde), dialdehydes (e.g., C.sub.2-C.sub.8 dialdehydes such as glutaraldehyde, glyoxal), mono-aldehydes having acid functionality (e.g., glyoxylic acid), polycarboxylic acids (e.g., oxydisuccinic acid, citric acid), etc. These compounds are capable of reacting with at least two hydroxyl (or amine) groups of a water-soluble polymer. Other crosslinking methods include thermal and radiation crosslinking methods (photo crosslinking, electron beam crosslinking, gamma crosslinking, etc.) of polymers optionally modified with, or mixed with, suitable cross-linking and radiation sensitizing agents/catalysts. In some embodiments a chitosan based polymer may comprise additional sugar or polysaccharide compounds to increase its osmotic activity; in one embodiment glucose type compounds are linked to a chitosan structure for increased osmotic activity.

[0053] Examples of acceptable membranes for separating an influent and effluent chamber are given in U.S.2008/0149561, including the prior art discussed therein.

[0054] In some embodiments a method for producing a purified effluent solution or concentrating an influent solution, comprises separating a first influent fluid solution comprising a first solvent from a second effluent fluid solution comprising a second solvent with at least one membrane; introducing at least one supported osmotic agent to the second effluent fluid solution in sufficient amounts to create an osmotic potential higher than exists in the first influent fluid solution such that diffusion of the first influent solution solvent to the second effluent fluid solution occurs through the at least one membrane to the second solution; optionally a method further comprises a step of adding a second osmotic agent to said second effluent fluid solution wherein the second osmotic agent in cooperation with said at least one supported osmotic agent increases the osmotic potential of said second effluent fluid solution; optionally a method further comprising a step of increasing the osmotic potential of the second effluent fluid solution by choosing at least one of the following steps on said first influent fluid solution wherein the step is raising the pressure, increasing the temperature or both; optionally a method includes said second solvent and said first solvent are the same, optionally water or a biological based fluid such as blood or other solution; optionally a method includes wherein said at least one supported osmotic agent comprises a modified chitosan and/or wherein the support of said at least one supported osmotic agent comprises a modified chitosan.

[0055] In some embodiments an apparatus for producing a purified effluent solution or concentrating an influent solution, comprises first and second fluid chambers;

a first fluid solution comprising a first solvent; at least one membrane, separating a portion of the first and second fluid chambers, wherein the at least one membrane is permeable to the first solvent in the first fluid chamber; and at least one supported osmotic agent within the interior space of the second fluid chamber, whereby upon exposure to the at least one membrane, the first solvent passes through the at least one membrane and establishes fluid communication with the at least one supported osmotic agent; optionally, the first fluid chamber has at least one discharge port to facilitate continuous discharge of the first fluid solution during operation of the apparatus; optionally, the second fluid chamber has at least one discharge port to facilitate continuous discharge of the first fluid solution solvent during operation of the apparatus; optionally, an apparatus further comprises at least one unsupported osmotic agent in said second fluid chamber cooperating with said at least one supported osmotic agent; optionally, at least one supported osmotic agent comprises a modified chitosan; optionally, at least one supported osmotic agent comprises a modified chitosan.

[0056] Foregoing described embodiments of the invention are provided as illustrations and descriptions. They are not intended to limit the invention to precise form described. In particular, it is contemplated that functional implementation of invention described herein may be implemented equivalently. Alternative construction techniques and processes are apparent to one knowledgeable with organic and/or physical chemistry. Other variations and embodiments are possible in light of above teachings, and it is thus intended that the scope of invention not be limited by this Detailed Description, but rather by Claims following.

Following are incorporated by reference in their entirety: [0057] Forward Osmosis: A new Approach to Water Purification and Desalination; Miller, James E., et al.; Sandia Report, SAND2006-4634, July 2006. Sandia National Laboratories. [0058] U.S.2007/0278153; Oriard, T., et al.; Forward Osmosis Utilizing A Controllable Osmotic Agent; May 4, 2006. [0059] Internal concentration polarization in forward osmosis: role of membrane orientation; Gray, G. T., et al.; Desalination 197 (2006) 1-8. [0060] Forward Osmosis: Principles, applications and recent developments; Cath, T. Y., et al.; Jl. Membrane Science, 281, (2006) 70-87. [0061] A novel ammonia-carbon dioxide forward (direct) osmosis desalination process; McCutcheon, J. R., et al.; Desalination 174 (2005) 1-11. [0062] Influence of concentrative and dilutive internal concentration polarization on flux behavior in forward osmosis; McCutcheon, J. R., et al.; Jl. Membrane Science, 284, (2006) 237-247. [0063] Desalination by ammonia-carbon dioxide forward osmosis: Influence of draw and feed solution concentrations on process performance; McCutcheon, J. R., et al.; Jl. Membrane Science, 278, (2006) 114-123. [0064] Energy requirements of ammonia-carbon dioxide forward osmosis desalination; McGinnis, R. L., et al.; Desalination 207 (2007) 370. [0065] Membrane contactor processes for wastewater reclamation in space II.; Cath, T. Y., et al.; Jl. Membrane Science, 257, (2005) 111-119. [0066] U.S. Pat. No. 6,849,184; Feb. 1, 2005; Lampi, K., et al.; Forward Osmosis Pressurized Device and Process for Generating Potable Water. [0067] The Ammonia-Carbon Dioxide Forward Osmosisi Desalination Process; McCutcheon, J. R., et al.; Water Conditioning & Purification, October 2006. [0068] Forward Osmosis for Concentration of Anaerobic Digester Centrate; Holloway, Ryan W.; University of Nevada, Reno, June 2006. [0069] Forward (Direct) Osmosis: A Novel and Prospective Process for Brine Control; Ng, H. Y., et al.; WEFTEC.06. [0070] Removal of Natural Steroid Hormones fro Wastewater using Membrane contactor Processes; Cartinella, J. L., et al.; Environ. Sci. Technol. 2006, 40, 7381. [0071] U.S. 2006/0011544; published Jan. 19, 2006; Sharma, Sunity, et al.; Membrane Purification System. [0072] U.S. 2006/0144789; published Jul. 6, 2006; Cath, T. Y., et al.; Systems and Methods for Purification of Liquids. [0073] U.S. 2006/0226067; published Oct. 12, 2006; Herron, Jack; Asymmetric Forward osmosis Membranes. [0074] U.S. 2004/0108274; published Jun. 10, 2004; Schulze-Makuch, D., et al.; Removal of Biological Pathogens using Surfactant-modified Zeolite. [0075] Adsorption of Proteins on Mesoporous Molecular Sieves; Kisler, J. M., et al.; Mater. Phys. Mech. 4 (2001) 89. [0076] Actinide Sequestration using self-assembled Monolayers on Mesoporous Supports; Fryxell, G. E., et al.; Environ Sci. Technol. 2005, 39, 1324. [0077] U.S. Pat. No. 6,846,554; Jan. 25, 2005; Fryxell, G. E., et al.; Self-assembled monolayer and method of making. [0078] U.S. Pat. No. 6,326,326; Dec. 1, 2001; Fryxell, G. E., et al.; Surface Functionalized Mesoporous material and method of making. [0079] Ethylenediamine-modified SBA-15 as Regenerable CO2 Sorbent; Zheng, F, et al.; 10.1021/iie049488t; American Chemical Society; February 2005. [0080] SAMMS Technical Summary; Fryxell, G. E., et al.; Pacific Northwest National Laboratory; Rev. 3, August 2003. [0081] Turner, David R., et al.; Molecular Containers: Design Approaches and Applications; Structure and Bonding, Vol. 108, 2004, 97. Springer-Verlag. [0082] Caulder, Dana L., et al.; The rational design of high symmetry coordination clusters; J. Chem. Soc. Dalton Trans., 1999, 1185. [0083] Castellano, Ronald K., et al.; Formation of Discrete Functional Assemblies and Informational Polymers through the Hydrogen-bonding Preferences of Calixarene Aryl and Sulfonyl Tetraureas; J. Am. Chem. Soc., 1998, 120, 3657. [0084] Vickaryous, W. J., et al.; Arsenic-II Interactions Stabilize a Self-assembled As2L3 Supramolecular Complex; Angew. Chem. Int. Ed. 2004, 43, 5831. [0085] U.S. Pat. No. 6,080,319, U.S. Pat. No. 6,838,005, U.S. Pat. No. 6,786,336, U.S.2002/0043496, U.S.20080149561, U.S. Pat. No. 6,849,184, U.S.2006/0144789, U.S.2006/0011544, U.S.2005/0133447, U.S.2006/0226067, U.S.2007/0278153, U.S.2008/0105618; U.S. Pat. No. 6,849,184, U.S. Pat. No. 6,846,554, U.S. Pat. No. 6,326,326. [0086] Renbi Bai, Jl. Membrane Science, 302, (2007) 150.