Hybrid TFC RO membranes with non-metallic additives

Abstract

A process for preparing a reverse osmosis membrane that includes: (A) providing a polyamine, a polyfunctional acid halide, and a flux increasing additive having the formula Z.sup.+B.sup., where Z.sup.+ is an easily dissociable cation and B.sup. is a beta-diketonate; (B) combining the polyamine, polyfunctional acid halide, and flux increasing additive on the surface of a porous support membrane; and (C) interfacially polymerizing the polyamine and the polyfunctional acid halide, and flux increasing additive on the surface of the porous support membrane to form a reverse osmosis membrane comprising (i) the porous support membrane and (ii) a discrimination layer comprising a polyamide. The reverse osmosis membrane is characterized by a flux that is greater than the flux of the same membrane prepared in the absence of the flux increasing additive.

Claims

1. A composition, comprising: a flux increasing additive having the formula Z.sup.+B.sup., wherein Z.sup.+ is an easily dissociable cation selected from among H.sup.+ and R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+, where R.sup.1, R.sup.2, R.sup.3, and R.sup.4, each independently is H, a C.sub.1-C.sub.6 hydrocarbyl group, a benzyl group, or a phenyl group, and B.sup. is a beta-diketonate; an aqueous phase containing a polar liquid; and a difunctional or polyfunctional nucleophilic monomer.

2. The composition of claim 1, wherein Z.sup.+ has the formula R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+, where R.sup.1, R.sup.2, R.sup.3, and R.sup.4, each independently is H, a C.sub.1-C.sub.6 hydrocarbyl group, a benzyl group, or a phenyl group.

3. The composition of claim 2, wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are ethyl groups.

4. The composition of claim 2, wherein R.sup.1, R.sup.2, and R.sup.3 each is an ethyl group, and R.sup.4 is H.

5. The composition of claim 1, wherein B.sup. has the formula: ##STR00004## where X and Y, independently, are H, a C.sub.1-C.sub.6 hydrocarbyl group, a benzyl group, a phenyl group, OR.sup.5, or NR.sup.6R.sup.7, each optionally substituted with fluorine, and R.sup.5, R.sup.6, and R.sup.7, each independently, is H, a C.sub.1-C.sub.6 hydrocarbyl group, a benzyl group or a phenyl group.

6. The composition of claim 5, wherein X and Y each independently is a C.sub.1-C.sub.6 hydrocarbyl group, a benzyl group, a phenyl group, OR.sup.5, or NR.sup.6R.sup.7 each substituted with fluorine.

7. The composition of claim 5, wherein X and Y are methyl groups.

8. The composition of claim 5, wherein X and Y are trifluoromethyl groups.

9. The composition of claim 5, wherein X and Y are selected so that B.sup. has a 5-carbon or larger carbon framework.

10. The composition of claim 1, wherein the nucleophilic monomer is a polyamine selected from the group consisting of diaminobenzene, triaminobenzene, m-phenylene diamine, p-phenylene diamine, 1,3,5-diaminobenzoic acid, 2-4-diaminotoluene, 2,4-diaminoanisole, xylylene diamine, ethylene diamine, propylene diamine, piperazine and tris(2-aminoethyl)amine.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a block diagram of hybrid TFC membrane 10 during fabrication in which aqueous phase 14 including -carbonyl additive 17, which may be positioned on support 12, which may be strengthened by fabric 20, contacted by organic phase 14 which may include nanoparticle additives 16 to create a thin film TFC membrane by interfacial polymerization (IFP).

(2) FIG. 2 is a block diagram of hybrid TFC membrane 10 during operation in which feed stream 29 is applied to discrimination membrane 24formed by IFP in the presence of a -carbonyl additive 17 and/or nanoparticle additives 16through which purified water 34 permeates while salts and other contaminants are rejected.

(3) FIG. 3 is a graph of the test results for 0.11 wt % and 0.26 wt % Et.sub.3NH(F.sub.6acac).sub.2 additive 17 with error bars indicating +/ standard deviation representing the numerical test results shown in Table 1.

(4) Like reference symbols in the various drawings indicate like elements.

DETAILED DESCRIPTION

(5) A TFC membrane may be advantageously formed by interfacial polymerization (IFP) between an organic phase which may optionally contain nanoparticle additives and an aqueous phase containing a -carbonyl anion, released from a -carbonyl additive, such as triethylammonium hexafluoro-acetylacetonate. In general, the -carbonyl additive is in the form of Z.sup.+B.sup. where Z may be H.sup.+ or Z may be R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+ where R.sup.1R.sup.2R.sup.3R.sup.4 may be independently H, C.sub.1-C.sub.6 hydrocarbyl, -benzyl or -phenyl. For example, in some embodiments, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are ethyl groups, while in other embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is an ethyl group, and R.sup.4 is H.

(6) B may be:

(7) ##STR00002##
where Y and X may be independently H, C.sub.1-C.sub.6-hydrocarbyl, -benzyl, -phenyl, OR.sup.5, or R.sup.6R.sup.7, each optionally substituted by fluorine, wherein R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.6-hydrocarbyl, -benzyl or -phenyl. In another preferred embodiment, X and Y may be CH.sub.3 so that B may be the -dicarbonyl compound acetylacetone, optionally substituted with fluorine. B.sup. may be in a from having a single hydrogen atom at the central carbon, such as:

(8) ##STR00003##

(9) Z.sup.+B.sup. is easily dissociated in the aqueous phase solution.

(10) B.sup. is preferably added in an amount that improves the permeability or flux of said reverse osmosis membrane and/or which maintains the salt rejection at a level greater than that of a control membrane made without additive. For example, the flux improvement preferably is on the order of at least 20%, at least 35% and preferably at least 50%. The salt rejection preferably is at a level of at least 99% and preferably at least 99.5%. The flux is preferably at least 27 gfd, more preferably at least 30 gfd, and most preferably on the order of about at least 35 gfd, while the salt rejection is on the order of about at least 99% or preferable on the order of about 99.5%.

(11) In addition to triethylamine, several other bases may be used to form the -diketonate salt. For instance, other alkyl or substituted alkyl groups may be present on the nitrogen, and the alkyl group may be either all the same, may be different. In addition to tri-substituted amines, ammonia, primary or secondary amines may be used. Quaternary ammonium hydroxide solutions may also be used to prepare quaternary salts. Other nitrogenous bases may also be used including aniline, or aromatic substituted nitrogens, and heterocycles such as piperazine, pyridine, or imidazole.

(12) Effective -diketonates include 5-carbon or larger carbon framework compounds where ketones are present on either side of a proton containing carbon atom. Atoms and substitutents may be present throughout the compound. Other electron withdrawing substituents such as fluorine can more preferably be present adjacent to the ketones to aid in the formation of the enolate compound.

(13) FIGS. 1 and 2 describe a representative process for preparing a reverse osmosis membrane by IFP using a Z.sup.+B.sup. flux enhancing additive. The discrimination layer of the membrane illustrated in FIGS. 1 and 2 also contains nanoparticles 16; the resulting TFC membrane is referred to as a hybrid TFC membrane. Such nanoparticles, however, are optional.

(14) In general, TFC membrane 10 may be synthesized using an interfacial polymerization process on a porous support, such as support membrane 12. Conventionally, two immiscible solvents are used, one in aqueous phase 14 and the other in organic phase 18, so that a monomer in one solvent reacts with a monomer in the other solvent. The interfacial polymerization reaction occurs at the interface between the two solutions when aqueous phase 14 and organic phase 18 are brought into contact with each other, to form a dense polymer matrix layerdiscrimination layer 24on the surface of support membrane 12.

(15) The polymerization reactions are very fast and relatively high molecular weights for the resultant polymer matrix are obtained. Once formed, the dense polymer matrixwhich becomes discrimination layer 24can advantageously act as a barrier to inhibit ongoing contact between the reactants in aqueous and organic phases 14 and 18 to slow the ongoing polymerization reaction. As a result, discrimination layer 24 is formed as a selective dense layer which is typically very thin and permeable to water, but relatively impermeable to dissolved, dispersed, or suspended solids, such as salts to be removed from sea or brackish water to produce purified water. Resultant membrane 10 is conventionally described as a thin film composite (TFC) membrane.

(16) The first monomer can be a dinucleophilic or a polynucleophilic monomer and the second monomer can be a dielectrophilic or a polyelectrophilic monomer. That is, each monomer can have two or more reactive (e.g., nucleophilic or electrophilic) groups. Both nucleophiles and electrophiles are well known in the art, and one of ordinary skill in the art can select suitable monomers for this use. The first and second monomers are conventionally selected to reactwhen aqueous and organic phases 14 and 18 are brought into contactby undergoing interfacial polymerization to form a three-dimensional polymer network, often called a polymer matrix.

(17) The first and second monomers can also be chosen to be capable of undergoing a polymerization reaction when aqueous and organic phases 14 and 18 brought into contact to form a polymer product that is capable of subsequent crosslinking by, for example, exposure to heat, light, radiation, or a chemical crosslinking agent.

(18) Regarding aqueous phase 14, the first monomer can be selected to be soluble in a polar liquid, preferably water, to form a polar mixture, referred to herein as aqueous phase 14. Generally, the difunctional or polyfunctional nucleophilic monomer can have primary or secondary amino groups and can be aromatic (e.g., a diaminobenzene, a triaminobenzene, m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, 1,3,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, and xylylene diamine) or aliphatic (e.g., ethylenediamine, propylene diamine, piperazine, and tris(2-diaminoethyl)amine).

(19) Examples of suitable amine species include primary aromatic amines having two or three amino groups, for example m-phenylenediamine, and secondary aliphatic amines having two amino groups, for example piperazine. The amine can typically be applied to microporous support 12 as a solution in a polar liquid, for example water. The resulting polar mixture typically includes in the range from about 1 to about 6 wt. % amine, preferably in the range of about 2 to about 4.0 wt. %, amine and most preferably about 3.0 wt. % amine. The polar mixture need not be aqueous, but the polar liquid should be immiscible with the apolar liquid. Although water is a preferred solvent, non-aqueous polar solvents can be utilized, such as acetonitrile and dimethylformamide (DMF) for aqueous phase 14.

(20) Phase 14 can be called a polar phase or an aqueous phase because such mixtures typically use water as the polar solvent. We believe most practitioners in this art refer to phase 14 as the aqueous phase. To avoid any confusion, that convention will be followed herein so that the term aqueous phase 14 is intended to refer to all polar phase liquids, e.g. whether or not the polar liquid is water.

(21) During interfacial polymerization, aqueous phase 14 may include one of the reactants, additive(s) such as nanostructured materials, e.g., nanoparticle additives 16, as well as processing aids such as surfactants, drying agents, catalysts, co-reactants, co-solvents, etc. The polar mixture, aqueous phase 14, is typically applied to microporous support membrane 12 by dipping, immersing, slot die coating, spray coating, gravure coating or other well known techniques. Once coated on porous support membrane 12, excess polar mixture can be optionally removed by evaporation, drainage, air knife, rubber wiper blade, nip roller, sponge, or other devices or processes.

(22) For monomers having sufficient vapor pressure, the monomer can be optionally delivered by vapor deposition from a vapor phase, or by heat, to support membrane 12.

(23) Regarding organic phase 18, the second monomer can be selected to be miscible with an apolar (organic) liquid, the mixture of which is shown in the figures as organic phase 18. Using the same convention discussed above with regard to aqueous phase 14, the typically used term organic phase is intended to refer to any appropriate nonpolar mixture, e.g. organic phase 18.

(24) The electrophilic monomer can be aromatic in nature and can contain two or more, for example three, electrophilic groups per molecule. For example, the second monomer can be a trimesoyl halide. For the case of acyl halide electrophilic monomers, acyl chlorides are generally more suitable than the corresponding bromides or iodides because of the relatively lower cost and greater availability.

(25) Suitable polyfunctional acyl halogens include trimesoyl chloride (TMC), trimellitic acid chloride, isophthaloyl chloride, terephthaloyl chloride and similar compounds or blends of suitable acyl halides. As a further example, the second monomer can be a phthaloyl halide.

(26) The polyfunctional acyl halidee.g., TMCcan be dissolved in the apolar organic liquid, e.g., organic phase 18, in a range of, for example, from about 0.09 to about 1.0 wt. %, preferably from about 0.17 to about 0.3 wt. %. and most preferably in the range of about 0.3 wt. % TMC. Suitable apolar liquids are capable of dissolving the electrophilic monomers (e.g. polyfunctional acyl halides) and which are immiscible with a polar liquid (e.g., water) in aqueous phase 14. In particular, suitable apolar liquids preferably include those which do not pose a threat to the ozone layer and yet are sufficiently safe in terms of their flashpoints and flammability to undergo routine processing without having to undertake extreme precautions.

(27) These include C.sub.5-C.sub.7 hydrocarbons and higher boiling hydrocarbons, i.e., those with boiling points greater than about 90 C., such as C.sub.8-C.sub.24 hydrocarbons and mixtures thereof, which have more suitable flashpoints than their C.sub.5-C.sub.7 counterparts, but are less volatile. The apolar mixtureorganic phase 18can typically be applied to contact aqueous phase 14 on microporous support membrane 12 by dipping, immersing, slot die coating, spray coating, gravure coating or other well known techniques. Any excess apolar liquid can be removed by evaporation or mechanical removal. It is often convenient to remove the apolar liquid by evaporation at elevated temperatures, for instance in a drying oven. Preferred ovens include flotation ovens, IR dryers, and laboratory convection or gravity ovens. Control of both web temperature and evaporation rate may be used to alter structure and performance.

(28) Referring now to FIGS. 1 and 2, a hybrid TFC membrane is shown in fabrication and then again in operation. In fabrication, aqueous phase 14 is applied to support membrane 12, which preferably rests on fabric 20. Support membrane 12 is typically a polymeric microporous support membrane, which in turn is often supported by non-woven or woven fabrics, such as fabric 20, for mechanical strength. Fabric 20 is preferably a polyester fabric having a basis weight of 60-120 grams per meter or gsm, and a thickness of 50-200 microns. Support membrane 12 may be made from polysulfone or other suitably porous membranes, such as polyethersulfone, poly(ether sulfone ketone), poly(ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, cellulose acetate, cellulose diacetate, or cellulose triacetate. Support membrane 12 may be 25-100 nm in thickness, preferably about 35 nm to about 75 nm and most preferably about 50 nm in thickness and may have the smallest pores located very near the upper surface. Porosity at the surface may be low, for instance from 5-15% of the total surface area.

(29) Aqueous phase 14 contains a -dicarbonyl additive 17, such as Et.sub.3NH(F.sub.6acac).sub.2. It is believed that Et.sub.3NH(F.sub.6acac).sub.2 is easily dissociated into an Et.sub.3NH.sup.+ cation Z.sup.+ and an (F.sub.6acac).sub.2.sup. anion in aqueous phase 14. Additive 17, as shown in FIG. 1, has the formula Z.sup.+B.sup., wherein B is an acetylacetonate moiety defined above and Z is an easily dissociated moiety such as ammonium ion defined above, which improves the permeability of the resulting reverse osmosis membrane 10 relative to a control membrane made without additive 17. Without wishing to be bound by theory, it is thought that additive 17 interferes with full cross linking of the polyfunctional acid halide (e.g., trimesoyl chloride) and polyamine (e.g., methylene phenylene diamine) compounds during IFP.

(30) Aqueous phase 14 is contacted with organic phase 18, which may contain another additive such as nanoparticles 16, to create discrimination membrane 24 by IFP as illustrated in FIG. 2. Examples of nanoparticles, including nanostructured materials such as carbon nanotubes and metal organic frameworks (MOF), that may be combined with the polyamine, polyfunctional acid halide, and beta-diketonate flux increasing additive, include:

(31) Linde Type A (LTA) zeolites available freeze dried, 100 nm diameter from Nanoscape AG, Am Klopferspitz 19, D-82152 Planegg, Germany;

(32) Linde Type Y (FAU) zeolites as described in MICROPOROUS AND MESOPOROUS MATERIALS Volume: 59 Issue: 1 Pages: 13-28 Published: Apr. 18, 2003 by Holmberg B A, Wang H T, Norbeck J M, Yan Y S;

(33) Zeolite Beta as described in MICROPOROUS AND MESOPOROUS MATERIALS Volume: 25 Issue: 1-3 Pages: 59-74 Published: Dec. 9, 1998 by Camblor M A, Corma A, Valencia S); and

(34) Cu MOF: A metal organic framework complex prepared from Cu and trimesic acid as described in Science 283, 1148 (1999); Stephen S.-Y. Chui, et al. [Cu3(TMA)2(H2O)3]n A Chemically Functionalizable Nanoporous Material.

(35) Either during IFP, or once the polymer matrix is formed, the anion believed to be present in this solution may interfere with the formation of covalent crosslinking Instead, ionic cross linkages between the hydrolyzed acyl halide groups and the terminal amines are formed. Such ionic cross-links, compared to the largely covalently crosslinked controls, promote increased water uptake and flux. At the same time, rejection may be maintained by virtue of these ionic crosslinks between the charged groups. Relative to ionic interactions in solution, these ionic crosslinks are stabilized by the rigidity of the polymer network keeping the two charged centers close to each other. The ionic crosslink may also allow a slight expansion of the matrix relative to a covalent bond, thereby increasing water uptake.

EXAMPLES

(36) The general procedure for the preparation of a flat cell test membrane was to prepare aqueous and organic phases, add the desired additives to one or both of these phases, apply the aqueous phase to a wet polysulfone membrane support on a glass plate, and then apply the organic phase to the aqueous phase on the membrane support as described in more detail immediately below. Control membranes were made in a similar way, except without the additive(s). All performance data unless otherwise noted was obtained from flat sheet testing on NaCl (32,000 ppm. 53 mS/cm) in tap water tested at 25 C. and 800 psi. Flow and rejection were measured after 1 hour of running.

(37) Aqueous Phase 14:

(38) An aqueous solution of MPD, 4.5 wt % of triethylammonium camphorsulfonate (TEACSA), and 0.06 wt % sodium lauryl sulfate (SLS) in DI water, and 0, 0.11, or 0.26 wt. % Et.sub.3NH(F.sub.6acac).sub.2 was prepared. Et.sub.3NH(F.sub.6acac).sub.2 was synthesized in-house and used without further purification. The procedure used was: Add 25 g ampoule hexafluoroacetylacetone (98%, Aldrich 238309, Lot MKBB2482) to 100 ml n-hexane that was stored over molecular sieves (96%, Acros 364370010, Lot 0930139) with stirring. Add 12.14 g triethylamine (Fluka 90342, Lot 1389546) added with stirring. 2 phases formed with bottom being a deep yellow color. After ca. 30 minutes, top layer decanted off and yellow phase stored overnight. Small amount of less dense phase collected overnight on top of the yellow phase and was removed the next day.
Organic Phase 18:
An Isopar G solution with 0.3 wt. % TMC and 4 wt. % mesitylene was also prepared and sonicated for up to 60 minutes. Isopar is a trademark of Exxon Corp.
Support Membrane 12:
A piece of wet polysulfone support was placed flat on a clean glass plate. An acrylic frame was then placed onto the membrane surface, leaving an area for the interfacial polymerization reaction to take place.
Discrimination Membrane 24:
Approximately 50 mL of the aqueous MPD solution was poured onto the framed membrane surface and remained for up to 2 min. The solution was drained by tilting the frame till no solution dripped from the frame. i) The frame was taken off, and was left horizontally for 1 minute. The membrane was then clamped with the glass plate in four corners. An air knife was used to finish drying the membrane surface. The membrane was reframed using another clean and dry acrylic frame and kept horizontally for 1 min. ii) Approximately 50 mL of the organic solution was poured onto the framed membrane surface and remained for 2 minutes. The solution was drained by tilting the frame (vertically) till no solution dripped from the frame. The acrylic frame was removed, and the membrane was kept horizontally for 1 minute. The membrane was then dried at 95 C. for 6 minutes.

(39) Two TFC membranes were synthesized and tested for each condition.

(40) Referring now to FIG. 3, the results of the testing above discussed above for 0.11 wt % and 0.26 wt % Et.sub.3NH(F.sub.6acac).sub.2 additive 17 are shown with error bars indicating +/ standard deviation. These tests show that both flux and rejection are affected by the concentration of Et.sub.3NH(F.sub.6acac).sub.2 in a similar manner as they are affected by the addition of certain other additives 17 such as alkaline earth additives. Table 1 below provides the test numerical results. Example 1, which contained no beta-diketonate additive, was used as a control.

(41) TABLE-US-00001 TABLE 1 Membranes with Et.sub.3NH(F.sub.6acac).sub.2 additives 17 x. # MPD TMC Ratio Aqueous 14 FLUX GFD REJ. 1 4% 0.3% 13.3 21.8 99.5% 2 4% 0.3% 13.3 0.11 wt % 26.9 99.53% Et.sub.3NH(F.sub.6acac).sub.2 3 4% 0.3% 13.3 0.26 wt % 29.6 99.27% Et.sub.3NH(F.sub.6acac).sub.2 4 4% 0.3% 13.3 0.13 wt % 30 99.57% Et.sub.3NH(F.sub.6acac).sub.2 5 4% 0.3% 13.3 0.36 wt % 32 99.52% Et.sub.3NH(F.sub.6acac).sub.2 6 4% 0.3% 13.3 0.13 wt % 32 99.57% Et.sub.4N (F.sub.6acac)2 7 4% 0.3% 13.3 0.28 wt % 34 99.5% Et.sub.4N (F.sub.6acac)2 8 4% 0.3% 13.3 0.08 wt % 32 99.57% F.sub.6acac 9 4% 0.3% 13.3 0.17 wt % 35.5 99.45% F.sub.6acac

(42) Without being restricted to this hypothesis, it is believed that the mechanism of action of these -diketonate salts may be a result of an interaction or reaction with one or more of the acyl chloride functionalities present on the TMC in organic phase 18. -diketonate compounds and their enolate salts may react with acyl halides either through the carbon adjacent to both ketones, a substituted ketone, or through the oxygen forming an ester. These formed compounds may either participate directly in the film formation, may react with end groups present after the initial polymerization, or the formed compound itself may undergo further reactions leading the true effective agent. These formed compounds are believed to be particularly effective when produced in concert with the IFP reaction itself, perhaps due to a decreased tendency to reduce molecular weight that may occur if the compound were present at the onset of the polymerization reaction. This may occur when the -diketonate is brought into contact with TMC at the same time, or after the amine reactant.

(43) This reaction may occur either in aqueous phase 18 after a small amount of TMC partitions into aqueous phase 14, at the aqueous-organic phase interface, or in organic phase 18 after the substituted ammonium -diketonate salt partitions into organic solution 18.

(44) A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.