WO2011152735A1 - Thin film composites - Google Patents

Thin film composites Download PDF

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Publication number
WO2011152735A1
WO2011152735A1 PCT/NO2011/000162 NO2011000162W WO2011152735A1 WO 2011152735 A1 WO2011152735 A1 WO 2011152735A1 NO 2011000162 W NO2011000162 W NO 2011000162W WO 2011152735 A1 WO2011152735 A1 WO 2011152735A1
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WO
WIPO (PCT)
Prior art keywords
thin film
liquid phase
water
polyfunctional
groups
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Application number
PCT/NO2011/000162
Other languages
French (fr)
Inventor
Tom Nils Nilsen
Inger Lise Alsvik
Original Assignee
Tom Nils Nilsen
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tom Nils Nilsen filed Critical Tom Nils Nilsen
Priority to EP11790058.9A priority Critical patent/EP2576027B1/en
Priority to US13/701,520 priority patent/US20130089727A1/en
Priority to CA2801638A priority patent/CA2801638C/en
Priority to JP2013513129A priority patent/JP5964292B2/en
Publication of WO2011152735A1 publication Critical patent/WO2011152735A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249981—Plural void-containing components

Definitions

  • the present invention relates to a method for the production of thin film composite membranes by interfacial polymerisation, in particular through the reaction of polyfunctional acyl halides with polyfunctional amines where the polyfunctional acyl halide is applied first to the support medium.
  • the method according to the invention produces membranes, suitable for osmosis applications, including reverse osmosis applications and pressure retarded osmosis applications, for example power production, water treatment or the like, and having an improved (i.e. reduced) water flow resistance.
  • the invention thus further provides an improved osmotic membrane, and a method for the desalination of water and a method of pressurisation of saline water in pressure retarded osmosis (PRO), and a method of concentrating solutions using forward osmosis (FO), comprising passing water through the improved membrane.
  • IP Interfacial polymerisation
  • RO reverse osmosis
  • nanofiltration membranes are employed in the manufacture of RO and nanofiltration membranes.
  • RO reverse osmosis
  • the membranes of the prior art also commonly suffer from low durability or resistance to compression, sensitivity to extremes of pH or temperature, and lack of resistance to microbial attack or oxidation by chlorine in the feed water.
  • IP the polymerisation takes place at the interface between two immiscible phases upon contact.
  • IP is frequently conducted on the surface of a microporous substrate, by first saturating the support with a water-based reagent and then bringing it into contact with an organic phase.
  • This type of Thin Film Composite (TFC) was first introduced by Cadotte (see US 4039440) and this is still the main type of membrane used in reverse osmosis and nanofiltration.
  • IP proceeds through polymerization of two fast reacting intermediates at the interface between two immiscible liquid phases.
  • the film tends to form and grow in the organic phase because of the low solubility of the acyl halide in water and relatively good solubility of the amine in the organic phase.
  • the relative diffusion rate of the two reactants determines the rate of polymerisation on each side of the polymer film formed.
  • the reaction is extremely fast and the film is instantaneously formed at the interface.
  • the continued polymerization leads to the formation of a dense layer that hinders diffusion of the amines and acyl halides across the film, hence such films are typically very thin.
  • the reactant diffusion rates and their relative diffusion rate are dependent on the swelling capacity of the polymer by the solvents used and the solubility of the reactants in the solvent mixture inside the film.
  • the thickness of the formed film varies with the type of reactants, solvents, concentration, and reaction time, ranging from 10 nm to several micrometers.
  • TFC membranes are characterized by an ultra-thin selective barrier layer laminated on a chemically different porous substrate, which is typically asymmetric, but not necessarily.
  • the selective layer is the key component controlling the separation properties of the membrane, while the porous substrate gives the necessary mechanical strength.
  • the porous support influences though the water and salt fluxes by its thickness, porosity and hydrophilic character.
  • TFC RO membranes have advantages over single-material asymmetric membranes in that the selective layer is formed in situ so the chemistry and performance of the top barrier layer and the bottom porous substrate can be independently studied and optimized to maximize the overall membrane performance.
  • TFC RO membranes have become dominant in the market because they offer a combination of high flux and high selectivity over other types of RO membranes. At present, most commercial TFC RO membranes are based on polyamide thin films.
  • the pressure retarded osmosis (PRO) process also relies on the semi-permeable character of a polymeric membrane to reject salt and let water pass, but in this case the character of the porous support membrane to let salt diffuse out is of crucial importance due to the opposite direction of the water flow and the salt flow. Also the water resistance at the interface of the two membranes is crucial to the performance of a PRO membrane.
  • US 4277344 discloses a technique for preparing an aromatic polyamide film by interfacial-polymerization of two primary amine substituents- containing aromatic polyfunctional amines with at least three acyl halide functional groups-containing aromatic acyl halides.
  • a porous polysulfone support is coated with m-phenylenediamine in water. After removal of excess m-phenylenediamine solution from the coated support, the coated support is covered with a solution of trimesoyl chloride (TMC) dissolved in FREON
  • Cadotte membrane exhibits good flux and salt rejection
  • various approaches have been taken to further improve the flux and salt rejection of composite polyamide reverse osmosis membranes.
  • other approaches have been taken to improve the resistance of said membranes to chemical degradation and the like.
  • TFC membranes with improved water flux without reduced salt rejection are of interest and research has focused on improvement either through design and synthesis of new polymers forming thin films of the TFC membranes or by physical/chemical modification of the existing thin-films.
  • the fouling properties of TFC membrane is of special interest searching for hydrophilic supports.
  • TFC Thin Film Composite
  • the current inventors have developed a process for the production of improved TFC membranes, which show very positive osmotic properties.
  • the membranes produced by the process of the invention can be formed on a hydrophilic porous support.
  • the membrane formed can be chemically bound to the microporous support, which addresses the problems that the membranes of the prior art have had with delamination in some applications.
  • the produced TFC membranes have a lower flow resistance of water on the interface between the two layers because the selective membrane faces the more hydrophilic surface towards the support.
  • the surface of the membrane has amine groups which can react with other groups.
  • they can be used to attach ionic groups on the membrane surface forming an electrical layer which will improve the salt rejection.
  • the invention provides a process for the preparation of a thin film composite, said process comprising:
  • the invention provides a thin film composite obtainable by the process as hereinbefore defined.
  • the invention provides the use of the thin film composite obtainable by the process as hereinbefore defined in osmotic membranes, gas separation, or nanofiltration.
  • the invention provides an osmotic method for the desalination of water comprising passing water through the thin film composition as hereinbefore defined.
  • the invention provides an osmotic method for pressurising a high salinity solution comprising passing water through the thin film composition from a lean salinity solution as hereinbefore defined.
  • the pressurized solution may be used for power production.
  • the invention provides a TFC membrane with improved fouling properties.
  • thin film composite is used herein to define the combination of a porous support on which is carried a thin film formed by the interfacial polymerisation reaction of the polyfunctional acyl halide and polyfunctional amino compounds.
  • the film which forms is inherently very thin due to the speed at which these compounds react and the slow diffusion rate of the compounds through the film formed.
  • inert is used herein with reference to solvents which are inert with respect to the membrane and relevant acyl halide and/or amino groups.
  • the porous support used in the present invention is preferably a microporous support. It is generally formed of a polymeric material containing pore sizes which are permitting the passage of permeate at a sufficient rate. However, the porous support should not have pores which are so big that the membrane cannot tolerate the pressure at which the membrane will be used. The working pressure will depend on the process chosen, for example in pressure retarded osmosis (PRO) the membrane can have larger pores than in reverse osmosis. If the pores are too large the thin film will be punctured by the high pressure. In practical terms the support membrane for a PRO process may have significantly larger pores than membranes intended for RO. In addition, if the pores are too large then the solvent will not be immobilised in the pore structure.
  • PRO pressure retarded osmosis
  • the pore size of the support will generally range from 1 to 100 nanometres.
  • the thickness of the porous support itself is not critical to the present invention, however, the total thickness of the porous support membrane and reinforcement is important in PRO.
  • the porous support is normally not strong enough to withstand the pressure in osmotic processes like RO and PRO, i.e. reinforcement is needed.
  • the reinforcement may be provided by any suitable mean known in the art, such as backing of polyamide web, non-woven polyamide or glass felt, or the reinforcement may be embedded in the substrate. In PRO the total thickness of the porous support and reinforcement should not exceed 100 ⁇ .
  • the hydrophilic character of the porous support membrane is of great importance in order to have as free flow as possible of the permeate and to have good fouling properties. If a hydrophobic support is used, pressure will be required at the inlet of the pores in order to overcome the capillary forces.
  • porous supports useful in the present invention include those having surfaces which are capable of reacting with the acyl halide, i.e. having -OH, -NH and/or -NH 2 groups Most preferably the support is a cross-linked polymer support or a cellulosic support such as cellulose acetate or regenerated cellulose acetate. Any cellulosic or polyetherimide (PEI) or indeed any hydrophilic support would be excellent.
  • PEI polyetherimide
  • the support may be functionalised to contain a number of groups that will react with the acyl halide and hence form an actual covalent bond between the acyl halide and the support.
  • the support may also inherently contain such groups. Suitable functional groups which can be introduced are amines, hydroxyls or other nucleophilic groups. Obviously, the concentration of acyl halide should be large enough to leave sufficient amount of the acyl halide to form the intended polymer film with the polyfunctional amine applied.
  • the basic concept is to add ions to the membrane surface by a surface reaction of amines with any kind of structure which will increase the ionic load of the surface. Basically by including either positive or negative ions on the membrane the salt rejection will increase greatly.
  • This polishing step is different from what have been disclosed in the prior art as a number of the compounds added in the present invention react much less well or not at all on these membranes.
  • ionic groups will be placed on the surface of the separation membrane during or after interfacial
  • the ionic groups may be pH dependant such as carboxylic acids or tertiary amines or pH independent ionic groups such as sulfonic acid or quaternary amines.
  • Carboxylic acids may be attached to the amine surface by using the same type of substances as in the first solution of acid halides and the same examples.
  • Sulpfonic acids may be attached to the membrane surface by any compound giving free sulfonic acids.
  • Sulfonic acids may be attached to the amine surface by substances such as sulfonyl chloride e.g. sulfonyl chlorides such as biphenyl-4,4'-disulfonyl chloride, benzene- 1,2- disulfonyl chloride, benzene- 1, 3 -disulfonyl chloride, benzene- 1,4-disulfonyl chloride Diphenylmethane-4,4'-disulfonyl chloride.
  • sulfonyl chloride e.g. sulfonyl chlorides such as biphenyl-4,4'-disulfonyl chloride, benzene- 1,2- disulfonyl chloride, benzene- 1, 3 -disulfonyl chloride, benzene- 1,4-disulfonyl chloride Diphenylmethane-4,4'-disulfonyl chloride
  • Tertiary, quaternary amines and sulfonic groups may be attached to the acid halide surface after the amine surface has been treated with acid halide.
  • Alkyl groups may be CI - C18, preferably CI - C8.
  • the aryl groups may be unsubstituted or full substituted, preferably unsubstituted to tri-substituted, the substituents preferably being inert to reactants in the system.
  • R may be the same or different from each other.
  • Alkyl groups may be CI - CI 8, preferably CI - C8.
  • the aryl groups may be unsubstituted or full substituted, preferably unsubstituted to tri-substituted, the substituents preferably being inert to reactants in the system.
  • Sulfonic acids may be attached to the acid halide surface by substances containing protic groups such as OH, NH or NH 2 and at leat one sulfonic group.
  • protic groups such as OH, NH or NH 2 and at leat one sulfonic group.
  • examples of such substances are 8-hydroxyquinoline-5-sulfonic acid, 2-aminobenzenesulfonic acid, 3- aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid aniline-2-sulfonic acid, aniline-3-sulfonic acid, aniline-4-sulfonic acid.
  • the porous support may be flat or hollow fibre, being reinforced or not, asymmetric or symmetric.
  • the support structure is wetted by a first liquid phase which contains a solution of at least one polyfunctional acyl halide in an inert solvent, preferably an aprotic solvent.
  • the term wetting is used herein to mean applying the first liquid phase so that it enters the pores of the support without applying pressure.
  • the first liquid phase is applied so as to completely enter i.e. saturate the pores of the support.
  • Solvents which may be used are dimethylsulfoxide (DMSO), dimethylformamide (DMF), di- methylethers, di-ethylethers, ethylmethyl-ethers and also mixtures of solvents of the types mentioned.
  • Preferred first solvent in this invention are methyl ethers of glycols, particularly as exemplified by diethyleneglycoldimethylether (Diglym) and
  • EGDME ethyleneglycoldimethylether
  • More preferred acyl halides include, 5-isocyanatoisophthalic chloride (ICIC), cyclohexane-l,3,5-tricarbonyl chloride (HTC), 3,3,5,5-biphenyl tetraacyl chloride (BTEC) and trimesoyl chloride (TMC).
  • the preferred first polymerisable species is trimesoyl chloride (TMC).
  • One polyfunctional acyl halide can be used on its own or a mixture of
  • polyfunctional acyl halides can be used. It is essential that the polyfunctional acyl halide has two or more acyl halide groups. It is also preferred if at least one of the acyl halides in step (I) or at least one of the amines in step (II) has at least three functional groups. Thus, if none of the amines have three or more amine groups, at least one of the acyl halides preferably has three or more acyl halide groups. It is preferred if the polyfunctional acyl halide has three or more acyl halide groups.
  • the polyfunctional acyl halides provide the first monomer needed for the interfacial polymerisation reaction which occurs in the present invention. As a monomer, it will typically be of low molecular weight e.g. 300 g/mol or less.
  • the acyl halides can be aromatic or aliphatic.
  • Diacyl halides which may be used include oxalyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, fumaryl chloride, itaconyl chloride, 1,2- cyclobutanedicarboxylic acid chloride, isophthaloyl chloride, terephthaloyl chloride, 2,6-pyridinedicarbonyl chloride, biphenyl-4,4- dicarboxylic acid chloride, naphthalene- 1,4-dicarboxylic acid chloride and naphthalene-2,6-dicarboxylic acid chloride.
  • Preferred diacyl halides in this invention are aromatic halides, particularly as
  • IPC isophthaloyl chloride
  • TPC terephthaloyl chloride
  • More preferred acyl halides include 5-isocyanatoisophthalic chloride (ICIC), cyclohexane-l,3,5-tricarbonyl chloride (HTC), 3,3,5,5-biphenyl tetraacyl chloride (BTEC) and trimesoyl chloride (TMC).
  • the preferred first polymerisable species is trimesoyl chloride (TMC).
  • the polyfunctional acyl halide species is dissolved in the first liquid phase.
  • the first liquid phase is formed by an inert solvent which does not react with the
  • polyfunctional acyl halide This will preferably be an aprotic solvent.
  • Suitable aprotic solvents for the first liquid phase are organic solvents and may be aromatic or aliphatic.
  • the first liquid phase solvent is a hydrophilic solvent.
  • the polyfunctional acyl halide should be dissolved in the first liquid phase in an amount constituting about 0.05-10 wt%, preferably, 0.15-5 wt%, of the first liquid phase. It will be appreciated that polyfunctional acyl halides react rapidly with water so it is preferred if any solvents employed are thoroughly dried before use. Moreover, the porous support can also be dried before use by immersion in the dried solvent containing a drying agent, e.g. silicagel, before application of the polyfunctional acyl halides.
  • a drying agent e.g. silicagel
  • the application of the first liquid phase to the porous support wets it.
  • Application of the acyl halide solution to the porous support can be accomplished by any convenient technique e.g. by casting, dipping, spraying or immersing the support in the solution.
  • After application it may be necessary to remove excess polyfunctional acyl halide before application of the polyfunctional amine. This can be achieved by pressing or rolling at pressures sufficient to remove excess solution without damaging the support.
  • a gas can be used to dry/blow off excess solution.
  • the skilled man can devise all sorts of ways of achieving the necessary drying step.
  • an extremely hydrophilic support membrane is formed if the surface of the support contains protic groups such as -OH, -NH- or -NH 2 . This will increase the water flux which is highly advantageous for RO and PRO.
  • the polyfunctional amine is applied, preferably in solution.
  • Solvents which may be used are dimethylsulphoxide (DMSO), dimethylformamide (DMF), di-methyl ethers, di-ethylethers, ethylmethyl-ethers and water, and also mixtures of solvents of the types mentioned.
  • Preferred second solvents in this invention are water and methyl ethers of glycols, particularly as exemplified by diethyleneglycoldimethylether (Diglym) and ethyleneglycoldimethylefher (EGDME).
  • the polyfunctional amine is essentially an amine having at least two amine functional groups.
  • the amine functional group is typically a primary or secondary amine functional group.
  • the use of tri functional (or more) amines is also contemplated, especially where the acyl halide employed is not trifunctional.
  • the polyfunctional amine is a monomer so will typically be of low Mw, e.g. less than 250 g/mol.
  • the polyfunctional amine may be aromatic or aliphatic, e.g. cycloaliphatic.
  • Preferred polyfunctional amines are aromatic (e.g. m-phenylenediamine (m-PDA), p- phenylenediamine (p-PDA), 1,3,5-triaminobenzene, 1,3,4-triaminobenzene, 3,5- diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, and xylylenediamine) or aliphatic (e.g., ethylenediamine, propylenediamine, and tris(2-diaminoethyl)amine).
  • Highly suitable compounds include piperazine or derivatives thereof such as 2- methylpiperazine, 2,5-dimethylpiperazine and piperazine itself.
  • the preferred second polymerisable species is phenylenediamine e.g. m-PDA.
  • the polyfunctional amine is dissolved in the second fluid phase.
  • This phase is preferably a liquid although feasibly, the polyfunctional amine could be applied as a vapour.
  • the second fluid phase contains a solvent which may be protic or aprotic.
  • the solvent used is aprotic.
  • the solvent may be aromatic or aliphatic.
  • the second fluid phase may employ the same solvent as the first liquid phase. The current process can form a membrane even when using the same solvent in the first and second liquid phases, since the first liquid phase solution is immobilized and thus forms a boundary layer.
  • the polyfunctional amine may be present in the second liquid phase in an amount constituting about 0.01 - 2.0 wt%, more preferably, 0.03 - 1.0 wt%, of the aqueous solution.
  • Suitable buffers are well known and include camphor sulfonic acid/triethyl amine buffer.
  • the polyfunctional acyl halide and polyfunctional amino compounds are mutually reactive by interfacial polymerisation to form a solid polymer that is insoluble in said first and second liquid phases and that adheres to the porous support.
  • No specific reaction conditions are needed as the reaction is rapid and easy. Ambient temperature and pressure can be used. It may be necessary to employ a base to neutralise the acid formed during the polymerisation reaction. The presence of this acid as a reaction product will slow the polymerisation so its neutralisation is preferred.
  • the materials formed in the present invention are thin film composites. They are formed from the porous support and an ultrathin film on top. The thickness of that film is typically of the order of 10 to 100 nm, preferably 20 to 50 nm.
  • polyfunctional amine solutions to the porous support can be accomplished by any convenient technique e.g. by casting, dipping, spraying or immersing the support in the solution as discussed above in connection with acyl halide application. If the pores on both sides of the support are sufficiently small for the film formed to withstand the osmotic pressure, only one sided application should be used as to achieve one sided coating.
  • a particularly preferred combination involves the use of a cellulosic support with a trimesoyl chloride (TMC) and a phenylene diamine.
  • TMC trimesoyl chloride
  • the thin film composite is preferably dried. This can employ ambient temperature or slightly elevated temperature or perhaps exposure to an inert gas flow and so on. The drying process is not to do any harm to neither the film nor the support.
  • the membrane formed may be post-treated by a number of methods known in the art.
  • a preferred treatment is to react the film with the further fluid phase containing acyl halide, e.g. polyfunctional acyl halide as hereinbefore defined. This will give a membrane surface with organic acid groups increasing the salt rejection.
  • any post-formation modification method can be employed as is well known in the art.
  • post-treatment of the polymer film to attach a strong acid can enhance the salt rejection.
  • the present inventors have found that the process described above allows the use of highly hydrophilic supports previously not usable for the formation of thin film composites.
  • the thin film composites of the invention offer excellent selective permeability properties and therefore have applications as osmotic membranes, e.g. reverse osmosis membranes and pressure retarded osmosis, and in gas separation in general. These membranes are used in power production, water purification, gas separation and the like.
  • the formed membranes are also hydrophilic and therefore offer less resistance to water flow than prior art membranes in which the interfacial polymerisation on the support is carried out the other way round (i.e. with polyfunctional amine applied to the support first).
  • the interface between the two layers typically forms a hindrance to water flow. This can be measured in terms of salt rejection and in particular permeate water flux.
  • the interface between the support and the separation membrane is typically also hydrophilic, resulting in an improved water flux.
  • the presence of ionic groups on the surface of the separation membrane results in an improved salt rejection.
  • Our membranes can exhibit a flux of the order of 3 x 10 "12 m 3 /m 2 sPa in RO for a feed solution of 0.3 wt.% NaCl at a pressure difference of 13 x 10 5 Pa with organic acids on the surface.
  • MDA (1), PDA (2) and TMC (3) from Aldrich and camphorsulfonic acid (CSA) and triethylamine (TEA) from Merck were used.
  • the bottles of MDA and TMC were flushed with argon gas after use to reduce decomposition.
  • the ethylene glycol diethyl ether used as solvent was dried over a column of anhydrous A1 2 0 3 and stored over activated molecular sieves (4 A).
  • Regenerated cellulose acetate (RCA) from Alpha- Laval was used as the porous support in all examples.
  • MDA m-Phenylene diamine
  • PDA p-Phenylene diamine
  • TMC Trimesoyl chloride
  • RCA membranes were soaked in ethylene glycol diethyl ether (EGDE) overnight (> 12 h). The membranes were soaked for a certain period of time (30 s to 120 s) in a solution of TMC in EGDE. The excess solvent on the membrane was removed using paper tissues and a rubber roller. The membranes were dried under argon or in vacuo for a certain period of time (30 min to 90 min). A solution of MDA (or PDA), CSA and TEA in water were prepared and the membranes were soaked for 30 s to 90 s. Excess solvent was removed by paper tissues and a rubber roller and the membranes were soaked in a solution of TMC in c-Hexan. The membranes were air dried (30 min to 1 hour) and soaked in water for storage. Ex l(g/g solvent) Ex 2 (g/g solvent) Ex 3 (g/g solvent)
  • Reaction 1 The reaction of cellulose with trimesoyl chloride
  • the membranes were tested for water flux in a reverse osmosis test cell at 1.3 x 10 "6 Pa with a NaCl concentration of 0.3 wt.%.
  • the salt retention was tested by measuring the conductivity in the permeate.

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Abstract

The present invention relates to a method for the production of thin film composite membranes by interfacial polymerisation, in particular through the reaction of polyfunctional acyl halides with polyfunctional amines where the polyfunctional acyl halide is applied first to the support medium.

Description

THIN FILM COMPOSITE
The present invention relates to a method for the production of thin film composite membranes by interfacial polymerisation, in particular through the reaction of polyfunctional acyl halides with polyfunctional amines where the polyfunctional acyl halide is applied first to the support medium.
The method according to the invention produces membranes, suitable for osmosis applications, including reverse osmosis applications and pressure retarded osmosis applications, for example power production, water treatment or the like, and having an improved (i.e. reduced) water flow resistance. The invention thus further provides an improved osmotic membrane, and a method for the desalination of water and a method of pressurisation of saline water in pressure retarded osmosis (PRO), and a method of concentrating solutions using forward osmosis (FO), comprising passing water through the improved membrane.
Interfacial polymerisation (IP) is a procedure used for rapid preparation of high molecular weight polymer thin films at room temperature. IP films are most commonly used as the rejection layer in separation membranes, but other uses include sensors, encapsulation for applications such as drug delivery, chemical separations and desalination. Polyamide films, in particular, are employed in the manufacture of reverse osmosis (RO) and nanofiltration membranes. However, while these materials have an acceptable salt rejection level, they have rather low water permeability, both properties which stem from the rigid cross-linked structure. The membranes of the prior art also commonly suffer from low durability or resistance to compression, sensitivity to extremes of pH or temperature, and lack of resistance to microbial attack or oxidation by chlorine in the feed water.
In IP, the polymerisation takes place at the interface between two immiscible phases upon contact. To provide stability to the thin film, IP is frequently conducted on the surface of a microporous substrate, by first saturating the support with a water-based reagent and then bringing it into contact with an organic phase. This type of Thin Film Composite (TFC) was first introduced by Cadotte (see US 4039440) and this is still the main type of membrane used in reverse osmosis and nanofiltration.
IP proceeds through polymerization of two fast reacting intermediates at the interface between two immiscible liquid phases. The film tends to form and grow in the organic phase because of the low solubility of the acyl halide in water and relatively good solubility of the amine in the organic phase. The relative diffusion rate of the two reactants determines the rate of polymerisation on each side of the polymer film formed. The reaction is extremely fast and the film is instantaneously formed at the interface. The continued polymerization leads to the formation of a dense layer that hinders diffusion of the amines and acyl halides across the film, hence such films are typically very thin. The reactant diffusion rates and their relative diffusion rate are dependent on the swelling capacity of the polymer by the solvents used and the solubility of the reactants in the solvent mixture inside the film. Hence, the thickness of the formed film varies with the type of reactants, solvents, concentration, and reaction time, ranging from 10 nm to several micrometers.
The reverse osmosis (RO) process which relies on the semi-permeable character of a polymeric membrane to reject salt and let water pass is an efficient technique to desalt seawater. The development of thin-film composite (TFC) membranes was a major breakthrough in the field of membrane science and technology, allowing improvement of the solute separation ability and efficiency. TFC membranes are characterized by an ultra-thin selective barrier layer laminated on a chemically different porous substrate, which is typically asymmetric, but not necessarily. The selective layer is the key component controlling the separation properties of the membrane, while the porous substrate gives the necessary mechanical strength. The porous support influences though the water and salt fluxes by its thickness, porosity and hydrophilic character. Composite membranes have advantages over single-material asymmetric membranes in that the selective layer is formed in situ so the chemistry and performance of the top barrier layer and the bottom porous substrate can be independently studied and optimized to maximize the overall membrane performance. TFC RO membranes have become dominant in the market because they offer a combination of high flux and high selectivity over other types of RO membranes. At present, most commercial TFC RO membranes are based on polyamide thin films.
The pressure retarded osmosis (PRO) process also relies on the semi-permeable character of a polymeric membrane to reject salt and let water pass, but in this case the character of the porous support membrane to let salt diffuse out is of crucial importance due to the opposite direction of the water flow and the salt flow. Also the water resistance at the interface of the two membranes is crucial to the performance of a PRO membrane.
Utilization of PRO in power generation (US 3906250 and US 4193267) has so far been limited by the poor performance of membranes.
US 4277344 (granted to Cadotte) discloses a technique for preparing an aromatic polyamide film by interfacial-polymerization of two primary amine substituents- containing aromatic polyfunctional amines with at least three acyl halide functional groups-containing aromatic acyl halides. In the preferred embodiment, a porous polysulfone support is coated with m-phenylenediamine in water. After removal of excess m-phenylenediamine solution from the coated support, the coated support is covered with a solution of trimesoyl chloride (TMC) dissolved in FREON
(trichlorotrifluoroethane) .
Although the Cadotte membrane exhibits good flux and salt rejection, various approaches have been taken to further improve the flux and salt rejection of composite polyamide reverse osmosis membranes. In addition, other approaches have been taken to improve the resistance of said membranes to chemical degradation and the like.
Many of these approaches have involved the use of various types of additives to the solutions used in the interfacial polymerization. In spite of the large amount of research which has been carried out in this area, there is still significant interest in developing more energy-efficient, contaminant selective, and fouling resistant TFC membranes for various applications. In particular, TFC membranes with improved water flux without reduced salt rejection are of interest and research has focused on improvement either through design and synthesis of new polymers forming thin films of the TFC membranes or by physical/chemical modification of the existing thin-films. The fouling properties of TFC membrane is of special interest searching for hydrophilic supports.
Recent developments in the field are described by S. Yu (Journal of Membrane Science, 342 (2009) pp. 313-320). Variation of polyacyl halide compounds, to form polymer films resulted in membranes having a higher flux, but these had lower salt rejection relative to the fully aromatic composite. The chemical modification of diamine has also been studied with this goal in mind. These modifications result in TFC membranes of enhanced water flux but simultaneously an accompanying and
considerable loss of salt rejection or vice versa. Additionally, other methods such as optimizing the formation of the thin-film by using solvent additives, or a catalyst, chemical modification of the aromatic polyamide thin-film after its formation, and/or treating the active skin layer of the membrane with ammonia or alkylamines have also been adopted to enhance water permeability of the TFC polyamide RO membranes at the expense of the salt rejection.
Traditionally, Thin Film Composite (TFC) membranes are made by soaking a porous membrane in amine/water solution, as disclosed in US 4277344. The amine- soaked membrane is then soaked in a solution of an acid chloride in an organic solvent. When the two immiscible monomer solutions are brought into contact, the monomers partition across the liquid-liquid interface and react to form a polymer. As the reaction continues, polymer film is formed at the interface, but the film is usually very thin because the growing interfacial polymer behaves as a barrier to diffusion of the monomers, and the polymerization levels off. Thus the IP method originally developed by Cadotte may be schematically described as:
A) Furnishing a polysulfone microporous support,
B) Coating, dipping or otherwise furnishing an amine comprising aqueous solution to the support such that it is essentially filled by this fluid,
C) Applying a halide comprising solution to the amine containing support, in which the halide solution is not water-soluble.
Despite the large amount of research which has been conducted in this area, there is still a need for membranes having improved water flux and improved fouling resistance. On a microporous support the current inventors have found that the inversion of steps B and C leads to significant improvements in these properties. By coating or filling the microporous support with the halide phase, such that the reaction occurs by the later application of the amine, the membrane produced has improved water flux and the possibility of using hydrophilic substrates gives improved fouling properties.
There is a general prejudice in the art against the reversal of steps B and C, because the wetting of the support by the amine comprising aqueous solution is very easy, and the polymerisation reaction occurs mainly in the organic phase. The current inventors have developed a process for the production of improved TFC membranes, which show very positive osmotic properties. The membranes produced by the process of the invention can be formed on a hydrophilic porous support. In addition, the membrane formed can be chemically bound to the microporous support, which addresses the problems that the membranes of the prior art have had with delamination in some applications. The produced TFC membranes have a lower flow resistance of water on the interface between the two layers because the selective membrane faces the more hydrophilic surface towards the support.
Using the method of the invention, the surface of the membrane has amine groups which can react with other groups. For example they can be used to attach ionic groups on the membrane surface forming an electrical layer which will improve the salt rejection.
Summary of Invention
Viewed from one aspect the invention provides a process for the preparation of a thin film composite, said process comprising:
(I) applying to a porous support, one sided or two sided, a first liquid phase comprising at least one polyfunctional acyl halide having two or more acid halide groups in an inert solvent; and thereafter
(II) contacting said porous support, one sided or two sided, with a second fluid phase comprising at least one polyfunctional amine having at least two amine functional groups; so as to form a thin film composite; and
(III) optionally reacting the formed composite with a second solution of acyl halide in an inert solvent being hydrophilic or hydrophobic.
Viewed from another aspect the invention provides a thin film composite obtainable by the process as hereinbefore defined.
Viewed from another aspect the invention provides the use of the thin film composite obtainable by the process as hereinbefore defined in osmotic membranes, gas separation, or nanofiltration. Viewed from another aspect the invention provides an osmotic method for the desalination of water comprising passing water through the thin film composition as hereinbefore defined.
Viewed from another aspect the invention provides an osmotic method for pressurising a high salinity solution comprising passing water through the thin film composition from a lean salinity solution as hereinbefore defined. The pressurized solution may be used for power production.
Viewed from another aspect the invention provides a TFC membrane with improved fouling properties.
Definitions
The term thin film composite is used herein to define the combination of a porous support on which is carried a thin film formed by the interfacial polymerisation reaction of the polyfunctional acyl halide and polyfunctional amino compounds. The film which forms is inherently very thin due to the speed at which these compounds react and the slow diffusion rate of the compounds through the film formed.
The term inert is used herein with reference to solvents which are inert with respect to the membrane and relevant acyl halide and/or amino groups.
Detailed Description
The porous support used in the present invention is preferably a microporous support. It is generally formed of a polymeric material containing pore sizes which are permitting the passage of permeate at a sufficient rate. However, the porous support should not have pores which are so big that the membrane cannot tolerate the pressure at which the membrane will be used. The working pressure will depend on the process chosen, for example in pressure retarded osmosis (PRO) the membrane can have larger pores than in reverse osmosis. If the pores are too large the thin film will be punctured by the high pressure. In practical terms the support membrane for a PRO process may have significantly larger pores than membranes intended for RO. In addition, if the pores are too large then the solvent will not be immobilised in the pore structure. The pore size of the support will generally range from 1 to 100 nanometres. The thickness of the porous support itself is not critical to the present invention, however, the total thickness of the porous support membrane and reinforcement is important in PRO. The porous support is normally not strong enough to withstand the pressure in osmotic processes like RO and PRO, i.e. reinforcement is needed. The reinforcement may be provided by any suitable mean known in the art, such as backing of polyamide web, non-woven polyamide or glass felt, or the reinforcement may be embedded in the substrate. In PRO the total thickness of the porous support and reinforcement should not exceed 100 μπι.
The hydrophilic character of the porous support membrane is of great importance in order to have as free flow as possible of the permeate and to have good fouling properties. If a hydrophobic support is used, pressure will be required at the inlet of the pores in order to overcome the capillary forces.
Examples of porous supports useful in the present invention include those having surfaces which are capable of reacting with the acyl halide, i.e. having -OH, -NH and/or -NH2 groups Most preferably the support is a cross-linked polymer support or a cellulosic support such as cellulose acetate or regenerated cellulose acetate. Any cellulosic or polyetherimide (PEI) or indeed any hydrophilic support would be excellent.
The support may be functionalised to contain a number of groups that will react with the acyl halide and hence form an actual covalent bond between the acyl halide and the support. The support may also inherently contain such groups. Suitable functional groups which can be introduced are amines, hydroxyls or other nucleophilic groups. Obviously, the concentration of acyl halide should be large enough to leave sufficient amount of the acyl halide to form the intended polymer film with the polyfunctional amine applied.
Chemical bonds between the support and separation membrane provide more robust membranes, especially with respect to washing procedures. This is important in both RO and PRO membranes.
This physical attachment also prevents delamination of the membrane from the support, a problem known in prior art composites. It is only by applying the acyl halide first that this advantage of delamination prevention easily can be realised.
For improving the salt rejection the basic concept is to add ions to the membrane surface by a surface reaction of amines with any kind of structure which will increase the ionic load of the surface. Basically by including either positive or negative ions on the membrane the salt rejection will increase greatly.
This polishing step is different from what have been disclosed in the prior art as a number of the compounds added in the present invention react much less well or not at all on these membranes. In order to achieve higher salt rejection ionic groups will be placed on the surface of the separation membrane during or after interfacial
polymerization. The ionic groups may be pH dependant such as carboxylic acids or tertiary amines or pH independent ionic groups such as sulfonic acid or quaternary amines.
Carboxylic acids may be attached to the amine surface by using the same type of substances as in the first solution of acid halides and the same examples.
Sulpfonic acids may be attached to the membrane surface by any compound giving free sulfonic acids.
Sulfonic acids may be attached to the amine surface by substances such as sulfonyl chloride e.g. sulfonyl chlorides such as biphenyl-4,4'-disulfonyl chloride, benzene- 1,2- disulfonyl chloride, benzene- 1, 3 -disulfonyl chloride, benzene- 1,4-disulfonyl chloride Diphenylmethane-4,4'-disulfonyl chloride.
Tertiary, quaternary amines and sulfonic groups may be attached to the acid halide surface after the amine surface has been treated with acid halide.
Examples of tertiary amines that may be attached to the acid halide surface are R3N (R= any chain such as alkyl, aryl, cyclic or branched and at least one chain contains at least one amine). R may be the same or different from each other. Alkyl groups may be CI - C18, preferably CI - C8. The aryl groups may be unsubstituted or full substituted, preferably unsubstituted to tri-substituted, the substituents preferably being inert to reactants in the system.
Examples of quaternary amines that may be attached to the acid halide surface are salts of R4N+ (R= any chain such as alkyl, aryl, cyclic or branched and at least one chain contains at least one amine). R may be the same or different from each other. Alkyl groups may be CI - CI 8, preferably CI - C8. The aryl groups may be unsubstituted or full substituted, preferably unsubstituted to tri-substituted, the substituents preferably being inert to reactants in the system.
Sulfonic acids may be attached to the acid halide surface by substances containing protic groups such as OH, NH or NH2 and at leat one sulfonic group. Examples of such substances are 8-hydroxyquinoline-5-sulfonic acid, 2-aminobenzenesulfonic acid, 3- aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid aniline-2-sulfonic acid, aniline-3-sulfonic acid, aniline-4-sulfonic acid.
The porous support may be flat or hollow fibre, being reinforced or not, asymmetric or symmetric.
Polyfunctional Acyl Halide
The support structure is wetted by a first liquid phase which contains a solution of at least one polyfunctional acyl halide in an inert solvent, preferably an aprotic solvent. The term wetting is used herein to mean applying the first liquid phase so that it enters the pores of the support without applying pressure. Preferably the first liquid phase is applied so as to completely enter i.e. saturate the pores of the support. Solvents which may be used are dimethylsulfoxide (DMSO), dimethylformamide (DMF), di- methylethers, di-ethylethers, ethylmethyl-ethers and also mixtures of solvents of the types mentioned. Preferred first solvent in this invention are methyl ethers of glycols, particularly as exemplified by diethyleneglycoldimethylether (Diglym) and
ethyleneglycoldimethylether (EGDME).
More preferred acyl halides include, 5-isocyanatoisophthalic chloride (ICIC), cyclohexane-l,3,5-tricarbonyl chloride (HTC), 3,3,5,5-biphenyl tetraacyl chloride (BTEC) and trimesoyl chloride (TMC). The preferred first polymerisable species is trimesoyl chloride (TMC).
One polyfunctional acyl halide can be used on its own or a mixture of
polyfunctional acyl halides can be used. It is essential that the polyfunctional acyl halide has two or more acyl halide groups. It is also preferred if at least one of the acyl halides in step (I) or at least one of the amines in step (II) has at least three functional groups. Thus, if none of the amines have three or more amine groups, at least one of the acyl halides preferably has three or more acyl halide groups. It is preferred if the polyfunctional acyl halide has three or more acyl halide groups.
The polyfunctional acyl halides provide the first monomer needed for the interfacial polymerisation reaction which occurs in the present invention. As a monomer, it will typically be of low molecular weight e.g. 300 g/mol or less. The acyl halides can be aromatic or aliphatic.
Diacyl halides which may be used include oxalyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, fumaryl chloride, itaconyl chloride, 1,2- cyclobutanedicarboxylic acid chloride, isophthaloyl chloride, terephthaloyl chloride, 2,6-pyridinedicarbonyl chloride, biphenyl-4,4- dicarboxylic acid chloride, naphthalene- 1,4-dicarboxylic acid chloride and naphthalene-2,6-dicarboxylic acid chloride.
Preferred diacyl halides in this invention are aromatic halides, particularly as
exemplified by isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC).
More preferred acyl halides include 5-isocyanatoisophthalic chloride (ICIC), cyclohexane-l,3,5-tricarbonyl chloride (HTC), 3,3,5,5-biphenyl tetraacyl chloride (BTEC) and trimesoyl chloride (TMC). The preferred first polymerisable species is trimesoyl chloride (TMC).
In one embodiment of the invention it is preferred if a mixture of polyfunctional acyl halides is employed in the first step of the process of the invention.
The polyfunctional acyl halide species is dissolved in the first liquid phase. The first liquid phase is formed by an inert solvent which does not react with the
polyfunctional acyl halide. This will preferably be an aprotic solvent. Suitable aprotic solvents for the first liquid phase are organic solvents and may be aromatic or aliphatic. Preferably, the first liquid phase solvent is a hydrophilic solvent.
The polyfunctional acyl halide should be dissolved in the first liquid phase in an amount constituting about 0.05-10 wt%, preferably, 0.15-5 wt%, of the first liquid phase. It will be appreciated that polyfunctional acyl halides react rapidly with water so it is preferred if any solvents employed are thoroughly dried before use. Moreover, the porous support can also be dried before use by immersion in the dried solvent containing a drying agent, e.g. silicagel, before application of the polyfunctional acyl halides.
The application of the first liquid phase to the porous support wets it. Application of the acyl halide solution to the porous support can be accomplished by any convenient technique e.g. by casting, dipping, spraying or immersing the support in the solution. After application, it may be necessary to remove excess polyfunctional acyl halide before application of the polyfunctional amine. This can be achieved by pressing or rolling at pressures sufficient to remove excess solution without damaging the support. Alternatively, a gas can be used to dry/blow off excess solution. The skilled man can devise all sorts of ways of achieving the necessary drying step.
After contact with the acyl halide, an extremely hydrophilic support membrane is formed if the surface of the support contains protic groups such as -OH, -NH- or -NH2. This will increase the water flux which is highly advantageous for RO and PRO.
Polyfunctional Amine
After the acyl halide has been applied, the polyfunctional amine is applied, preferably in solution. Solvents which may be used are dimethylsulphoxide (DMSO), dimethylformamide (DMF), di-methyl ethers, di-ethylethers, ethylmethyl-ethers and water, and also mixtures of solvents of the types mentioned. Preferred second solvents in this invention are water and methyl ethers of glycols, particularly as exemplified by diethyleneglycoldimethylether (Diglym) and ethyleneglycoldimethylefher (EGDME).
The polyfunctional amine is essentially an amine having at least two amine functional groups. The amine functional group is typically a primary or secondary amine functional group. As noted above however, the use of tri functional (or more) amines is also contemplated, especially where the acyl halide employed is not trifunctional. The polyfunctional amine is a monomer so will typically be of low Mw, e.g. less than 250 g/mol. The polyfunctional amine may be aromatic or aliphatic, e.g. cycloaliphatic.
Preferred polyfunctional amines are aromatic (e.g. m-phenylenediamine (m-PDA), p- phenylenediamine (p-PDA), 1,3,5-triaminobenzene, 1,3,4-triaminobenzene, 3,5- diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, and xylylenediamine) or aliphatic (e.g., ethylenediamine, propylenediamine, and tris(2-diaminoethyl)amine). Highly suitable compounds include piperazine or derivatives thereof such as 2- methylpiperazine, 2,5-dimethylpiperazine and piperazine itself. The preferred second polymerisable species is phenylenediamine e.g. m-PDA.
The use of primary polyfunctional amines is preferred.
The polyfunctional amine is dissolved in the second fluid phase. This phase is preferably a liquid although feasibly, the polyfunctional amine could be applied as a vapour. The second fluid phase contains a solvent which may be protic or aprotic.
Water is therefore a potential option here however it is preferred if the solvent used is aprotic. The solvent may be aromatic or aliphatic. In one embodiment, the second fluid phase may employ the same solvent as the first liquid phase. The current process can form a membrane even when using the same solvent in the first and second liquid phases, since the first liquid phase solution is immobilized and thus forms a boundary layer.
It is conventional in the art to use immiscible solvents to ensure the formation of a boundary for interfacial polymerisation to occur. By reversing the conventional order of reaction and applying the polyfunctional acyl halide first, the inventors have found that a boundary exists for interfacial polymerisation simply because the acyl halide solution becomes immobilised in the support. This therefore allows the use of any solvent with the amine and not just one which has to be immiscible with the solvent used for the acyl halide. This therefore means that water and other protic solvents which could react with the components in surface modifying reaction, and which are hard to remove, can be completely avoided. It is especially preferred therefore if the solvent for the polyfunctional amine is not water.
The polyfunctional amine may be present in the second liquid phase in an amount constituting about 0.01 - 2.0 wt%, more preferably, 0.03 - 1.0 wt%, of the aqueous solution.
It may be necessary to buffer the amine used e.g. to a pH of 7 to 13. Suitable buffers are well known and include camphor sulfonic acid/triethyl amine buffer.
The polyfunctional acyl halide and polyfunctional amino compounds are mutually reactive by interfacial polymerisation to form a solid polymer that is insoluble in said first and second liquid phases and that adheres to the porous support. No specific reaction conditions are needed as the reaction is rapid and easy. Ambient temperature and pressure can be used. It may be necessary to employ a base to neutralise the acid formed during the polymerisation reaction. The presence of this acid as a reaction product will slow the polymerisation so its neutralisation is preferred.
The materials formed in the present invention are thin film composites. They are formed from the porous support and an ultrathin film on top. The thickness of that film is typically of the order of 10 to 100 nm, preferably 20 to 50 nm.
Application of the polyfunctional amine solutions to the porous support can be accomplished by any convenient technique e.g. by casting, dipping, spraying or immersing the support in the solution as discussed above in connection with acyl halide application. If the pores on both sides of the support are sufficiently small for the film formed to withstand the osmotic pressure, only one sided application should be used as to achieve one sided coating.
A particularly preferred combination involves the use of a cellulosic support with a trimesoyl chloride (TMC) and a phenylene diamine.
After the polymerisation, the thin film composite is preferably dried. This can employ ambient temperature or slightly elevated temperature or perhaps exposure to an inert gas flow and so on. The drying process is not to do any harm to neither the film nor the support.
The membrane formed may be post-treated by a number of methods known in the art. A preferred treatment is to react the film with the further fluid phase containing acyl halide, e.g. polyfunctional acyl halide as hereinbefore defined. This will give a membrane surface with organic acid groups increasing the salt rejection.
Any post-formation modification method can be employed as is well known in the art. Thus, post-treatment of the polymer film to attach a strong acid can enhance the salt rejection.
The present inventors have found that the process described above allows the use of highly hydrophilic supports previously not usable for the formation of thin film composites.
The thin film composites of the invention offer excellent selective permeability properties and therefore have applications as osmotic membranes, e.g. reverse osmosis membranes and pressure retarded osmosis, and in gas separation in general. These membranes are used in power production, water purification, gas separation and the like.
An important feature of the invention is that the formed membranes are also hydrophilic and therefore offer less resistance to water flow than prior art membranes in which the interfacial polymerisation on the support is carried out the other way round (i.e. with polyfunctional amine applied to the support first). The interface between the two layers typically forms a hindrance to water flow. This can be measured in terms of salt rejection and in particular permeate water flux. However, in the current invention the interface between the support and the separation membrane is typically also hydrophilic, resulting in an improved water flux. The presence of ionic groups on the surface of the separation membrane results in an improved salt rejection. Our membranes can exhibit a flux of the order of 3 x 10"12 m3/m2sPa in RO for a feed solution of 0.3 wt.% NaCl at a pressure difference of 13 x 105 Pa with organic acids on the surface.
The inversed process thus makes it very easy to manipulate the system giving higher water flux and higher salt retention in osmotic processes.
Examples
Materials:
MDA (1), PDA (2) and TMC (3) from Aldrich and camphorsulfonic acid (CSA) and triethylamine (TEA) from Merck were used. The bottles of MDA and TMC were flushed with argon gas after use to reduce decomposition. The ethylene glycol diethyl ether used as solvent was dried over a column of anhydrous A1203 and stored over activated molecular sieves (4 A). Regenerated cellulose acetate (RCA) from Alpha- Laval was used as the porous support in all examples.
Figure imgf000016_0001
(1) (2)
m-Phenylene diamine (MDA) p-Phenylene diamine (PDA)
Figure imgf000016_0002
(3)
Trimesoyl chloride (TMC)
Experimental:
RCA membranes were soaked in ethylene glycol diethyl ether (EGDE) overnight (> 12 h). The membranes were soaked for a certain period of time (30 s to 120 s) in a solution of TMC in EGDE. The excess solvent on the membrane was removed using paper tissues and a rubber roller. The membranes were dried under argon or in vacuo for a certain period of time (30 min to 90 min). A solution of MDA (or PDA), CSA and TEA in water were prepared and the membranes were soaked for 30 s to 90 s. Excess solvent was removed by paper tissues and a rubber roller and the membranes were soaked in a solution of TMC in c-Hexan. The membranes were air dried (30 min to 1 hour) and soaked in water for storage. Ex l(g/g solvent) Ex 2 (g/g solvent) Ex 3 (g/g solvent)
TMC (in EGDE) 0.0018 0.0026 0.0031
MDA (in water) 0.0029 0.0053 0.0070
TMC (in c- 0.0043 0.0026 0.0048
Hexane)
CSA (in water) 0.01 0.01 0.01
TEA (in water) 0.01 0.01 0.01
Table 1: Formulations
Figure imgf000017_0002
Table 2: Residence time
Figure imgf000017_0001
Reaction 1 : The reaction of cellulose with trimesoyl chloride
Figure imgf000018_0001
Reaction 2: Schotten-Bauman reaction of PDA/MDA and TMC
Results:
The membranes were tested for water flux in a reverse osmosis test cell at 1.3 x 10"6 Pa with a NaCl concentration of 0.3 wt.%. The salt retention was tested by measuring the conductivity in the permeate.
Figure imgf000018_0002
Table 3: Flux and salt retention of membranes (Feed: 0.3 wt.% NaCl in water)

Claims

1. A process for the preparation of a thin film composite, said process comprising:
(I) applying to a porous support a first liquid phase comprising at least one polyfunctional acyl halide having two or more acid halide groups in an inert solvent; and thereafter
(II) contacting said porous support with a second fluid phase comprising at least one polyfunctional amine having at least two amine functional groups; so as to form a thin film composite.
2. A process as claimed in claim 1 further comprising a step (III) as the film is formed during post-treating formed membrane with liquid phase comprising at least one polyfunctional acyl halide having two or more acid halide groups in an inert solvent being hydrophilic or hydrophobic.
3. A process as claimed in claim 1 or 2 wherein either at least one of the acyl halides in step (I) and (III) or at least one of the amines in step (II) has at least three functional groups.
4. The process according to claim 1 to 3 wherein the reaction of the porous support and the acyl halide forms a covalent bond if the porous support has protic groups selected from -OH, -NH2 and/or -NH- on the surface.
5. The process according to any preceding claim wherein the polyfunctional acyl halide has at least two acid halide groups and/or is preferably selected from the group consisting of TMC, HTC and BTEC.
6. The process according to any preceding claim wherein the polyfunctional amine has at least two amine functional groups, and/or is preferably selected from the group consisting of m-PDA, p-PDA, TEA, 1,3,5-triaminobenzene and 1,3,4-triaminobenzene.
7. The process according to any preceding claim wherein the first liquid phase and/or the second liquid phase and/or the third liquid phase comprise Diglyme, EGDME or EGDE.
8. The process according to any preceding claim wherein the second liquid phase is water, an alkane or lamp oil.
9. The process according to any preceding claim wherein the third liquid phase comprise an alkane or lamp oil.
10. The process according to any preceding claim wherein the support is hydrophilic comprising cellulose acetate or regenerated cellulose acetate.
11. The process according to any one of the preceding claims wherein ionic groups are placed on the surface of the thin film composite membrane.
12. A thin film composite obtainable by the process as hereinbefore defined.
13. Use of the thin film composite obtainable by the process as hereinbefore defined in osmotic processes, gas separation, nanofiltration, reverse electro dialysis and/or fuel cells.
14. A method for the desalination of water comprising passing water through the thin film composition as hereinbefore defined.
15. A method for the pressurization of water for power production comprising passing water through the thin film composition as hereinbefore defined.
PCT/NO2011/000162 2010-06-04 2011-05-31 Thin film composites WO2011152735A1 (en)

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CA2801638A CA2801638C (en) 2010-06-04 2011-05-31 Polyamide thin film composite formed by interfacial polymerization
JP2013513129A JP5964292B2 (en) 2010-06-04 2011-05-31 Thin film composite

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NO335286B1 (en) 2014-11-03
CA2801638A1 (en) 2011-12-08
EP2576027B1 (en) 2020-08-26
EP2576027A4 (en) 2016-10-05
JP5964292B2 (en) 2016-08-03
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CA2801638C (en) 2020-03-24
NO20100814A1 (en) 2011-12-05

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