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    • 专利摘要:
    MEMBRANE FOR NANOFILTRATION, USE OF A MEMBRANE, AND, PROCESS TO FORM AN ASYMMETRIC MEMBRANE OF COMPLETELY RECYCLED POLYBENZIMIDAZOLE COVERED WITH SOLVENT NANOFILTRATION SKIN Asymmetric membranes fully covered with skin optimized for use in organic and nanofiltration methods . The membranes are formed from polybenzimidazoles by phase inversion and are then cross-linked by the addition of cross-linking agents. These stabilize the membranes and allow the solvent nanofiltration to be maintained even in the solvents from which the membranes were formed by phase inversion, and in strongly acidic and strongly basic solvents.
    公开号:BR112013001380B1
    申请号:R112013001380-0
    申请日:2011-07-19
    公开日:2021-01-12
    发明作者:Andrew Guy Livingston；Yogesh Suresh Bhole
    申请人:Imperial Innovations Limited；
    IPC主号:
    专利说明:

    [0001] [001] The present invention relates to asymmetric membranes for nanofiltration, particularly nanofiltration of solutes dissolved in organic solvents, and particularly the nanofiltration of solutes dissolved in environments of strongly basic and acidic organic solvents. Background of the Invention
    [0002] [002] Membrane processes are well known in the art of separation science, and can be applied to a range of separations of species of different molecular weights in liquid and gas phases (see, for example, "Membrane Technology and Applications" 2nd edition , RWBaker, John Wiley and Sons Ltd, ISBN 0-470-85445-6).
    [0003] [003] Nanofiltration is a membrane process using membranes whose pores are generally in the 0.5-5 nm range, and which have molecular weight cuts in the region of 200-2,000 Daltons. Cutting the molecular weight of a membrane is generally defined as the molecular weight of a molecule that must exhibit 90% rejection when subjected to membrane nanofiltration. Nanofiltration has been widely applied for the filtration of aqueous fluids, but due to the lack of stable membranes in an appropriate solvent it has not been widely applied for the separation of solutes in organic solvents. This is despite the fact that organic solvent nanofiltration (OSN) has many potential applications in the manufacturing industry, including solvent exchange, catalyst recovery and recycling, purifications, and concentrations. US patents. No. 5,174,899 5,215,667; 5,288,818; 5,298,669 and 5,395,979 describe the separation of organometallic compounds and / or carbonyls from metals from their solutions in organic media. UK Patent No. GB2373743 describes the application of OSN for solvent exchange; UK Patent No. GB2369311 describes the application of OSN for recycling phase transfer agents, and EP1590361 describes the application of OSN for the separation of syntons during oligonucleotide synthesis. However, there are no reports to date describing the application of OSN in environments of strongly basic or acidic organic solvents.
    [0004] [004] Polyimides have been widely used to form membranes used in separation processes, particularly gas separations, and also for the separation of liquids. US 5,264,166 and US 6,180,008 describe processes for the production of asymmetric polyimide membranes entirely covered with skin. These membranes are prepared as flat sheet membranes on a support substrate, using a phase inversion technique, which results in an ultra-thin top layer of the asymmetric membrane characterized by pore sizes of less than 5 nm in diameter. After formation, the membranes are treated with a non-volatile conditioning agent dissolved in solvent. The conditioning agent maintains the membrane properties for the nanofiltration of low molecular weight solutes from organic solvents, and allows the membrane to be processed, stored and handled in a dry state. The application of these membranes for the recovery of solvents from lubricating oil filtrates is that described in US Patent Nos. 5,360,530; 5,494,566 and 5,651,877. GB 2437519 reports membranes formed by phase inversion of polyimide solutions, followed by crosslinking of the resulting polyimide membrane, and then treatment with a non-volatile conditioning agent dissolved in solvent. However, fully coated skin polyimide membranes formed by phase inversion are not stable in all solvents, even when crosslinked according to GB 2437519. In particular, they are not stable in strongly basic or acidic organic environments.
    [0005] [005] Polybenzimidazole membranes have been widely described for use in gas separations and aqueous fluid processing. US 3,699,038, US 3,720,607, US 3,841,492, US 4,448,687 and US 4,693,824 describe the formation of skin-coated polybenzimidizole membranes formed by phase inversion from a doping solution. US 3,737,402 reports the formation of polybenzimidazole membranes by phase inversion from a doping solution, followed by heat treatment at temperatures of at least 135 ° C to improve the performance of membrane reverse osmosis. US 4693825 reports the production of polybenzimidazole membranes from a doping solution containing benzyl alcohol as an additive.
    [0006] [006] It has been reported that cross-linking of polybenzimidizole (PBI) membranes improves their chemical resistance. US 4,666,996, US 6,986,844, US 4,734,466, US 4,020,142 and describe all processes for crosslinking PBI. However, these methods are known to lead to a dramatic increase in the fragility of the membranes, making them difficult to manufacture and use. Summary of the Invention
    [0007] [007] The present invention provides asymmetric polybenzimidazole nanofiltration membranes, which are particularly suitable for use in organic solvents.
    [0008] [008] In a first aspect, the invention provides a membrane for nanofiltration of a feed stream solution comprising a solvent and dissolved solutes and showing preferential rejection of the solutes at room temperature, comprising an asymmetric polybenzimidazole membrane fully coated with skin is impregnated with a conditioning agent.
    [0009] [009] In a particular embodiment, the polybenzimidazole is cross-linked in order to improve the chemical resistance of the membrane.
    [0010] [0010] In yet another aspect, the present invention provides for the use of a polybenzimidazole membrane as defined herein for the nanofiltration of a feed stream, wherein the feed stream comprises a solvent that is strongly acidic or strongly basic and / or the feed stream comprises one or more of the strongly acidic or strongly basic compounds present in the solvent.
    [0011] [0011] In yet another aspect, the present invention provides a method of separating dissolved solutes from a nanofiltration feed stream, said feed stream comprising a solvent that is strongly acid or strongly basic and / or the feed stream. feed comprises one or more strongly acidic or strongly basic compounds present in the solvent; wherein said method comprises passing the feed through a polybenzimidazole membrane, as defined herein.
    [0012] (i) um polímero de polibenzimidazol, e (ii) um sistema solvente para o referido polibenzimidazol que é miscível em água; (b) moldar uma película da referida solução dopante em um substrato de suporte;(c) permitir que a solução dopante evapore durante um período de evaporação e, então, imergir o molde de película sobre o substrato em um meio de coagulação;(d) opcionalmente, tratar a membrana assimétrica resultante com um solvente compreendendo um ou mais agentes de reticulação para polibenzimidazol; e(e) tratar a membrana assimétrica com um banho de lavagem ou banhos compreendendo um agente condicionador.[0012] In another aspect, the invention provides a process to form an asymmetric polybenzimidazole membrane fully coated with skin for solvent nanofiltration, comprising the steps of: (a) preparing a polybenzimidazole doping solution comprising: (i) a polybenzimidazole polymer, and (ii) a solvent system for said polybenzimidazole that is miscible with water; (b) molding a film of said doping solution onto a support substrate; (c) allowing the doping solution to evaporate during a period of evaporation and then immersing the film mold on the substrate in a coagulation medium; (d) optionally treating the resulting asymmetric membrane with a solvent comprising one or more cross-linking agents for polybenzimidazole; and (e) treating the asymmetric membrane with a washing bath or baths comprising a conditioning agent.
    [0013] [0013] In another aspect the present invention provides a membrane obtained by any of the methods defined herein.
    [0014] [0014] In another aspect the present invention provides a membrane obtained by any of the methods defined herein.
    [0015] [0015] In another aspect the present invention provides a membrane directly obtained by any of the methods defined herein.
    [0016] [0016] The membranes of the invention can be used for nanofiltration operations in organic solvents. In particular, they can be used for solvent nanofiltration operations in which the base polybenzimidazole is soluble. This is advantageous over many of the asymmetric solvent nanofiltration membranes of the prior art, which lose structure and dissolve in typical doping solvents such as dimethylacetimide (DMAc), and exhibit low or no flow, in some chlorinated solvents such as dichloromethane. In addition, the membranes of the present invention can be employed in a nanofiltration feed stream in which the solvent is strongly acidic or basic, or in which the feed stream contains components which are strongly acidic or basic. This is advantageous over asymmetric solvent nanofiltration membranes of the prior art, which lose structure and dissolve under strongly acidic or basic conditions. The membranes of the present invention, however, are stable in these solvents, offering acceptable flow and rejections. However, an additional advantage of the membranes of the present invention is that they can exhibit higher flows than known membranes when mixtures of water and organic solvent are being processed. Brief Description Of Drawings
    [0017] [0017] Figure 1 shows the intrinsic viscosity of the synthesized polybenzimidazole measured in dimethylacetimide at 30 ° C.
    [0018] [0018] Figure 2 shows the flow to various 30 bar (3 MPa) polybenzimidazole membranes with a nanofiltration feed stream comprising acetone as a solvent and with polystyrene oligomers as solutes.
    [0019] [0019] Figure 3 shows the flow and rejection data for various polybenzimidazole membranes prepared from a doping solution containing 17 wt% polybenzimidazole at 30 bar (3 MPa) with a nanofiltration feed stream comprising acetone as a solvent and with polystyrene oligomers as solutes.
    [0020] [0020] Figures 4 (a) and 4 (b) show the flow and rejection data for several polybenzimidazole membranes prepared from a doping solution, containing 15 wt% polybenzimidazole at 30 bar (3 MPa) with a current nanofiltration feed comprising acetone as a solvent and with polystyrene oligomers as solutes.
    [0021] [0021] Figure 5 shows the flow and molecular weight cut curves (MWCO) of polybenzimidazole membranes prepared from doping solutions at 15 and 17% by weight with DMAc as a solvent. Nanofiltration of a feed solution comprising the polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    [0022] [0022] Figure 6 shows the flow and MWCO curves of polybenzimidazole membranes prepared from doping solutions at 15 and 17% by weight with a mixture of DMAc: THF at a ratio of 4: 1 as a solvent. Nanofiltration of a feed solution comprising the polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C (% R on the y axis means% rejection).
    [0023] [0023] Figure 7 shows the flow and MWCO curves of polybenzimidazole membranes prepared from doping solutions at 15 and 17% by weight with DMAc as a solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in dichloromethane was carried out at 30 bar (3 MPa) and 30 ° C.
    [0024] [0024] Figure 8 shows the flow and MWCO curves of polybenzimidazole membranes prepared from doping solutions at 15 and 17% by weight with a mixture of DMAc: THF in a ratio of 4: 1 as a solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in dichloromethane was carried out at 30 bar (3 MPa) and 30 ° C (% R on the y axis means% rejection).
    [0025] [0025] Figure 9 shows the flow and MWCO curves of cross-linked polybenzimidazole membranes prepared from doping solutions at 17% by weight with DMAc as a solvent. Nanofiltration of feed solutions comprising polystyrene oligomers dissolved in THF and DMF was carried out at 30 bar (3 MPa) and 30 ° C (% R on the y axis means% rejection).
    [0026] [0026] Figure 10 shows flow versus time for cross-linked polybenzimidazole membranes prepared from 17% by weight doping solutions with DMAc as a solvent. Nanofiltration of feed solutions comprising polystyrene oligomers dissolved in DMF was carried out at 30 bar (3 MPa) and 30 ° C. Description of the Various Forms of Realization
    [0027] [0027] Asymmetric membranes will be familiar to anyone versed in this technique and include an entity consisting of a layer of ultra-thin top "skin" on a thicker porous substructure of the same material, that is, as being entirely covered with skin. Typically, the asymmetric membrane is supported on an appropriate porous support liner or support material.
    [0028] [0028] The polybenzimidazole membranes of the invention can be produced from a number of polybenzimidazole polymer sources. The identities of such polymers are shown in the prior art, including US 3,699,038, US 3,720,607, US 3,737,402, US 3,841,492, US 4,448,687, US 4,693,824 and US 4,693,825. Processes for producing appropriate polybenzimidazoles are known to those skilled in the art and include those described in US Patent 2,895,948, US Patent No. Re 26,065, US 3,313,783, US 3,509,108, US 3,555,389, US 3,433,772, US 3,408,336, US 3,549,603, US 3,708. 439, US 4,154. 919, 4,312,976, US 5,410,012, US 5,554,715 and in the Journal of Polymer Science, Vol 50, pages 511-539 (1961).
    [0029] [0029] A preferred class of polybenzimidazole polymer useful for preparing the membranes of the invention has the following general repeat structure I shown below:
    [0030] [0030] Appropriately, the group R in the general repetition structure I shown above has the structure shown below:
    [0031] [0031] In one embodiment, Q is a direct link.
    [0032] [0032] The R1 substituents on the general repeat structure I may include (1) an aromatic ring, (2) an arylene group, (3) an alkylene group, (4) an arylene-ether group, and (5) a ring heterocyclic. An appropriate example of an aromatic ring is phenyl. An appropriate example of an arylene group is phenylene. The "alkylene group" includes (1-20C) alkylene groups. In one embodiment, an alkylene group is a (1-6C) alkylene group. An arylene-ether group is suitably a group of formula III
    [0033] [0033] Another preferred class of polybenzimidazole polymers useful for preparing the membranes of the invention has the following general repeat structure II shown below:
    [0034] [0034] Appropriately Z is a fused phenyl ring.
    [0035] [0035] A preferred polybenzimidazole to form the membranes of the invention is poly (2,2 '- [m-phenylene]) -5,5'-bis-benzimidazole, which has the formula shown below:
    [0036] [0036] Appropriately, n is an integer within the range 10 to 5000, more typically 20 to 3000 and even more typically 50 to 2000.
    [0037] [0037] The membranes of the invention can be prepared by dissolving the desired polybenzimidazole polymer in a solvent together with optional viscosity enhancers, optional void suppressors, and optionally discrete particles of a non-miscible matrix, to give a viscous polymer doping solution, spreading the solution on a porous support to form a film, partially evaporating the solvent, cooling the film abruptly in water. This precipitates the polymer and forms an asymmetric membrane by the phase inversion process.
    [0038] (i) um polímero de benzimidazol presente em quantidades de 5 a 30% em peso da referida solução dopante, (ii) um sistema solvente para o referido polibenzimidazol que é miscível em água, (iii) opcionalmente, um melhorador de viscosidade presente em quantidades inferiores a 5% em peso da referida solução dopante, (iv) opcionalmente, um supressor de vazio presente em quantidades de menos do que 10% em peso da referida solução dopante, (v) opcionalmente, um tensoativo presente em quantidades de menos de 5% em peso da referida solução dopante, (vi) opcionalmente, uma matriz discreta inorgânica ou orgânica em suspensão na solução dopante em uma quantidade menor do que 20% em peso da referida solução dopante; (b) moldar uma película da referida solução dopante sobre um substrato de suporte;(c) permitir que a solução dopante evapore durante um período de evaporação, e em seguida imergir a película moldada sobre o substrato em um meio de coagulação;(d) opcionalmente, tratar a membrana assimétrica resultante com um solvente compreendendo um ou mais agentes de reticulação para polibenzimidazol, e;(e) tratar a membrana assimétrica com um agente de condicionamento.[0038] The invention includes a process for forming an asymmetric nanofiltration membrane of cross-linked polybenzimidazole solvent fully coated with skin comprising the steps of: (a) preparing a polybenzimidazole doping solution consisting essentially of (i) a benzimidazole polymer present in amounts of 5 to 30% by weight of said doping solution, (ii) a solvent system for said polybenzimidazole that is miscible in water, (iii) optionally, a viscosity enhancer present in amounts less than 5% by weight of said doping solution, (iv) optionally, a vacuum suppressor present in amounts of less than 10% by weight of said doping solution, (v) optionally, a surfactant present in amounts of less than 5% by weight of said doping solution, (vi) optionally, a discrete inorganic or organic matrix suspended in the doping solution in an amount less than 20% by weight of said doping solution; (b) molding a film of said doping solution onto a support substrate; (c) allowing the doping solution to evaporate during a period of evaporation, and then immersing the molded film on the substrate in a coagulation medium; (d) optionally treating the resulting asymmetric membrane with a solvent comprising one or more cross-linking agents for polybenzimidazole, and; (e) treating the asymmetric membrane with a conditioning agent.
    [0039] [0039] Optionally, the membranes can be dried, as an additional step (f) following step (e).
    [0040] [0040] The polybenzimidazole polymer doping solution can be prepared by dissolving the polybenzimidazole polymer in one or a mixture of organic solvents, including the following water-miscible solvents: Ν, Ν-dimethylacetamide, also referred to as DMAc, N- methyl-2-pyrrolidone, hereinafter referred to as NMP, tetrahydrofuran, hereinafter referred to as THF, N, N-dimethylformamide, hereinafter referred to as DMF, dimethyl sulfoxide, 1,4dioxane, gamma-butyrolactone, water, alcohols, ketones, and formamide.
    [0041] [0041] The weight percentage of the polymer in the polybenzimidazole solution can vary from 5% to 30% in the broadest sense, although a range of 12% to 20% is preferable and a range of 14% to 18% is even more preferred.
    [0042] [0042] Additives such as viscosity enhancers can be present in amounts of up to 10% by weight of said polybenzimidazole polymer doping solution and these include polyvinyl pyrrolidones, polyethylene glycols and urethanes. In addition, additives such as vacuum suppressors can be used in amounts of up to 5% by weight of said polybenzimidazole polymer doping solution, including maleic acid. Additives such as surfactants, which can influence pore structure, can be used in amounts up to 5% by weight of said polybenzimidazole polymer doping solution, for example, Triton X-100 (available from Sigma-Aldrich UK Ltd. ( octylphenoxy polyethoxyethanol)).
    [0043] [0043] Organic or inorganic matrices in the form of powdered solids can be present in amounts of up to 20% by weight of said polymer doping solution. Molecular carbon sieve matrices can be prepared by pyrolysis of any suitable material, as described in US Patent No. 6,585,802. Zeolites, as described in the US Patent. No. 6,755,900 can also be used as an inorganic matrix. Metal oxides such as titanium dioxide, zinc oxide and silicon dioxide can be used, for example, the materials available from Evonik Degussa AG (Germany) under its trademarks Aerosol and AdNano. Mixed metal oxides, such as mixtures of cerium, zirconium and magnesium can be used. Preferred matrices will be particles smaller than 1.0 microns in diameter, preferably less than 0.1 microns in diameter, and preferably less than 0.01 microns in diameter. In some cases, it may be advantageous to disperse the matrices in a separate solution from the doping solution, preferably an organic solvent solution, and then subsequently adding this solution to the doping solution containing the polymer. In a preferred embodiment, crystals or nanoparticles of an inorganic matrix, for example, zeolites or metal oxides, can be grown in a selected size in a separate solution from the doping solution, and this dispersion solution is subsequently added to the solution dopant containing the polymer. This separate solution may comprise water or an organic solvent with nanoparticles dispersed in the continuous liquid phase. In yet another preferred embodiment, the solvent in which the matrix is dispersed can be volatile, and can be removed from the doping solution before molding the membrane by evaporation.
    [0044] [0044] Once the polybenzimidazole polymer is dissolved in the described solvent system, and optionally organic or inorganic matrices are added to the doping solution so that the matrices are well dispersed, it is molded on an appropriate porous support or substrate. The support may take the form of an inert porous material, which does not prevent the permeate from passing through the membrane and does not react with the membrane material, the molding solution, the freezing bath solvent or the solvents whose membrane will be permeate in use. Typical of such inert supports are metal mesh, sintered metal, porous ceramic, sintered glass, paper, non-dissolved porous plastic and woven or non-woven material. Preferably, the support material is a non-woven polymeric material, such as a polyester, polyethylene, polypropylene, polyetherether ketone (PEEK), polyphenylin sulfide (PPS), ethylene-chlorotrifluorethylene (Halar® ECTFE), or fiber material carbon.
    [0045] [0045] Following the molding operation, a part of the solvent can be evaporated under conditions sufficient to produce a dense, ultrafine layer, top "skin" on the polybenzimidazole membrane. Typical evaporation conditions suitable for this purpose include exposure to air for less than 100 seconds, preferably less than 30 seconds. In yet another more preferred embodiment, air is blown over the membrane surface at 15 ° C to 25 ° C for a duration of less than 30 seconds.
    [0046] [0046] The coagulation or sudden cooling medium may consist of water, alcohols, ketones or mixtures thereof, as well as other additives such as surfactants, for example, Triton® X-100 (available from Sigma-Aldrich UK Ltd (octylphenoxy polyethoxyethanol)). The conditions for effecting coagulation are well known to those skilled in the art.
    [0047] [0047] The asymmetric polybenzimidazole membranes formed can be washed according to the following techniques. Typically, a water-soluble organic compound, such as low molecular weight alcohols, and ketones, including, but not limited to, methanol, ethanol, acetone, isopropanol, methyl ethyl ketone, or mixtures thereof and mixtures with water can be used to removing residual molding solvent (eg DMAc) from the membrane. Alternatively, the membrane can be washed with water. The removal of residual molding solvent may require mixtures with successive washing in a sequential solvent exchange process. Both the efficiency of the membrane (solute rejection) and the permeate flow rate can be improved with the appropriate solvent exchange process.
    [0048] [0048] Crosslinking agents suitable for treating the polybenzimidazole polymer described in US 4,666,996, US 6,986,844, US 4,734,466, 4,020,142 and US, are all incorporated herein. These include alkyl halides, divinyl sulfones and strong polyfunctional organic acids.
    [0049] [0049] Multifunctional alkyl halides include those containing at least two halide substituents, and with the general structure:
    [0050] [0050] Other suitable cross-linking agents include divinyl sulfones with the general formula:
    [0051] [0051] Strong polyfunctional organic acids suitable for use in the present invention include carboxylic acids, sulfonic acids, sulfuric acid or phosphoric acid. Representative examples are perfluoroglutaric acid, benzene hexacarboxylic acid, benzene pentacarboxylic acid, 1,2,3,4-benzenotetracarboxylic acid, 1,2,3,5-benzenotetracarboxylic acid, 1,2,4,5-benzenotetracarboxylic acid, 1, 3,5- benzenotricarboxylic acid, dibromo succinic acid, polyacrylic acid, 1,4,5,8-naphthalene tetra-carboxylic acid, 2,6-naphthalenedisulfonic acid, aryl-sulfonic acids, aryl-sulfinic acids, aryl-phosphonic acids, aryl-phosphonic acids . Suitable solvents for cross-linking polybenzimidazole using strong polyfunctional organic acids are known to those skilled in the art and include glacial acetic acid.
    [0052] [0052] The cross-linking agent can be dissolved in a solvent to form a cross-linking solution. The solvent can be an organic solvent chosen from ketones, ethers, alcohols, acids or any solvent that dissolves the crosslinking agent. In a preferred embodiment, the solvent in the crosslinking solution will also swell the asymmetric membrane to allow good penetration of the crosslinking agent into the membrane.
    [0053] [0053] The solvent used to dissolve the alkyl halide must not react with the alkyl halide and must not dissolve the non-crosslinked PBI membrane. Preferred solvents include ketones, such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and pentanone, and ethers, such as isopropyl ether and butyl ether.
    [0054] [0054] The solvent used to dissolve divinylsufone can optionally also comprise a strong base catalyst, including alcohol metal hydroxides, such as sodium and potassium hydroxide, alcohol metal alkoxides having alkyl of one to six carbon atoms, such as sodium methoxide, sodium ethoxide, and alkyl aryl amine hydroxides, such as especially preferred benzyl trimethyl ammonium hydroxide. The base catalyst is generally added in amounts in the range of about 5 percent to 150 percent based on the total weight of the divinyl sulfone that is added. The preferred range is about 25 to about 50 weight percent.
    [0055] [0055] The concentration of the cross-linking agent in the cross-linking solution can be adjusted with respect to the amount of asymmetric polybenzimidazole membrane to be added per unit volume of solution, in order to control the extent of cross-linking that occurs, so that The ratio between the reactive groups in the crosslinking agent and the hydrogen amine groups of polybenzimidazole on the treated membrane is in the range of 0.01 to 100, preferably in the range of 0.01 to 10, and even more preferably in the range of 0.1 to 5.
    [0056] [0056] The time for crosslinking can vary between 0.01 and 120 hours, more preferably between 0.5 and 60 hours. The cross-linking temperature can vary between 0 ° C and the boiling point of the solvent, preferably between 0 ° C and 150 ° C, even more preferably between 50 ° C and 120 ° C.
    [0057] [0057] The asymmetric membrane is then conditioned by contacting the membrane with a conditioning agent, dissolved in a solvent to impregnate the membrane. The conditioning agent is a low volatility organic liquid. The conditioning agent can be chosen from synthetic oils (for example, polyolefin oils, silicone oils, polyalphaolefin oils, polyisobutylene oils, synthetic wax isomerate oils, ester oils and aromatic alkyl oils), mineral oils ( including oils refined in hydro-processed mineral oils and solvents and petroleum wax isomerate oils), vegetable fats and oils, higher alcohols (such as decanol, dodecanol, heptadecanol), glycerols, and glycols or derivatives thereof (such as polypropylene glycols, polyethylene glycols, polyalkylene glycols or derivatives thereof). Suitable solvents for dissolving the conditioning agent include alcohols, ketones, hydrocarbons, aromatics, or mixtures thereof. The use of a conditioning agent according to the invention allows an appropriate pore structure to be maintained in a dry state, and produces a flat sheet membrane with improved flexibility and handling characteristics. Before use, the conditioning agent must be washed from the membrane, that is, the conditioning agent of the present invention has the purpose of maintaining the desired membrane structure to preserve the performance characteristics when the membrane is in the dry state, and this is not a component of the functional membrane when used for the purpose of solvent nanofiltration. This contrasts the conditioning agents of the present invention with the agents that become part of the functional membrane.
    [0058] [0058] After treatment with the conditioning agent, the membrane is typically air-dried under ambient conditions to remove residual solvent.
    [0059] [0059] Heat treatment can also be used to increase rejection by the solute membrane. After the conditioning step, the membrane can be heated to between 150 ° C and 300 ° C, for between 1 minute and 2 hours.
    [0060] [0060] The membranes of the present invention can be used for nanofiltration operations, particularly in organic solvents. By the term "nanofiltration" is meant a membrane process that will allow the passage of solvents while delaying the passage of larger solute molecules, when a pressure gradient is applied across the membrane. This can be defined in terms of rejection of the Ri membrane, a common measure known to those skilled in the art and defined as:
    [0061] [0061] The term "solvent" will be well understood by the skilled reader and includes an organic or aqueous liquid with a molecular weight less than 300 Daltons. It is understood that the term solvent also includes a mixture of solvents.
    [0062] [0062] As a non-limiting example, solvents include aromatics, alkanes, ketones, glycols, chlorinated solvents, esters, ethers, amines, nitriles, aldehydes, phenols, amides, carboxylic acids, alcohols, furans, and dipolar aphotic solvents , water, and mixtures thereof.
    [0063] [0063] As a non-limiting example, specific examples of solvents include toluene, benzene, xylene, styrene, anisol, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, dichloroethane, methyl acetate, ethyl acetate, butyl acetate, methyl ether ketone (MEK), methyl iso butyl ketone (MIBK), acetone, ethylene glycols, ethanol, methanol, propanol, butanol, hexane, cyclohexane, dimethoxyethane, methyl tert-butyl ether (MTBE), diethyl ether, adiponitrile , N, N-dimethylformamide, dimethyl sulfoxide, N, N dimethylacetamide, dioxane, nitromethane, nitrobenzene, pyridine, carbon disulfide, tetrahydrofuran, methyltetrahydrofuran, N-methyl-pyrrolidone, acetonitrile, water, and mixtures thereof.
    [0064] [0064] The membranes of the present invention are particularly suitable for nanofiltration operations in which the solvent is strongly acidic or basic, or where the feed stream contains components which are strongly acidic or basic.
    [0065] [0065] The term "strongly acidic" is used here to refer to a compound that has a pKa less than 5. The term "strongly basic" is used here to refer to a compound that has a pKa greater than 9 The strongly acidic or basic compound can be a solvent and / or a compound, dissolved in a solvent.
    [0066] [0066] As a non-limiting example, specific strongly basic solvents include amines, alkanolamines in particular, alkyl amines and polyamines, such as alkyl diamines, alkyl triamines, piperidine and derivatives including alkylated piperidine, pyridine and alkyl pyridines including alkyl, dialkyl and trialkyl pyridines, and including ethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monomethylamine, mimethylamine trimethylamine, monoethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, mono-n-propylamine, di-n-propylamine, tri-n-propylamine, tri-n-propylamine, tri butylamine, tri-n-butylamine, cyclohexylamine, dicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, pentamethyl dipropylenetriamine, tetramethyldipropylene triamine, benzildimethylamine, tetramethylbis (aminoethyl) ether. N, N-dimethyl-2 (2-amino-ethoxy) ethanol, 3-amino-propanol, N-ethylmethylamine, 2-ethoxy-ethylamine Ν, Ν-diethyl hydroxylamine, N-ethyl-N- (1,2-dimethylpropyl ) amine, diisopropylmethylamine, 2-ethylhexylamine, dimethylbutyl amine, 3-methoxypropylamine, 3- (2-ethylhexoxy) -1-propanamine, methylaminopropylamine, dimethylaminopropylamine, methoxypropylamine, 3-ethoxy propylamine, Ν, Ν, Ν, Ν, Ν , dimethylisopropylamine, bis-2-ethylhexylamine, diethylmethylamine, N-methylisopropylamine, dibenzyl hydroxylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methylldiethanolamine, monomethylethanolamine, 2 - (2-amino-ethoxy) ethanol, amine, polyoxyalamine ; monopropanol, N-methylmorpholine, N-ethylmorpholine, N-methylmorpholine oxide, aminopropylmorpholine, quinoline, and alcohol solutions of metal alkoxides having 1-6 carbon atoms in the alkyl group, such as sodium methoxide, sodium ethoxide, and hydroxides alkyl aryl amine such as the particularly preferred benzyl trimethyl ammonium hydroxide.
    [0067] [0067] As a non-limiting example, highly acidic specific solvents include carboxylic acids and derivatives thereof, incorporating trifluoro acetic acid and acetic acid.
    [0068] [0068] Solvent can be understood as meaning solvents, acidic solvents or basic solvents and their mixtures.
    [0069] [0069] The "solute" will be well understood by the skilled reader and includes an organic molecule present in a liquid solution comprising a solvent and at least one solute molecule such that the weight fraction of the solute in the liquid is less than the weight fraction of the solvent, and where the molecular weight of the solute is at least 20 g mol-1 higher than that of the solvent.
    [0070] [0070] The membrane of the present invention can be configured according to any of the models known to those skilled in the art, such as plate and frame, wrap and tube, spiral-wound and drawings derived therefrom.
    [0071] [0071] The following Examples illustrate the invention.
    [0072] [0072] In Examples 1-4, on a laboratory scale a cross-flow nanofiltration unit was used with four cross-flow cells. The membrane discs, with an active area of 14 cm2, were cut from flat sheets and placed in four cross-flow cells in series. A feed solution consisting of <1% by weight of the test solutes was loaded into a 5 L feed tank and recirculated at a flow rate of 1.5 L min-1, using a diaphragm pump (Hydra- Cell, Wanner, US). Pressure in the cells was generated using a back pressure regulator, which was located downstream from a pressure calibrator. The pressure drop across the four cells was measured to be less than 0.5 bar (50 kPa). The liquid recirculation was maintained at 30 ° C by a heat exchanger. During the start, the conditioning agent was removed by recirculating pure solvent for one hour, without applying any pressure and discarding the initial permeate. During the operation, permeate samples were collected from individual sampling openings for each cross flow cell and the retentate a sample was collected from the feed tank. The preconditioning of the membranes was necessary to reduce the effect of compaction to achieve steady-state flows and rejections. The solvent flow Nv was calculated from the equation:
    [0073] [0073] A feed solution consisting of a homologous series of styrene oligomers was used to obtain the MWCO curve during nanofiltration with polystyrene solutes. The styrene oligomer mixture contained a mixture of 1 g of PS580 and PS 1050 (purchased from Polymer Labs, UK) and 0.1 g of α-methylstyrene dimer (purchased from Sigma Aldrich, UK). The styrene oligomers were all totally soluble in the tested solvents at this concentration EXAMPLE 1
    [0074] [0074] The polybenzimidazole polymer was synthesized as follows.
    [0075] [0075] 625 g of polyphosphoric acid (PPA) were weighed in a 3-neck, 1-liter round-bottom flask at room temperature followed by fixing the flask to the top shaking set equipped with an oil bath. The oil was heated to 155 ° C, at about 125 ° C the addition of tetraamine was started with a constant flow of dry nitrogen. The addition was very slow, in such a way that it lasted more than 15 minutes. Upon completion of the addition of tetraamine, the temperature was further raised to 170 ° C and kept constant for 45 minutes followed by addition of diacid. The reaction was kept under stirring for the next 4 hours at 170 ° C. After 4 hours the reaction temperature was then raised to 210 ° C for the next 2.5 hours, followed by 230 ° C for 2 hours. At the end of the reaction, the viscous polymer solution was poured into a large excess of water, in the form of fine continuous fiber.
    [0076] [0076] The crude PBI fibers were crushed into fine pieces and later processed with a sodium bicarbonate solution to neutralize the phosphoric acid. The chopped fine fibers were crushed in the mixture to make fine powder. The fine polymer powder was washed with water followed by acetone and dried in a vacuum oven overnight. The dry polymer was further purified by dissolving the polymer in hot dimethylacetamide (DMAc), followed by centrifugation and precipitation in large excess of water. The precipitated polymer was washed with water 3 times and crushed into a fine powder. The fine polymer powder was soaked in acetone to replace the water absorbed in the polymer followed by drying in a vacuum oven at 120 ° C overnight.
    [0077] [0077] The polymer, which had been synthesized, was characterized as follows:
    [0078] [0078] The synthesized PBI was characterized by GPC for determining the molecular weight, as shown below in Table 1:
    [0079] [0079] The intrinsic viscosity of the polymer was determined by the diluted solution method using DMAc as a solvent at 30 ° C, and is shown in Figure 1.
    [0080] [0080] The membranes were manufactured from the polybenzimidazole polymer as follows:
    [0081] [0081] The membranes were formed using the prepared polymer. The composition of the doping solution was as given in Table 2. The high molecular weight of the starting polymer limited the concentration of the doping solution to 15% by weight - 17% by weight of the polymer. The heavy amount of DMAc was taken in a flask and heated to 80 ° C first, once the solvent temperature reached the desired temperature, the purified polymer was added to the flask. Dissolution of the polymer at an elevated temperature resulted in a highly viscous polymer solution without any residue. After complete dissolution of the polymer, the heating was removed to cool the doping solution. Once the doping solution was cooled, it was transferred to a 50 ml centrifuge tube to centrifuge the doping solution at 7000 rpm for 30 minutes. The doping solution was left to stand overnight to allow any air bubbles to be removed. Details of membrane molding conditions are also presented in Table 2.
    [0082] [0082] The coding used to designate the membranes was as follows, that is, 15PBI-1 / 0-0-UX-0 refers to
    [0083] [0083] The doping solution was used to mold 250 μm thick films on a polypropylene lining material using an adjustable molding knife on an automatic film applicator (Braive Instruments). The solvent was allowed to evaporate from the surface of the film at controlled time intervals, after which the film was immersed, in parallel with the surface, in a precipitation water bath at room temperature. The membranes were then immersed in isopropanol solvent exchange baths, to remove residual DMAc and water. After that, the membrane was immersed in an IPA / polyethylene glycol 400 bath (40/60, v / v%) to prevent it from drying out. The membranes were then air dried to remove excess solvent.
    [0084] [0084] The membranes were then tested for flow and rejection in cross flow nanofiltration. The data obtained in these tests are shown in Figures 2-8. EXAMPLE 2
    [0085] [0085] The membranes were formed as in Example 1 above and then cross-linked as follows.
    [0086] [0086] The membranes were immersed in a methyl isobutyl ketone bath and crosslinker (dibromobutane) for 12 hours at 60 ° C. The membrane was then removed from the crosslinking bath and washed with IPA to remove any residual crosslinking agent. After that, the membrane was immersed in an IPA / polyethylene glycol 400 bath (40/60, v / v%) to prevent it from drying out. The membranes were then air dried to remove excess solvent. The dry membrane was fixed to the glass plate with the help of PVC tape and heated in an oven at 100 ° C for 1 h.
    [0087] [0087] These cross-linked membranes were then tested by flow and rejection, as described above. The data obtained in these tests are shown in Figures 9 and 10. EXAMPLE 3
    [0088] [0088] Cross-linked polybenzimidazole membranes were prepared as in Example 3 and were immersed in dilute solutions of monoethanolamine and trifluoroacetic acid, and maintained at 30 ° C. The membranes were monitored for stability over 4 weeks. No changes in the appearance or properties of the membranes were observed. EXAMPLE 4
    [0089] [0089] Cross-linked polybenzimidazole membranes were prepared as in Example 2. These were used to test the nanofiltration of a solution containing a photo-resistant material supplied by TOKYO OHKA KOGYO EUROPE BV, catalog number TFR 970, dissolved in 1 g L-1 in a mixture of butyl diglycol: monoethanolamine: water (60:20:20) The membranes showed a positive rejection for the photoresistor (PR), as shown in Table 3 below:
    * MWCO of the membrane based on standard OS rejection analysis after 24 hours of filtration
    权利要求:
    Claims (15)
    [0001]
    Process to form an asymmetric cross-linked polybenzimidazole membrane covered with skin for organic solvent nanofiltration, characterized by the fact that it comprises the steps of: (a) preparing a polybenzimidazole doping solution comprising: (i) a polybenzimidazole polymer, and (ii) a solvent system for said polybenzimidazole that is miscible with water; (b) molding a film of said doping solution onto a support substrate, wherein the support substrate is a non-woven polymeric material selected from the group consisting of polyester, polyethylene, polypropylene, polyetherether ketone, polyphenylin sulfide and ethylene-chlorotrifluorethylene ; (c) let the doping solution evaporate for a period of evaporation, and then immerse the molded film on the support substrate in a coagulation medium; (d) treating the resulting asymmetric membrane with a solvent comprising one or more of the crosslinking agents for polybenzimidazole; (e) treating the asymmetric membrane with a conditioning agent, wherein the polybenzimidazole doping solution in step (a) comprises about 14% to about 18% by weight of the polybenzimidazole polymer; and step (d) is conducted at a temperature of about 50 ° C to about 120 ° C.
    [0002]
    Process according to claim 1, characterized in that it additionally comprises step (f) drying the membrane.
    [0003]
    Process according to claim 1 or 2, characterized in that the process additionally comprises the step of heating the membrane to about 150 ° C or higher.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that the polybenzimidazole polymer is poly (2,2 '- [m-phenylene]) - 5,5'-bis-benzimidazole.
    [0005]
    Process according to any one of claims 1 to 4, characterized in that the polybenzimidazole doping solution further comprises a viscosity enhancer in amounts of up to 10% by weight of said doping solution.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the polybenzimidazole doping solution further comprises a vacuum suppressor used in amounts up to 5% by weight of said polybenzimidazole doping solution.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that the crosslinking agent is chosen from multifunctional alkyl halides, divinyl sulfones, perfluoroglutaric acid, hexacarboxylic benzene acid, benzene pentacarboxylic acid, 1,2,3, 4-benzenotetracarboxylic acid, 1,2,3,5-benzenotetracarboxylic acid, 1,2,4,5-benzenotetracarboxylic acid, 1,3,5-benzenotricarboxylic acid, dibromo succinic acid, polyacrylic acid, 1,4,5,8 -naphthalenetetracarboxylic acid, 2,6-naphthalenedisulfonic acid, aryl-sulfonic acids, aryl-sulfinic acids, aryl-phosphonic acids, aryl-phosphonic acids.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the cross-linking agent is dissolved in a solvent chosen from ketones, ethers, carboxylic acids and alcohols.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the amount of crosslinking agent used to treat a polybenzimidazole membrane is adjusted so that the reactive groups on the crosslinking agent and hydrogen polybenzimidazole amine groups in the treated membrane are in the range of 0.1 to 10.
    [0010]
    Process according to claim 7, characterized in that the multifunctional alkyl halide is a di- or trifunctional alkyl halide.
    [0011]
    Process according to any one of claims 1 to 10, characterized in that the polybenzimidazole doping solution comprises one or more solvents chosen from N-methyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, N, N -dimethylacetamide, 1,4 dioxane and gamma-butyrolactone.
    [0012]
    Process according to any one of claims 1 to 11, characterized in that the conditioning agent is selected from one or more of synthetic oils, mineral oils, vegetable fats and oils, higher alcohols, glycerols and glycols.
    [0013]
    Asymmetric film membrane of cross-linked polybenzimidazole completely covered with skin, characterized by the fact that it is obtained by the process as defined in any one of claims 1 to 12.
    [0014]
    Use of the asymmetrical cross-linked polybenzimidazole membrane covered with skin as defined in claim 13, characterized by the fact that it is for the nanofiltration of a feed stream solution comprising an organic solvent and dissolved solutes.
    [0015]
    Use according to claim 14, characterized in that the feed stream solution comprises a solvent or compound having a pKa less than 5, or a solvent or compound having a pKa greater than 9.
    类似技术:
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    同族专利:
    公开号 | 公开日
    CN103079685B|2016-03-30|
    AU2011281326A1|2013-02-21|
    WO2012010886A1|2012-01-26|
    EA201390135A1|2013-10-30|
    BR112013001380A2|2016-05-17|
    JP6055406B2|2016-12-27|
    AU2011281326B2|2015-03-26|
    MY171822A|2019-10-31|
    UA115963C2|2018-01-25|
    CA2805780C|2021-08-10|
    JP2013532578A|2013-08-19|
    EP2595733A1|2013-05-29|
    SG187556A1|2013-03-28|
    CA2805780A1|2012-01-26|
    ES2870873T3|2021-10-27|
    MX2013000770A|2013-07-05|
    KR102101707B1|2020-04-20|
    GB201012080D0|2010-09-01|
    KR20140085372A|2014-07-07|
    CN103079685A|2013-05-01|
    EP2595733B1|2021-04-14|
    IL224282A|2018-01-31|
    EA027868B1|2017-09-29|
    US20130118983A1|2013-05-16|
    CL2013000167A1|2013-12-06|
    US20170165614A1|2017-06-15|
    US10328396B2|2019-06-25|
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    CN111514768B|2020-05-11|2021-07-13|苏州大学|Solvent-resistant polymer nanofiltration membrane as well as preparation method and application thereof|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-01-14| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-07-07| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GB1012080.6|2010-07-19|
    GBGB1012080.6A|GB201012080D0|2010-07-19|2010-07-19|Asymmetric membranes for use in nanofiltration|
    PCT/GB2011/051361|WO2012010886A1|2010-07-19|2011-07-19|Asymmetric membranes for use in nanofiltration|
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