CN1110354C - Polyamide reverse osmosis composite film and its producing method - Google Patents
Polyamide reverse osmosis composite film and its producing method Download PDFInfo
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- CN1110354C CN1110354C CN99125639A CN99125639A CN1110354C CN 1110354 C CN1110354 C CN 1110354C CN 99125639 A CN99125639 A CN 99125639A CN 99125639 A CN99125639 A CN 99125639A CN 1110354 C CN1110354 C CN 1110354C
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- 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
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- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The present invention provides a polyamide reverse osmosis composite film having two properties of good osmosis capacity and high desalination rate and a producing method thereof. A water solution containing multifunction base amine, a polar solvent, at least a quaternary ammonium salt and at least an amino amine salt compound is in reaction with an organic solution containing an amine reaction compound which is selected from multifunction base acyl halide, multifunction base sulfonic halide and multifunction base isocyanate and has amino-group reaction, and then a polyamide film is formed on a porous supporting layer.
Description
The invention relates to polyamide composite film and manufacture method thereof.
Utilize various films solute and the solvent in the separation solution selectively, secondary filter film, ultrafiltration membrane are arranged, also have reverse osmosis membrane as such film.
For with salt solution, seawater fresh waterization, a large amount of in industry and domestic. applications, use the method for reverse osmosis membrane extremely useful.The desalination of using this reverse osmosis membrane to carry out salt solution or seawater is handled, be that salt solution etc. is passed through reverse osmosis membrane filtration, removal can not be by the salinity of film, the ion that dissociates or particle, what pass purifies waste water, at this moment, solute concentration in the water supply is high more, and osmotic pressure just increases, and the pressure that is utilized in the reverse osmosis process is also high more.
The commercial reverse osmosis membrane that utilizes when salt solution or seawater are carried out the fresh water processing, as the performance of reverse osmosis membrane, requires the desalination rate to be higher than 97%.And require to apply lower pressure, just can handle a large amount of water, and have very high infiltration capacity.
Ignore this special circumstances of infiltration capacity except only paying attention to the desalination rate, the general infiltration capacity that requires during to seawater, applies under the 800psi pressure, is 10 gallons/foot
2My god when (gfd), salt solution, apply under the 220psi pressure, more than 15gfd, in fact, under the situation of salt solution, require more than the 22gfd.
The formation of reverse osmosis membrane generally is the aramid layer that forms the film shape on the porous supporting mass, and the manufacturing of this aramid layer is to form by the interfacial polymerization with polyfunctional basic amine and multiple functional radical acyl halide.
Manufacture method as this reverse osmosis composite membrane; in United States Patent (USP) No. 4277344 (registration on July 7th, 1981); Cadotte discloses a kind of manufacture method of aromatic polyamide film; he uses has the aromatic amine of 2 primary amino radicals at least and has the halid interfacial polymerization of aromatic acyl of 3 acyl halide bases at least and prepare; in detail; be that the m-phenylene diamine (MPD) aqueous solution is coated on the porous polysulfones supporting mass surface; after removing the m-phenylene diamine (MPD) solution of going up surplus in the surface; making with " FREON " TF (trichorotrifluoroethane) is that trimesic acid chloride (the ト リ メ ゾ イ Le Network ロ ラ イ De) solution of solvent carries out interfacial polymerization in the contact of the surface of supporting course (is 10 seconds the time of contact of interfacial polymerization again; but this promptly finished reaction in 1 second); polysulfones/polyamide complex of generating at air drying, is obtained reverse osmosis composite membrane.
The infiltration capacity and the desalination rate of polyamide reverse osmosis composite film will be improved, and the chemical resistance that improves film has been carried out a large amount of research as purpose to the composite membrane manufacture method of using various additives.
As an example; Tomashke discloses a kind of method of utilizing interfacial polymerization to make reverse osmosis composite membrane in No. the 4872984th, United States Patent (USP); comprising that (A) applies on fine porous property supporting mass contains the aromatic polyamine monomer that has two amino at least and the aqueous solution of amine salt; after forming solution layer; (B) organic solution that will contain amine reactive compound monomer, multiple functional radical acyl halide or their mixture that per molecule has 2.2 above acyl halide bases contacts with above-mentioned solution layer; after carrying out interfacial polymerization, (C) with the product drying.
The monomer that the disclosed above-mentioned amine salt of Tomashke is a monoamine, the preferably water soluble salt of strong acid and tertiary amine.Example as above-mentioned tertiary amine, trialkylamine, the N-alkyl ring grease shape amine of 1-methyl piperidine one class, N that Trimethylamine, triethylamine, tripropylamine one class are arranged, N-dimethylethyl amine and N, the N of N-diethylmethyl amine one class, N-dialkylamine, N, the N of N-dimethylethanolamine one class, N-dialkyl group monoethanolamine, two cyclic tertiary amine compounds of 3-quinine cyclol one class or their mixture.As above-mentioned amine salt, tetraalkylammonium hydroxide, and the hydroxide benzyl trialkyl ammonium of hydroxide benzyltrimethylammon.um, hydroxide benzyl triethyl ammonium ammonium, hydroxide benzyl tripropyl ammonium one class that tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide one class of quaternary ammonium salt are arranged, or their mixture.
In United States Patent (USP) No. 4983291 (registration on January 8th, 1991), people such as Chau disclose a kind of on the porous supporting mass, by the film of interface polymerization reaction acquisition.At length recorded and narrated manufacture method, coating contains the amine aqueous solution of the polyol of non-proton property polar solvent and acid acceptor on the porous supporting mass, in the above-mentioned aqueous solution,, contain the compound of a plurality of carbon numbers such as ethylene glycol, propane diols, glycerine and ethylene glycol of 0.1～50% as above-mentioned polyol.After removing the excess solution on the coating supporting mass; contact with the organic solution of polyacyl halide thing again and carry out interfacial polymerization (at this moment; in order fully to form product of polymerization; but proper extension time of contact); after the complex that generates handled with hydroxypolycarboxylic acid, polyamino alkylidene polycarboxylic acid, sulfonic acid, amine salt, amino acid, amino-acid salt, polymer acid, inorganic acid etc.; drying makes composite membrane.
In United States Patent (USP) No. 5576057 (registration on November 19th, 1996), people such as Hirose disclose a kind of method of making reverse osmosis composite membrane, and polyamide film is coated on the porous supporting mass.In detail, after the solution that comprises the steps: to contain at least two amino-compounds (A) is coated on the porous supporting mass, contact and prepare with (B) solution that contains the multiple functional radical hydracid, the numerical difference between of the solubility constant of solution (A) and solution (B) is 7～15 (cal/cm
3)
1/2As the solvent of above-mentioned solution (A), ethanol is for example arranged, propyl alcohol, butanols, the 1-amylalcohol, the 2-amylalcohol, uncle-amylalcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecyl alcohol, the 2-ethyl butanol, 2-Ethylhexyl Alcohol, octanol, cyclohexanol, tetrahydrofurfuryl alcohol, dimethyltrimethylene glycol, uncle-butanols, benzyl alcohol, 4-methyl-2-amylalcohol, 3-methyl-2-butanols, amylalcohol, allyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, TEG, propane diols, butanediol, pentanediol, the mixture of the alcohol and water of one class such as glycerine, or nitromethane, formamide, NMF, acetonitrile, dimethyl formamide, the nitrogen compound of one class such as ethyl-formamide and the mixture of water.
As solution (A), the example of the mixing ratio of water and solvent (weight ratio) when water and ethanol, is (50～90)/(50～10), (60～90)/(40～10) preferably.
In JP-A-2-187135 (No. the 4872984th, United States Patent (USP)), the salt that people such as Hirose disclose halogenation tetra-allkylammonium or trialkylamine and organic acid formation adds in the solution (A), can improve the absorbability of amine aqueous solution to supporting mass, accelerated reaction is easy to the formation of film.
In United States Patent (USP) No. 5614099 (registration on March 25th, 1997); people such as Hirose are disclosed to be the reverse osmosis composite membrane that is at least 55nm about the average surface roughness of aramid layer; have amino compound and have the reaction of acyl group acid functional group's multiple functional radical hydracid compound by making, and make this polyamide surface layer.In detail, disclosed be on porous polysulfones supporting mass with contain that m-phenylene diamine (MPD) solution contacts and after forming solution layer, contact with the trimesic acid chloride solution and react again, the film that generates is dry in drier, on supporting mass, form macromolecule membrane, subsequently, handle the surface of aramid layer again with quaternary ammonium salt, apply with organic cross-linked polymer again with positive electricity base.
People such as Hirose are open, are alcohols, ethers, ketone, ester class, halogenated hydrocarbons, sulfur-containing compound as the compound that adds in the solution (A), preferably have various amino, solubility constant is 8～14 (cal/cm
2)
1/2Compound.
In addition, the invention of relevant reverse osmosis membrane is also disclosed in people's such as the United States Patent (USP) No. 4761234 (registration on August 2nd, 1988) of the United States Patent (USP) No. 4950404 (registration on August 21 nineteen ninety) of Chau, Uemura, Fibiger United States Patent (USP) No. 4769148 (registration on September 6th, 1998).
The film of people such as relevant Cadotte invention has higher water permeability, good penetration amount and desalination rate comparatively speaking.And, aspect practical application, can be in order to save operating cost and to satisfy with higher salinity clearance, the low pressure of 120psi, handle the requirement of more good reverse osmosis membrane such as the performance of seawater etc. in a large number, also must do further research to the raising of infiltration capacity and desalination rate.In addition, film also is still waiting to improve to the resistance of chemical breakdown.
In view of above situation, the purpose of this invention is to provide a kind of polyamide reverse osmosis composite film and manufacture method thereof with high infiltration capacity and two kinds of good characteristics of high desalination rate.
The main points that can finish the relevant reverse osmosis membrane of the present invention of above-mentioned problem be make have polyfunctional basic amine, polar solvent, at least 1 quaternary ammonium salt and have the aqueous solution of the amine salt compound of 1 amino at least; be selected from multiple functional radical acyl halide, polyfunctional basic sulfonyl halide and the polyfunctional basic isocyanic ester with containing, and and amino organic solution with reactive amine reactive compound react and obtain.
Above-mentioned polyfunctional basic amine preferably is selected from least a kind compound in aromatic series primary diamines, alkane primary diamines, ring grease shape primary diamines, ring grease shape secondary diamine, the aromatic series secondary diamine.
Above-mentioned amine reactive compound is at least a kind of compound that is selected from a phenyl-diformyl halide, four phenyl-diformyl halide, the equal trigalloyl of benzene (the ト リ メ ゾ ィ Le) halide.
Above-mentioned polar solvent is alkyloxyalkanol, ethylene glycol derivative, propanediol derivative, alkanol, 1 preferably, a kind or above solvent in ammediol derivative, sulfoxide derivant, sulfone derivative, carbonitrile derivatives and the urea derivative.
Above-mentioned amine salt compound is preferably by the reactant of strong acid and multiple functional radical tertiary amine.
Above-mentioned polar solvent preferably uses and is selected from following a kind of solvent, above-mentioned ethylene glycol derivative, the triethylene glycol dimethyl ether is arranged, above-mentioned propanediol derivative, the propane diols butyl ether is arranged, or propylene glycol propyl ether, above-mentioned alkanol, the 1-amylalcohol is arranged, or 1-butanols, above-mentioned 1, the ammediol derivative, 2-ethyl-1 is arranged, the 3-hexylene glycol, above-mentioned sulfoxide derivant, tetramethylene sulfoxide is arranged, or butyl sulfoxide, or methylbenzene sulfoxide, or dimethyl sulfoxide (DMSO), above-mentioned sulfone derivative, the butyl sulfone is arranged, or sulfolane, above-mentioned urea derivative, have 1,3-dimethyl-2-imidazolidinone, above-mentioned combination polar solvent more than 2 kinds, 2-ethyl-1 is arranged, 3-hexylene glycol and dimethyl sulfoxide (DMSO), or diethylene glycol (DEG) hexyl ether and dimethyl sulfoxide (DMSO), or 2-ethyl-1,3-hexylene glycol and acetonitrile, or a kind of in alkoxyethanol and the dimethyl sulfoxide (DMSO).
Following percentage numerical value all is meant weight percent.
Be selected from following solvent, i.e. alkyloxyalkanol as what above-mentioned polar solvent preferably used: be 0.05～4% in the above-mentioned aqueous solution, the 1-amylalcohol: be 0.01～2% in the above-mentioned aqueous solution, the 1-butanols: be 0.01～0.3% in the above-mentioned aqueous solution, dimethyl sulfoxide (DMSO) is that 0.01-8%, sulfolane are 0.01～4% in the above-mentioned aqueous solution, alkyloxyalkanol in the above-mentioned aqueous solution: be 0.05-4% and dimethyl sulfoxide (DMSO): be the mixed solution of 0.01-8% in the above-mentioned aqueous solution in the above-mentioned aqueous solution.
The manufacture method of above-mentioned polyamide reverse osmosis composite film, preferably include following operation, the above-mentioned aqueous solution is coated on operation on the porous supporting course, makes above-mentioned solution layer contact with organic solution, form the operation of aramid layer and product is carried out dry operation on the porous supporting mass by interfacial polymerization.At this moment the above-mentioned aqueous solution, making pH by the interpolation acid acceptor is 7～13.
The manufacture method of above-mentioned polyamide reverse osmosis composite film, preferably include following operation, that is, the 1st aqueous solution that will contain above-mentioned polar solvent and above-mentioned amine salt compound is coated on and forms the operation of the 1st solution layer on the porous supporting course, coating contains the 2nd solution of above-mentioned polyfunctional basic amine to form the operation of the 2nd solution layer on the 1st solution layer.Above-mentioned solution layer is contacted with above-mentioned organic solution, on the porous supporting course, form the operation of aramid layer and product is carried out dry operation by interfacial polymerization.
The manufacture method of above-mentioned polyamide reverse osmosis composite film, preferably include following operation, promptly, to contain form the operation of the 1st solution layer on the applying porous property of the 1st aqueous solution supporting course of above-mentioned polar solvent, coating contains above-mentioned polyfunctional basic amine and above-mentioned amine salt compound on the 1st solution layer the 2nd solution with the operation that forms the 2nd solution layer, above-mentioned solution layer is contacted with above-mentioned organic solution, on the porous supporting course, form the operation of aramid layer by interfacial polymerization, and product is carried out the operation of drying.
Below specify the present invention:
The present invention provides a kind of novel reverse osmosis composite membrane; this reverse osmosis composite membrane is by constituting with the lower part; promptly; (A) the porous supporting mass and (B) (a) contain the aqueous solution of polyfunctional group amine, more than one polar solvent and amine salt compound; reach the amine reactive compound that (b) is selected from from multiple functional radical acyl halide, multiple functional radical sulfonyl halide and polyfunctional basic isocyanic ester; react, on above-mentioned supporting mass, form PA membrane.In above-mentioned amine salt compound, use compound with at least 1 quaternary ammonium salt and at least 1 amino.
Used the fine porous property supporting course of being made by general macromolecular material in the above-mentioned porous supporting course, though it is not had particular determination, what preferably use is its aperture, the supporting course than macropore that infiltration water is passed through fully.Yet when surpassing 500nm, film as thin as a wafer can subside between the space, is difficult to obtain needed open and flat film, so the aperture of above-mentioned porous supporting course is preferably 1～500nm.
For the material of above-mentioned porous supporting course, main, preferably use various halogenation macromolecules such as polysulfones, polyethers, poly-imines, polyamide, polypropylene or Kynoar.In addition, also can use the material of putting down in writing in the above-mentioned list of references.
Though the thickness to above-mentioned porous supporting course does not have special provision, be preferably 25～125 μ m, be more preferably 40～75 μ m.
For above-mentioned polyfunctional basic amine, the preferred use has compound amino more than 2.This amino-compound is primary amino radical or secondary amino group preferably, is more preferably primary amino radical.Among the present invention, polyfunctional basic amine is not had special provision, can use the mixture more than a kind or 2 kinds.
Example for above-mentioned polyfunctional basic amine, as the aromatic series primary diamines, m-phenylene diamine (MPD), p-phenylenediamine (PPD) are arranged or be substituent m-phenylene diamine (MPD) derivative, p-phenylene diamine derivative etc. with the alkoxyl of the alkyl of methyl or ethyl one class, methoxy or ethoxy one class, hydroxyalkyl, hydroxyl, halogen atom etc.In addition, also have with 1,3-propane diamine or 1, the 3-propane diamine is a basic framework, have the alkane diamines of N-alkyl or N-aryl, the cyclohexanediamine of ring grease shape primary diamines, the piperazine or the bridged piperazine derivatives of ring grease shape secondary diamine, the N of aromatic series secondary diamine, N '-dimethyl-1,3-phenylenediamine, N, N-diphenyl ethylene diamine, benzidine, dimethylphenylene diamine or dimethylphenylene diamine derivative etc.In addition, the polyamines that also can use other aspects to obtain.In the present invention, the aromatic series primary diamines is preferred, and m-phenylene diamine (MPD) is better.
The concentration of above-mentioned polyfunctional basic amine preferably is 0.1～20% in the above-mentioned aqueous solution, more preferably 0.5～8%.The pH of the above-mentioned aqueous solution is adjusted to 7～13.Regulate for pH, preferably add 0.001～5% alkaline acid neutralizing agent,, except trialkylamine, also have alkali-metal hydroxide, carboxylate, carbonate, borate, phosphate etc. as above-mentioned acid acceptor.
For above-mentioned amine salt compound, can use at least 1 quaternary ammonium salt and the compound that has 1 amino at least.Above-mentioned amino is uncle's amino preferably.
Above-mentioned amine salt compound preferably has 3 or 4 nitrogen-atoms, the compound of alkyl, ring grease shape alkyl, benzyl, alkoxyl and/or hydroxyalkyl, and therefore, amine salt compound is quaternary ammonium salt preferably, or the reaction product of strong acid and tertiary amine.
Example as above-mentioned quaternary ammonium salt, the hydroxide benzyl trialkyl ammonium that tetraalkylammonium hydroxide, hydroxide benzyltrimethylammon.um, hydroxide benzyl triethyl ammonium ammonium and hydroxide benzyl tripropyl ammonium one class of tetramethyl ammonium hydroxide and tetrapropylammonium hydroxide one class are arranged, or their mixture etc.
Amine salt compound, when the reaction product of strong acid and tertiary amine, above-mentioned tertiary amine preferably uses any in monofunctional tertiary amine or the multiple functional radical tertiary amine.
As above-mentioned strong acid example, methanesulfonic acid, toluenesulfonic acid (ト Le エ Application ス Le ホ Application), camphorsulfonic acid, ethyl sulfonic acid, benzene sulfonic acid, are in addition arranged, also have aromatic series or aliphatic sulfonic, trifluoracetic acid, nitric acid, hydrochloric acid, sulfuric acid or their mixture etc., preferably methanesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, ethyl sulfonic acid, benzene sulfonic acid.
As above-mentioned monofunctional tertiary amine, N-alkyl ring grease shape amine, N such as the trialkylamine of one class such as Trimethylamine, triethylamine, tripropylamine and 1-methyl piperidine are arranged, N '-dimethylethyl amine, N, N '-diethylmethyl amine or N, the N of N '-dimethylethanolamine etc., N '-dialkyl group monoethanolamine etc.
As with the above-mentioned multiple functional radical tertiary amine of strong acid reaction, preferably use 1,4-diazabicylo [2.2.2] octane, (DABCD), 1,8-diazabicylo [5.4.0] hendecane-7-alkene, N, N, N ', N '-tetramethyl-1,3-butanediamine (TMBD), N, N, N ', N '-tetramethyl-1, the 6-hexamethylene diamine, N, N, N ', N ', N " five methyl diethylentriamine; 1; 1,3,3-TMG (TMGU); N; N, N ', N '-tetramethylethylenediamine (TMED); as the imidazoles substituent, have 1,2-methylimidazole (MDI), 1-alkyl imidazole substituent and in addition is at U.S.N.09/991, the imidazoles substituent of type described in 110, or their mixture etc.For this multiple functional radical tertiary amine, preferred use can not form high molecular monomer.
When using above-mentioned multiple functional radical tertiary amine and strong acid reaction forming amine salt compound, have n (n greater than 2, as follows) the multiple functional radical tertiary amine of uncle's amino and the mol ratio of strong acid, preferably below the 1:(1, n is following) (U.S.S.N.09/067,891, address in the list of references).Be more preferably more than the 1:(1,0.95n is following), more than the 1:(1,0.9n is following) particularly good.
Among the present invention, as the reason that can obviously improve infiltration capacity, can think the space binder of quaternary ammonium salt as PA membrane, and arbitrarily play a role, on the other hand, uncle's amino is as at polyfunctional basic amine (for example m-phenylene diamine (MPD)) with amine reactive compound (for example, the trimesic acid chloride) acidic nertralizer in the interface polymerization reaction, and work.By using such amine salt compound, have quaternary ammonium salt than use, and when not having the amine salt compound of uncle's amino relatively, improved infiltration capacity significantly.
The amine salt compound that uses among the present invention, being preferably formed in the above-mentioned aqueous solution is 0.3～12%, is more preferably 0.6～8%.
As previously mentioned, in the aqueous solution, the polar solvent that contains more than one will be added in above-mentioned polyfunctional basic amine and the above-mentioned amine salt compound.For this polar solvent preferably use be selected from following, promptly, alkyloxyalkanol, ethylene glycol derivative, propanediol derivative, alkanol, 1, ammediol derivative, sulfoxide derivant, sulfone derivative, carbonitrile derivatives, urea derivative or their mixture.
As the example of above-mentioned alkyloxyalkanol, 2-methyl cellosolve, cellosolvo, 2-propoxyl group ethanol are arranged.
As above-mentioned ethylene glycol derivative example, diethylene glycol (DEG)-tert-butyl methyl ether, diethylene glycol (DEG) hexyl ether, triglyme are arranged, as above-mentioned propanediol derivative example, propane diols butyl ether, propylene glycol propyl ether are arranged.
As above-mentioned alkanol, 1-amylalcohol, 1-butanols are arranged, as above-mentioned 1, the ammediol derivative has 1,3-heptandiol, 2-ethyl-1,3-hexylene glycol, 1,3-hexylene glycol, 1,3-pentanediol.
As above-mentioned sulfoxide derivant, tetramethylene sulfoxide, butyl sulfoxide, methylbenzene sulfoxide, dimethyl sulfoxide (DMSO) are arranged, as above-mentioned sulfone derivative, sulfolane, butyl sulfone are arranged, as above-mentioned carbonitrile derivatives, acetonitrile, propionitrile are arranged, as above-mentioned urea derivative, have 1,3-dimethyl-2-imidazolidinone.
As the polar solvent more than 2 kinds, can use 2-ethyl-1,3-hexylene glycol and dimethyl sulfoxide (DMSO); Diethylene glycol (DEG) hexyl ether and dimethyl sulfoxide (DMSO); 2-ethyl-1,3-hexylene glycol and acetonitrile; Alkyloxyalkanol and dimethyl sulfoxide (DMSO) etc.
Above-mentioned polar solvent, being preferably formed in the above-mentioned aqueous solution is 0.01～8%.Above-mentioned concentration, though lower than disclosed polar solvent concentration in No. the 5576057th, the United States Patent (USP), obtained in the present invention on an equal basis or excellent results more.
As polar solvent, when using alkyloxyalkanol, preferably be 0.05～4% in the above-mentioned aqueous solution.When using the 1-amylalcohol, be 0.01～2% in the preferred above-mentioned aqueous solution, when using the 1-butanols, the preferably above-mentioned aqueous solution is 0.01～3%.When using the diethylene glycol (DEG) hexyl ether, in the aqueous solution, be 0.01～0.3% preferably, be more preferably 0.01～8% in the aqueous solution.Using 2-ethyl-1, during the 3-hexane diol, is 0.1～1% in the above-mentioned aqueous solution preferably, when using dimethyl sulfoxide (DMSO), in the above-mentioned aqueous solution, be 0.01～8% preferably, be more preferably 0.1～7%: when using sulfolane or methylbenzene sulfoxide, in the above-mentioned aqueous solution, be 0.01～4% preferably.When using the butyl sulfone, in the above-mentioned aqueous solution, be 0.01～0.5% preferably.
When using the mixed solution of alkyloxyalkanol and dimethyl sulfoxide (DMSO), preferably alkyloxyalkanol is that 0.05-4% and dimethyl sulfoxide (DMSO) are 0.01～8% mixed solutions in the above-mentioned aqueous solution.
The film that obtains according to the present invention as the reason that can obtain high infiltration capacity, can be thought the applied in any combination owing to above-mentioned amine salt compound and above-mentioned polar solvent, the improvement that can obviously improve infiltration capacity.That is, amine salt compound works as the space binder, and on the other hand, polar solvent is in the interstitial process of film heat supply, can think the effect of playing catalyst.
Among the present invention,, can use at least a kind of compound that is selected from multiple functional radical acyl halide, polyfunctional basic sulfonyl halide and the polyfunctional basic isocyanic ester as reacting the amine reactive compound that obtains with amine.And amine reactive compound preferably is selected from a kind or above compound in a phenyl-diformyl halide, four phenyl-diformyl halide, the equal tricarboxylic acid halide of benzene.
Embodiment
Below enumerate embodiment being described more specifically the present invention, but the present invention is because of following embodiment limits, can changes in the scope that context adapts and implement, any situation all is included in the technical scope of the present invention.
Embodiment 1
To on the thick nonwoven of 140 μ m, form the polysulfones supporting mass of fine porous property, contain 2.0% m-phenylene diamine (MPD) (MPD), 2.3% camphorsulfonic acid (camphorsulfonlc acid, CSA), 40 seconds of dipping in the aqueous solution of 1.1% triethylene amine (TEA) and 2.0%2-butyl cellosolve (BE).After removing the organic solution that is coated in surplus on the supporting mass, dipping is 1 minute in the 0.1% trimesic acid halide solution that with isoparaffin (Iso par) (EXXON society system) is solvent, carries out interfacial polymerization, removes superfluous organic solution subsequently.The composite membrane that obtains was heated 3 minutes down at 90 ℃, then at room temperature, in 0.2%Na
2CO
3Dipping was measured the performance of film after 30 minutes in the aqueous solution.Consequently, infiltration capacity is 37gfd, and the desalination rate is 99%.
Embodiment 2～36, Comparative examples A～W
The listed polar solvent, other are to implement with embodiment 1 identical method in using following table 1 and table 2.Measure the physical property of gained film, the results are shown in table 1 and the table 2.
[table 1]
| Routine number | Polar solvent | Concentration (weight %) | Transit dose (gfd) | Desalination rate (%) |
| Embodiment 2 | Methyl-sulfoxide (DMSO) | 1 | 40 | 98.2 |
| Embodiment 3 | 2-ethyl-1,3-hexylene glycol (EHD) | 0.1 | 35.2 | 94.5 |
| Embodiment 4 | EHD | 0.2 | 42.6 | 96.0 |
| Embodiment 4 | EHD | 0.3 | 47.9 | 97.6 |
| Embodiment 6 | EHD | 0.4 | 47.5 | 97.1 |
| Embodiment 7 | DMSO/EHD | 2/0.3 | 75.6 | 93.5 |
| Embodiment 8 | DMSO/EHD | 2/0.2 | 76.8 | 92.8 |
| Embodiment 9 | DMSO/EHD | 0.5/0.3 | 58.4 | 96.6 |
| Embodiment 10 | DMSO/EHD | 5/0.3 | 72.4 | 90.7 |
| Embodiment 11 | DMSO/EHD | 7/0.3 | 69.5 | 86.6 |
| Embodiment 12 | The EHD/ acetonitrile | 0.2/4 | 50.7 | 83.5 |
| Embodiment 13 | DMSO/2-butyl cellosolve (BE) | 2/2 | 65.3 | 93.2 |
| Embodiment 14 | DMSO/BE | 0.5/2 | 46.0 | 98.0 |
| Embodiment 15 | DMSO/BE | 0.1/0.1 | 44.8 | 97.9 |
| Embodiment 16 | BE | 0.1 | 34.5 | 98.4 |
| Embodiment 17 | BE | 4 | 36.4 | 96.7 |
| Comparative examples A | BE | 6 | 28.7 | 94.0 |
| Comparative example B | BE | 8 | 26.0 | 91.4 |
| Embodiment 18 | 2-propoxyl group ethanol (PE) | 0.1 | 22.1 | 95.1 |
| Embodiment 19 | PE | 2 | 43.5 | 97.0 |
| Embodiment 20 | PE | 4 | 40.6 | 95.4 |
| Embodiment 21 | Cellosolvo (EE) | 2 | 39.2 | 96.6 |
| Embodiment 22 | EE | 4 | 45.7 | 94.5 |
| Embodiment 23 | 2-methyl cellosolve (EE) | 2 | 38.2 | 96.6 |
| Embodiment 24 | ME | 4 | 36.7 | 88.6 |
| Comparative example C | Propane diols | 2 | 23.1 | 96.9 |
| Comparative Example D | Ethylene glycol dimethyl ether | 2 | 36.3 | 92.9 |
| Comparative Example E | Ethylene glycol dimethyl ether | 2 | 31.4 | 95.6 |
| Embodiment 25 | Diethylene glycol (DEG) hexyl ether (DEGHE) | 0.2 | 36.6 | 97.7 |
| Comparative Example F | Butyl carbitol | 2 | 31.2 | 95.9 |
| Comparative example G | Butyl carbitol | 0.1 | 32.7 | 93.1 |
| Comparative Example H | DGDE | 2 | 34.7 | 96.1 |
| Comparative Example I | Diethylene glycol methyl ether | 2 | 32.5 | 96.4 |
| Comparative Example J | Diethylene glycol diethyl ether | 2 | 31.0 | 95.9 |
| Embodiment 26 | The diethylene glycol (DEG) t-butyl methyl ether | 2 | 38.2 | 95.6 |
| Embodiment 27 | The propane diols butyl ether | 2 | 39.7 | 96.9 |
| Embodiment 28 | Propylene glycol propyl ether | 2 | 37.3 | 94.5 |
[table 2]
| Routine number | Polar solvent | Concentration (weight %) | Transit dose (gfd) | Desalination rate (%) |
| Embodiment 29 | The 1-amylalcohol | 1 | 33.2 | 97.3 |
| Embodiment 30 | The 1-butanols | 2 | 38.3 | 97.1 |
| Compare K | The 1-propyl alcohol | 2 | 32.4 | 91.2 |
| Comparative example L | Isopropyl alcohol | 3 | 30.8 | 90.7 |
| Comparative example M | Isopropyl alcohol | 10 | 34.7 | 89.4 |
| Embodiment 31 | 1,3-dimethyl-2-imidazoline glycol | 1 | 54.2 | 92.1 |
| Embodiment 32 | Tetramethylene sulfoxide | 1 | 46.6 | 94.8 |
| Embodiment 33 | The fourth sulfoxide | 1 | 42.2 | 95.6 |
| Embodiment 34 | The tolyl sulfoxide | 1 | 38.0 | 97.5 |
| Comparative example O | Ethyl sulfone | 1 | 29.9 | 93.6 |
| Embodiment 35 | Sulfolane (TMSO) | 1 | 44.6 | 91.8 |
| Embodiment 36 | The butyl sulfone | 0.5 | 40.2 | 98.0 |
| Comparative example P | N, dinethylformamide | 1 | 35.9 | 94.4 |
| Comparative example Q | The N-methyl pyrrolidone | 2 | 26.9 | 94.5 |
| Comparative example R | Acetone | 2 | 30.8 | 96.3 |
| Comparative example S | Acetone | 0 | 26.0 | 98.0 |
| Comparative example T | 1, the 6-hexylene glycol | 1 | 37.8 | 95.6 |
| Comparative example U | 1, the 6-hexylene glycol | 0.5 | 34.4 | 97.6 |
| Comparative example V | 1, the 6-hexylene glycol | 0.25 | 31.4 | 97.7 |
| Comparative example W | 1, the 2-hexylene glycol | 1 | 29.3 | 98.0 |
Embodiment 37
Use 0.3%2-ethyl-1 as polar solvent, 3-hexane diol (EHD), use 1%1,1 as quaternary ammonium salt, 3,1.6% toluenesulfonic acid (TSA) is used in 3-TMG (TMGU), conduct acid, in addition, and to make reverse osmosis composite membrane with embodiment 1 identical method.Measure the physical characteristic of gained film, the result is that infiltration capacity is that 43.4gfd, desalination rate are 96.3%.
Embodiment 38～78, comparative example X-AI
Use polar solvent, amine and acid or quaternary ammonium salt shown in following table 3 and the table 4, in addition, other are to implement with embodiment 37 identical methods.Measure the physical characteristic of gained film, the results are shown in table 3 and table 4.
[table 3]
| Routine number | Amine (weight %)/acid (weight %) or quaternary ammonium salt (weight %) | Polar solvent (weight %) | Transit dose (gfd) | Desalination rate (%) |
| Embodiment 38 | 1,2-methylimidazole (DM1) 1.0/TSA1.9 | EHD0.3 | 46.1 | 95.2 |
| Comparative example X | TMGU1/TSA1.6 | - | 25.4 | 93.3 |
| Embodiment 39 | TMGU1/TSA1.6 | EHD0.3/DMSO2 | 63.7 | 90.8 |
| Embodiment 40 | TMGU1/TSA1.6 | DEGHE0.2/DMSO2 | 59.5 | 86.9 |
| Comparative example Y | TMGU1/CSA2.0 | - | 26.7 | 97.6 |
| Embodiment 41 | TMGU1/CSA2.0 | EHD0.3 | 42.0 | 97.4 |
| Comparative example Z | DM1/TSA1.9 | - | 42.8 | 91.5 |
| Embodiment 42 | DM1/TSA1.9 | EHD0.3 | 46.1 | 95.2 |
| Embodiment 43 | DM1/TSA1.9 | EHD0.3/DMSO4 | 56.6 | 86.9 |
| Embodiment 44 | DM1/TSA1.9 | BE1 | 41.7 | 97.5 |
| Embodiment 45 | DM1/TSA1.9 | BE1/DMSO4 | 49.7 | 90.1 |
| Embodiment 46 | DM1/CSA2 | BE1/DMSO3 | 56.9 | 87.2 |
| Embodiment 47 | DM1/CSA2 | EHD0.3/DMSO4 | 46.1 | 95.2 |
| Comparative examples A A | DM1/CSA2 | - | 38.7 | 89.1 |
| Embodiment 48 | DM1/CSA2 | BE1 | 47.4 | 95.5 |
| Embodiment 49 | DM1/CSA2 | EHD0.3 | 52.9 | 95.5 |
| Embodiment 50 | DM1/CSA2 | Triglyme (TEGO) 1 | 42.5 | 92.6 |
| Comparative examples A B | TMBD1/TSA1.3 | - | 29.1 | 97.1 |
| Embodiment 51 | TMBD1/TSA1.3 | EHD0.3 | 36.7 | 97.8 |
| Embodiment 52 | TMBD1/TSA1.3 | EHD0.3/DMSO4 | 56.5 | 86.7 |
| Embodiment 53 | TMBD1/TSA1.3 | BE1 | 35.5 | 97.8 |
| Embodiment 54 | TMBD1/TSA1.3 | BE1/DMSO3 | 55.7 | 90.2 |
| Comparative examples A C | TMBD1/CSA1.6 | - | 24.5 | 97.5 |
| Embodiment 55 | TMBD1/CSA1.6 | EHD0.3 | 40.0 | 97.4 |
| Embodiment 56 | TMBD1/CSA1.6 | EHD0.3/DMSO4 | 52 | 93.4 |
| Comparative examples A D | TMED1/ methanesulfonic acid (MSA) 0.83 | - | 32.5 | 72.9 |
| Embodiment 57 | TMED1/MSA0.83 | BE1 | 35.6 | 89.1 |
| Embodiment 58 | TMED1/MSA0.83 | EHD0.3 | 38.7 | 94.6 |
| Embodiment 59 | TMED1/MSA0.83 | DMSO1 | 41.1 | 90.0 |
| Embodiment 60 | TMED1/TSA1.32 | EHD0.3 | 25.7 | 95.1 |
| Embodiment 61 | TMED1/TSA1.32 | EHD0.3/DMSO2 | 39.2 | 92.4 |
| Comparative examples A E | DABCO1/MSA0.85 | - | 32.3 | 97.0 |
| Embodiment 62 | DABCO1/MSA0.85 | BE1/DMSO4 | 48.6 | 88.3 |
| Embodiment 63 | DABCO1/MSA0.85 | BE1/TMSO4 | 24.4 | 88.5 |
| Embodiment 64 | DABCO2/MSA1.7 | BE2 | 36.9 | 96.2 |
[table 4]
| Routine number | Amine (weight %)/acid (weight %) or quaternary ammonium salt (weight %) | Polar solvent (weight %) | Transit dose (gfd) | Desalination rate (%) |
| Comparative examples A F | ?DABCO1/TSA1.7 | - | 31.3 | 95.7 |
| Embodiment 65 | ?DABCO1/TSA1.7 | BE1 | 33.2 | 96.9 |
| Embodiment 66 | ?DABCO1/TSA1.7 | BE1/DMSO4 | 48.8 | 88.8 |
| Embodiment 67 | ?DABCO1/TSA1.7 | EHD0.3 | 30.2 | 95.3 |
| Embodiment 68 | ?DABCO1/TSA1.7 | EHD0.3/DMSO4 | 48.0 | 88.9 |
| Comparative examples A G | Benzyl trimethyl ammonium chloride (BTAC) | - | 30.2 | 90.7 |
| Embodiment 69 | ?BTAC1.5 | BE1/DMSO3 | 46.5 | 91.6 |
| Embodiment 70 | ?BTAC1.5 | EHD0.3/DMSO3 | 48.0 | 92.3 |
| Comparative examples A H | ?TEA2/TSA3.4 | - | 34.1 | 98.1 |
| Embodiment 71 | ?TEA2/TSA3.4 | EHD0.3 | 38.0 | 97.3 |
| Embodiment 72 | ?TEA2/TSA3.4 | EHD0.3/DMSO3 | 57.1 | 87.5 |
| Embodiment 73 | ?TEA2/TSA3.4 | BE1 | 45.2 | 97.3 |
| Embodiment 74 | ?TEA2/TSA3.4 | BE1/DMSO3 | 52.4 | 83.3 |
| Embodiment A I | N, N-dimethyl benzyl amine (DMBA) 1/TSA1.4 | - | 34.5 | 97.9 |
| Comparative example 75 | ?DMBA1/TSA1.4 | EHD0.3 | 32.2 | 96.0 |
| Embodiment 76 | ?DMBA1/TSA1.4 | EHD0.3/DMSO3 | 47.1 | 87.2 |
| Embodiment 77 | ?DMBA1/TSA1.4 | BE1 | 34.0 | 97.9 |
| Embodiment 78 | ?DMBA1/TSA1.4 | BE1/DMSO3 | 56.9 | 82.8 |
From The above results as can be known, by selecting specific polar solvent.The reverse osmosis composite membrane that is obtained has obviously good infiltration capacity and desalination rate.
For example, embodiment 1,16, and 17 uses 2%, 0.1%, 4%2-butyl cellosolve (ethylene glycol monobutyl ether) make the infiltration capacity and the desalination rate of film, the film that more be higher than Comparative Example D, E uses 2% glycol dimethyl ether, ethylene glycol diethyl ether to make.
In embodiment 25, the film that uses 0.2% diethylene glycol (DEG) hexyl ether to obtain, in Comparative Example F～I, employed solvent with similar diethylene glycol (DEG) hexyl ether structure compares, and obtains higher infiltrate amount and desalination rate.
Aspect infiltration capacity or infiltration capacity and desalination rate, can obtain remarkable excellent results, as polar solvent, as with Comparative Example J, compare during employed 2% diethyl carbitol, embodiment 26 uses 2% diethylene glycol (DEG)-tert-butyl methyl ethers.In addition, with comparative example O, compare when using ethyl sulfone, embodiment 35, when using sulfolane, can obtain all very good effect aspect infiltration capacity and the desalination rate.
And, as can be known, as polar solvent, with Comparative Example E～J, T-W; Use ethylene glycol diethyl ether, butyl carbitol, DGDE, diethylene glycol methyl ether, diethyl carbitol, 1,6-hexane diol, 1, the 2-hexane diol is compared, and embodiment 3～6, use 0.1%, 0.2%, 0.3%, when 0.4%EHD makes polar solvent, can obtain better effect.
And then as can be known, the polar solvent of particular combinations and amine salt compound are used simultaneously, obtained unimaginable excellent results.For example, BE and DMSO, or the combination of EHD and DMSO, with these solvents each separately and amine salt compound comparison when using jointly, infiltration capacity significantly increases.As an example, embodiment 13 (2%DMSO and 2%BE), embodiment 14 (0.5%DMSO and 2%BE) or embodiment 15 (0.1%DMSO and 0.1%BE) have obtained the film of the infiltration capacity higher than embodiment 2 (1%DMSO) or embodiment 1 (2%BE).Yet, in the embodiment 63 that uses 2 kinds of polar solvents, but do not see this effect, in the combination of whole polar solvent, do not show good effect.
The present invention such as above formation, among the present invention, added the amine aqueous solution of polar solvent and amine salt compound, made reverse osmosis composite membrane by use, can be provided in the fresh water processing of seawater or salt solution useful, the reverse osmosis composite membrane with good desalination rate and infiltration capacity two specific characters.
Claims (12)
1. polyamide reverse osmosis composite film; it is characterized in that; on the porous supporting course, be coated with the aqueous solution that contains polyfunctional basic amine, polar solvent and at least a kind of quaternary ammonium salt and have the amine salt compound of 1 amino at least; make above-mentioned solution layer be selected from multiple functional radical acyl halide, polyfunctional basic sulfonyl halide and the polyfunctional basic isocyanic ester, have with the organic solution of amino reactive amine reactive compound and contact with containing; by interfacial polymerization; on the porous supporting course, form the polymerization amide layer, and product is carried out drying.
2. according to the polyamide reverse osmosis composite film of record in the claim 1, it is characterized in that above-mentioned polyfunctional basic amine is at least a kind of compound that is selected from primary aromatic amine, alkane primary diamines, ring grease shape primary diamines, ring grease shape secondary diamine, the aromatic series secondary diamine.
3. according to the polyamide reverse osmosis composite film of record in the claim 1, it is characterized in that above-mentioned amine reactive compound is at least a kind of compound that is selected from a phenyl-diformyl halide, four phenyl-diformyl halide, equal three etherides of benzene.
4. according to the polyamide reverse osmosis composite film of record in the claim 2, it is characterized in that above-mentioned amine reactive compound is at least a kind of compound that is selected from a phenyl-diformyl halide, four phenyl-diformyl halide, equal three etherides of benzene.
5. according to the polyamide reverse osmosis composite film of each record in the claim 1～4, it is characterized in that, above-mentioned polar solvent is to be selected from alkyloxyalkanol, ethylene glycol derivative, propanediol derivative, alkanol, 1, at least a kind solvent in ammediol derivative, sulfoxide derivant, sulfone derivative, carbonitrile derivatives and the urea derivative.
6. according to the polyamide reverse osmosis composite film of each record in the claim 1～4, it is characterized in that above-mentioned amine salt compound is the reactant of strong acid and multiple functional radical tertiary amine.
7. according to the polyamide reverse osmosis composite film of each record in the claim 14, it is characterized in that, above-mentioned polar solvent is above-mentioned ethylene glycol derivative: the triethylene glycol dimethyl ether, or above-mentioned propanediol derivative: propane diols butyl ether, or propylene glycol propyl ether, or above-mentioned alkanol: 1-amylalcohol, or 1-butanols, or above-mentioned 1,3-propane diol derivative: 2-ethyl-1, the 3-hexane diol, or above-mentioned sulfoxide derivant: tetramethylene sulfoxide, or butyl sulfoxide, or methylbenzene sulfoxide, or dimethyl sulfoxide (DMSO), or above-mentioned sulfone derivative: butyl sulfone, or sulfolane, or above-mentioned urea derivative: 1,3-dimethyl-2-imidazolidinone, or above-mentioned combination polar solvent more than 2 kinds: 2-ethyl-1,3-hexane diol and dimethyl sulfoxide (DMSO), or diethylene glycol (DEG) hexyl ether and dimethyl sulfoxide (DMSO), or 2-ethyl-1,3-hexane diol and acetonitrile, or alkoxyethanol and dimethyl sulfoxide (DMSO).
8. according to the polyamide reverse osmosis composite film of each record in the claim 1～4, it is characterized in that, use as above-mentioned polar solvent to be selected from following solvent:
Alkyloxyalkanol, in the above-mentioned aqueous solution be 0.05-4% (weight %),
The 1-amylalcohol, in the above-mentioned aqueous solution be 0.01～2% (weight %),
The 1-butanols, in the above-mentioned aqueous solution be 0.01～3% (weight %),
Dimethyl sulfoxide (DMSO), in the above-mentioned aqueous solution be 0.01～8% (weight %),
Sulfolane, in the above-mentioned aqueous solution be 0.01～4% (weight %) and
The mixed solution of alkyloxyalkanol and dimethyl sulfoxide (DMSO), wherein alkyloxyalkanol in the above-mentioned aqueous solution be 0.05～4% and dimethyl sulfoxide (DMSO) be 0.01～8% (weight %) in the above-mentioned aqueous solution.
9. the manufacture method of the polyamide reverse osmosis composite film of a claim 1 is characterized in that, comprises following operation,
On the porous supporting course operation of the above-mentioned aqueous solution of coating, above-mentioned solution layer contact with above-mentioned organic solution, by interfacial polymerization, the operation of formation polymerization amide layer and product is carried out the operation of drying on the porous supporting course.
10. according to the manufacture method of the polyamide reverse osmosis composite film of record in the claim 9, it is characterized in that, the above-mentioned aqueous solution, making pH by the nertralizer that adds acid is 7～13.
11. the manufacture method of the polyamide reverse osmosis composite film of a claim 1 is characterized in that, comprises following operation:
Coating contains the 1st aqueous solution of above-mentioned polar solvent and above-mentioned amine salt compound on the porous supporting course, the 2nd solution that form the operation of the 1st solution layer, coating contains above-mentioned polyfunctional basic amine on the 1st solution layer with the operation that forms the 2nd solution layer, above-mentioned solution layer is contacted with above-mentioned organic solution, by interfacial polymerization, on the porous supporting course, form the operation of aramid layer and product is carried out dry operation.
12. the manufacture method of the polyamide reverse osmosis composite film of a claim 1, feature are to comprise following operation,
Coating contains the 1st aqueous solution of above-mentioned polar solvent on the porous supporting course, forms the operation of the 1st solution layer,
Coating contains the 2nd solution of above-mentioned polyfunctional basic amine and above-mentioned amine salt compound on the 1st solution layer, form the operation of the 2nd solution layer, above-mentioned solution layer is contacted with above-mentioned organic solution, by interfacial polymerization, on the porous supporting course, form the operation of aramid layer, and product is carried out dry operation.
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| EP1483033A4 (en) * | 2002-03-01 | 2005-04-13 | Osmonics Inc | A process for preparing semipermeable membranes having improved permeability |
| KR100680109B1 (en) * | 2005-07-27 | 2007-02-07 | 웅진코웨이주식회사 | Polyamide reverse osmosis composite membrane and preparation method thereof |
| GB2492677B (en) * | 2010-04-30 | 2018-07-25 | Woongjin Chemical Co Ltd | Forward osmosis membrane for seawater desalination, and method for manufacturing same |
| CN103349922B (en) * | 2013-07-09 | 2015-03-11 | 淮海工学院 | Method of surface functionalization of aramatic polyamides reverse osmosis thin film composite membrane |
| CN105396471A (en) * | 2015-12-19 | 2016-03-16 | 杭州水处理技术研究开发中心有限公司 | Preparation method of high water flux reverse osmosis membrane |
| CN113083032B (en) * | 2021-04-26 | 2022-10-28 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853122A (en) * | 1987-09-15 | 1989-08-01 | Bend Research, Inc. | P-xylylenediamide/diimide composite RO membranes |
| US5324538A (en) * | 1991-03-12 | 1994-06-28 | Toray Industries, Inc. | Process for producing composite semipermeable membrane employing a polyfunctional amine solution and high flash point - solvent |
| US5576057A (en) * | 1993-06-24 | 1996-11-19 | Nitto Denko Corporation | Method of producing high permeable composite reverse osmosis membrane |
| US5658460A (en) * | 1996-05-07 | 1997-08-19 | The Dow Chemical Company | Use of inorganic ammonium cation salts to maintain the flux and salt rejection characteristics of reverse osmosis and nanofiltration membranes during drying |
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1999
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853122A (en) * | 1987-09-15 | 1989-08-01 | Bend Research, Inc. | P-xylylenediamide/diimide composite RO membranes |
| US5324538A (en) * | 1991-03-12 | 1994-06-28 | Toray Industries, Inc. | Process for producing composite semipermeable membrane employing a polyfunctional amine solution and high flash point - solvent |
| US5576057A (en) * | 1993-06-24 | 1996-11-19 | Nitto Denko Corporation | Method of producing high permeable composite reverse osmosis membrane |
| US5658460A (en) * | 1996-05-07 | 1997-08-19 | The Dow Chemical Company | Use of inorganic ammonium cation salts to maintain the flux and salt rejection characteristics of reverse osmosis and nanofiltration membranes during drying |
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