CN100339153C - 一种具有改进了渗透率的半透膜的制备方法 - Google Patents
一种具有改进了渗透率的半透膜的制备方法 Download PDFInfo
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- CN100339153C CN100339153C CNB038086883A CN03808688A CN100339153C CN 100339153 C CN100339153 C CN 100339153C CN B038086883 A CNB038086883 A CN B038086883A CN 03808688 A CN03808688 A CN 03808688A CN 100339153 C CN100339153 C CN 100339153C
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- reverse osmosis
- osmosis membrane
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- nitric acid
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 230000035699 permeability Effects 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 50
- 229920000768 polyamine Polymers 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- -1 sulfuryl halides Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001266 acyl halides Chemical class 0.000 claims description 9
- XRDNFNGIKTYHAN-UHFFFAOYSA-N n,n-diethylethanamine;nitric acid Chemical compound O[N+]([O-])=O.CCN(CC)CC XRDNFNGIKTYHAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- WAWBMJIRULKJPO-UHFFFAOYSA-N tetraethylazanium borate Chemical compound [O-]B([O-])[O-].CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC WAWBMJIRULKJPO-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QDDJFNCPALBLEO-UHFFFAOYSA-N n-ethylethanamine;nitric acid Chemical compound O[N+]([O-])=O.CCNCC QDDJFNCPALBLEO-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- MFWWPDIFJWFUCB-UHFFFAOYSA-N nitric acid;n-propylpropan-1-amine Chemical compound O[N+]([O-])=O.CCCNCCC MFWWPDIFJWFUCB-UHFFFAOYSA-N 0.000 claims description 6
- JTJKNAJRGLQKDZ-UHFFFAOYSA-N tetraethylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[N+](CC)(CC)CC JTJKNAJRGLQKDZ-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000006482 condensation reaction Methods 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 description 11
- 230000004907 flux Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- UQBNGMRDYGPUOO-UHFFFAOYSA-N 1-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CNC1=CC=CC(NC)=C1 UQBNGMRDYGPUOO-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- LGCBVEQNSDSLIH-UHFFFAOYSA-N 4-pyridin-3-ylbutanal Chemical compound O=CCCCC1=CC=CN=C1 LGCBVEQNSDSLIH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- GSIUWXLLNUXQCX-UHFFFAOYSA-N OC(C(C=C1)=CC=C1C(O)=O)=O.I Chemical compound OC(C(C=C1)=CC=C1C(O)=O)=O.I GSIUWXLLNUXQCX-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- YAZXITQPRUBWGP-UHFFFAOYSA-N benzene-1,3-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=CC(C(Br)=O)=C1 YAZXITQPRUBWGP-UHFFFAOYSA-N 0.000 description 1
- KRJYMHQSKZCAEL-UHFFFAOYSA-N benzene-1,3-dicarbonyl iodide Chemical compound IC(=O)C1=CC=CC(C(I)=O)=C1 KRJYMHQSKZCAEL-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- SEOMTQNOPDIZEI-UHFFFAOYSA-O diethylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[NH2+]CC SEOMTQNOPDIZEI-UHFFFAOYSA-O 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-O dipropylazanium Chemical compound CCC[NH2+]CCC WEHWNAOGRSTTBQ-UHFFFAOYSA-O 0.000 description 1
- COELXAPQNYWAAM-UHFFFAOYSA-O dipropylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCC[NH2+]CCC COELXAPQNYWAAM-UHFFFAOYSA-O 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NNEGXZRHWIFNMG-UHFFFAOYSA-O ethyl-di(propan-2-yl)azanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[NH+](C(C)C)C(C)C NNEGXZRHWIFNMG-UHFFFAOYSA-O 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- XONGDEOKKBSUIF-UHFFFAOYSA-N terephthalic acid;hydrobromide Chemical compound Br.OC(=O)C1=CC=C(C(O)=O)C=C1 XONGDEOKKBSUIF-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- VOXVCYMHFQQEMC-UHFFFAOYSA-O triethylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[NH+](CC)CC VOXVCYMHFQQEMC-UHFFFAOYSA-O 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
本发明提供了制备具有改进了渗透率的反渗透膜的方法和用该方法制备的膜。
Description
优先权
本申请要求2002年3月1日提交的美国临时申请60/360696的优先权。
背景技术
采用不对称或复合膜包括选择性渗透、超滤和反渗透,各种技术已用于有效分离。反渗透分离的一个例子是使海水、污水或含盐水成为可饮用水的脱盐过程。这些水的脱盐常常是为工业、农业或家用提供大量淡水所必不可少的。该脱盐作用可以通过使水经过反渗透膜而留下污物或盐分来实现。典型的反渗透膜具有很高的阻盐系数(salt rejection coefficient),拥有在较低的压力下,使较大量的水通过膜的能力。
各种美国专利描述了在工业过程中实用的反渗透膜和支撑物(support)。例如,美国专利4,830,885、3,744,642、4,277,344、4,619,767、4,830,885、4,830,885。
美国专利4,765,897和4,812,270讨论了聚酰胺膜,其被报道可用于水软化应用中。该膜通过将聚酰胺反渗透膜用强矿物酸处理后再用阻隔增强剂(rejection enhancing agent)处理而制备。
随后,美国专利4,983,291报道了半透膜,该半透膜用酸或某些酸衍生物处理并干燥以提供具有高通量(flux)且同时保持了高阻隔率(rejectionrate)的膜。
尽管有上述申请,但仍需要具有实用的通量和保持性(retentionproperties)的反渗透膜。特别是需要在保持实用的阻隔特性的同时还拥有改进了通量特性的反渗透膜。
发明内容
申请人发现了一种制备具有改进了通量特性的半透性反渗透膜的方法。因此,本发明提供了一种用于制备具有改进了通量特性的反渗透膜的方法,包括用硝酸二丙基铵(dipropylammonium nitrate)、硝酸二异丙基乙基铵(diisopropylethylammonium nitrate)、硝酸三乙基铵(triethylammoniumnitrate)、硝酸四乙基铵(tetraethylammonium nitrate)、硝酸二乙基铵(diethylammonium nitrate)或硼酸四乙基铵(tetraethylammonium borate),或其混合物处理(并任选干燥)起始(starting)反渗透膜,以供给具有改进了通量性的反渗透膜。
本发明还提供了一种改进反渗透膜的渗透率(permeability)的方法,该方法包括用有机硝酸盐或硼酸盐的水溶液处理反渗透膜,干燥;及任选恢复(recovering)该膜。
本发明还提供了用本发明的方法制备的反渗透膜。
美国专利4,983,291报道了膜的通量可以通过酸处理后进行干燥来保持,所用酸选自羟基聚羧酸(hydroxypolycarboxylic acids)、聚氨基亚烷基聚羧酸(polyaminoalkylene polycarboxylic acids)、磺酸(sulfonic acids)、氨基酸、氨基酸盐、酸的胺盐、聚合酸(polymeric acid)和无机酸。申请人发现用特定系列的铵盐处理反渗透膜,特别是用硝酸根和硼酸根阴离子处理,可以得到显著提高了通量的膜。此外,本发明中的处理没有明显降低膜的阻盐性能。
发明详述
反渗透膜
能够用本发明的方法进行处理的反渗透膜包括多酰基卤化物(polyacylhalide)、多磺酰卤化物(polysulfonyl halid)或多异氰酸酯(polyisocyanate),和多胺(polyamine)或双酚的反应产物。该反应产物通常沉积在多孔背部支撑材料(porous support backing material)上和/或材料内。
反渗透膜可以用本领域通常已知的方法制备,例如,用类似于描述在美国专利3,744,642、4,277,344、4,948,507和4,983,291中的方法。这些方法必须将多胺或双酚,优选多胺的水溶液涂覆在多孔支撑背材上。之后被涂覆的载体材料的表面任选除去过量的胺溶液,并与多酰基卤化物、多磺酰卤化物或多异氰酸酯的有机溶液接触,以提供可用作本发明方法中的起始材料的反渗透膜。这些膜还可以用甘油或前述专利公开的干燥剂进行干燥。
多孔支撑背材通常包含聚合物材料,其含有足够大的孔径允许渗透物通过但没有大到干扰所形成的超薄反渗透膜的阻挡(bridging over)。可以用于制备本发明所需的膜复合物的多孔支撑背材的例子包括聚合物如聚砜、聚碳酸酯、微孔聚丙烯、各种聚酰胺、聚酰亚胺、聚苯醚、各种卤代聚合物如聚偏1,1-二氟乙烯,等。
多孔支撑背材可以通过手工涂布或连续操作,用多胺单体水溶液进行涂覆以提高所得膜对仲多胺单体(monomeric secondary polyamines)的环境侵蚀的抵抗力。这些多胺单体包含环状多胺,如哌嗪等;取代的环状多胺,如甲基哌嗪、二甲基哌嗪等;芳族多胺,如间苯二胺、邻苯二胺、对苯二胺等;取代的芳族多胺,如氯代苯二胺、N,N′-二甲基-1,3-苯二胺等;多芳环多胺,如联苯胺等;取代的多芳环多胺,如3,3′-二甲基联苯胺、3,3′-二氯联苯胺等,或根据分离要求和对所得到薄膜的环境稳定性的要求而包含这些单体的混合物。
用作芳族多胺的载体的溶液通常包含水,其中芳族多胺以占溶液重量0.1至20%的量存在,其pH值为大约7至大约14。pH值可以是胺溶液本来的pH值,或可以由存在的碱来提供。这些碱受体(acceptor)的一些例子包括氢氧化钠、氢氧化钾、碳酸钠、三乙基铵、N,N′-二甲基哌嗪等。在胺溶液中的其它添加剂包括表面活性剂、胺盐(例如见美国专利4,984,507)和/或溶剂(例如见美国专利5,733,602)。
用芳族多胺水溶液涂覆多孔支撑背材之后,任选用适当的方法清除过量的溶液。随后,涂覆后的背部支撑材料与芳族多酰基卤化物的有机溶液进行接触。所应用的芳族多酰基卤化物的例子包括二或三羧酸卤化物如1,3,5-苯三酰基氯化物(trimesoylchloride)(1,3,5-苯三甲酸氯化物(1,3,5-benzene tricarboxylic acid chloride))、间苯二酰氯化物、对苯二酰氯化物、1,3,5-苯三酰基溴化物(1,3,5-苯三甲酸溴)、间苯二酰溴化物、对苯二酰溴化物、1,3,5-苯三酰基碘化物(1,3,5-苯三甲酸碘化物)、间苯二酰碘化物、对苯二酰碘化物,以及二和三羧酸卤化物、三和三羧酸卤化物的混合物,也就是1,3,5-苯三酰基卤化物和异构化的邻苯二甲酰卤化物。芳族多酰基卤化物的替代反应物包括芳族的二或三磺酰基卤化物、芳族二或三异氰酸酯、芳族二或三氯甲酸酯或用上述替代物的混合物所取代的芳环。多酰基卤化物可以被取代以使其对进一步的环境侵蚀更具抵抗力。
在本发明方法中使用的有机溶剂包含不溶于水、不溶或微溶于多羟基化合物的溶剂,也可包含烷烃如正戊烷、正己烷、正庚烷、环戊烷、环己烷、甲基环戊烷、石脑油、异链烷烃(Isopars)等,或卤代烃如氟利昂(Freon)系列或种类的卤代溶剂。
本发明的处理方法
本发明的反渗透膜,例如用上述方法制备的膜,暴露于硝酸二丙基铵、硝酸二异丙基乙基铵、硝酸三乙基铵、硝酸四乙基铵、硝酸二乙基铵或硼酸四乙基铵,或其混合物中一段时间,大约1秒至24小时。膜的暴露通常在一定温度下进行,温度从室温到90℃或更高,优选温度范围为大约20℃至大约40℃。
膜暴露之后在更高的温度下干燥(高达大约170℃)一段时间,从大约30秒到大约2小时或更长。
根据本发明的方法制备的膜通常在膜上或在膜中含有有机硝酸盐或硼酸盐。因此,本发明提供具有改进了渗透率的反渗透膜,在膜上或在膜中以及多孔支撑背材的孔中含有有机硝酸盐或硼酸盐。在一个具体实施方式中,在膜上或膜中含有硝酸二丙基铵、硝酸二异丙基乙基铵、硝酸三乙基铵、硝酸四乙基铵、硝酸二乙基铵或硼酸四乙基铵。
给出下面的实施例用于说明,但没有限制。
实施例
实施例1
将干燥的Osmonics AK RO膜样品在硝酸三乙基铵(4%W/W)水溶液中浸泡1分钟。排尽过量的溶液,然后将膜置于烘箱(100℃)中4分钟。处理过的膜置于反渗透室中,在DI水中50psig的压力下对输入的包含氯化钠(500ppm)的溶液进行测试。操作1小时后测量渗透率(测量值A,单位为10-5cm3/(cm2*sec*atm))和通过百分数(percent passage)。该膜具有26.1的渗透率和7.7%的通过百分数。
对比实施例A
所测试的未经处理的AK膜具有19.4的渗透率和3%的通过百分数。
实施例2
按实施例1的方法但用四乙基铵代替三乙基铵而制备的膜具有27.4的渗透率和3.4%的通过百分数。
实施例3
按实施例1的方法但用二异丙基乙基铵代替三乙基铵而制备的膜具有24.9的渗透率和2.7%的通过百分数。
实施例4
按实施例1的方法但用二丙基铵代替三乙基铵而制备的膜具有24.1的渗透率和3.9%的通过百分数。
实施例5
按实施例1的方法但用硼酸四乙基铵代替硝酸三乙基铵而制备的膜具有25.6的渗透率和4.4%的通过百分数。
实施例6
用实施例1的方法处理Osmonics AG RO膜的样品。该膜具有15.2的渗透率和0.9%的通过百分数。
实施例7
按实施例2制备膜,但添加1%的三乙基铵到中性溶液使处理溶液的pH值达到12。该膜具有34.1的渗透率和5.2%的通过百分数。
对比实施例B
所测试的未处理的AG膜具有11.4的渗透率和0.9%的通过百分数。
对比实施例C
按实施例1的方法但用四甲基胺代替三乙基铵而制备的膜具有13.8的渗透率和2.0%的通过百分数。
对比实施例D
按实施例1的方法但用甲苯磺酸四乙基铵代替硝酸三乙基铵而制备的膜具有18.1的渗透率和2.0%的通过百分数。
尽管分别引入参考,但此申请中引入的所有出版物、专利和专利文件都可作为参考。参考各种具体的和优选的实施方式和方法描述了本发明。然而,应该可以理解在本发明的实质和范围内可以进行各种变化和修改。
Claims (35)
1.一种用于制备具有改进了渗透率的反渗透膜的方法,包括用选自硝酸二丙基铵、硝酸二异丙基乙基铵、硝酸三乙基铵、硝酸四乙基铵、硝酸二乙基铵或硼酸四乙基铵,或其混合物的处理溶液处理起始反渗透膜,然后进行干燥以提供具有改进了渗透率的反渗透膜。
2.权利要求1所述的方法,其中所述起始反渗透膜用硝酸二丙基铵、硝酸二异丙基乙基铵、硝酸三乙基铵、硝酸四乙基铵、或硝酸二乙基铵,或其混合物进行处理。
3.权利要求1所述的方法,其中所述起始反渗透膜用硼酸四乙基铵进行处理。
4.权利要求1至3中任一项所述的方法,还包括制备起始反渗透膜,包括通过用多胺的水溶液涂覆多孔支撑背材,任选除去过量的溶液,及将涂覆过的多孔支撑背材与多酰基卤化物、多磺酰卤化物或多异氰酸酯的有机溶液接触以提供作为缩合反应产物的起始反渗透膜。
5.权利要求4所述的方法,其中所述多胺是芳族二元或三元胺,或其混合物。
6.权利要求4所述的方法,其中所述多胺是间苯二胺。
7.权利要求4所述的方法,其中所述多酰基卤化物是芳族二或三酰基卤化物。
8.权利要求4所述的方法,其中所述多酰基卤化物是1,3,5-苯三酰基氯化物、间苯二酰氯化物,或其混合物。
9.权利要求1所述的方法,其中所述起始反渗透膜在处理前已经干燥。
10.一种具有改进了渗透率的反渗透膜,其是按照权利要求1至9任一项所述的方法制备的。
11.权利要求10所述的反渗透膜,具有比制备它的起始反渗透膜至少高25%的渗透率。
12.权利要求10所述的反渗透膜,具有比制备它的起始反渗透膜至少高50%的渗透率。
13.权利要求10所述的反渗透膜,具有比制备它的起始反渗透膜至少高65%的渗透率。
14.权利要求10所述的反渗透膜,具有比制备它的起始反渗透膜至少高75%的渗透率。
15.权利要求10所述的反渗透膜,其渗透率为制备它的起始反渗透膜的至少两倍。
16.一种改进反渗透膜的渗透率的方法,包括用有机硝酸盐或硼酸盐的水溶液处理反渗透膜,和干燥,所述有机硝酸盐或硼酸盐选自硝酸二丙基铵、硝酸二异丙基乙基铵、硝酸三乙基铵、硝酸四乙基铵、硝酸二乙基铵或硼酸四乙基铵,或其混合物。
17.权利要求16所述的方法,其中所述有机硝酸盐或硼酸盐包含含氮阳离子。
18.权利要求17所述的方法,其中含氮阳离子是(C1-C6烷基)nN+H(4-n);其中n是1、2、3或4。
19.权利要求18所述的方法,其中每个C1-C6烷基是具有少于4个碳原子的有支链或没有支链的基团。
20.权利要求18所述的方法,其中n是2、3或4,并且每个C1-C6烷基都相同。
21.权利要求18所述的方法,其中n是2、3或4,并且每个C1-C6烷基不相同。
22.权利要求16所述的方法,其中所述有机硝酸盐或硼酸盐包含多于一个的含氮阳离子。
23.权利要求18所述的方法,其中n是2。
24.权利要求18所述的方法,其中n是3。
25.权利要求18所述的方法,其中n是4。
26.权利要求16所述的方法,其中所述反渗透膜在用有机硝酸盐或硼酸盐的水溶液处理之前已经干燥。
27.权利要求1至3、5至8或16至26中的任一项所述的方法,其中处理溶液的pH值大于7。
28.权利要求1至3、5至8或16至26中的任一项所述的方法,其中处理溶液的pH值大于8。
29.权利要求1至3、5至8或16至26中的任一项所述的方法,其中处理溶液的pH值大于10。
30.一种与制备它的起始反渗透膜相比改进了渗透率的反渗透膜,其是按照权利要求16至29中任一项所述的方法制备的。
31.权利要求30所述的反渗透膜,具有比制备它的起始反渗透膜至少高25%的渗透率。
32.权利要求30所述的反渗透膜,具有比制备它的起始反渗透膜至少高50%的渗透率。
33.权利要求30所述的反渗透膜,具有比制备它的起始反渗透膜至少高65%的渗透率。
34.权利要求30所述的反渗透膜,具有比制备它的起始反渗透膜至少高75%的渗透率。
35.权利要求30所述的反渗透膜,其渗透率为制备它的起始反渗透膜的至少两倍。
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2003
- 2003-03-03 EP EP03723677A patent/EP1483033A4/en not_active Ceased
- 2003-03-03 KR KR1020117013203A patent/KR20110086141A/ko active Search and Examination
- 2003-03-03 CA CA002477427A patent/CA2477427A1/en not_active Abandoned
- 2003-03-03 JP JP2003572660A patent/JP4246070B2/ja not_active Expired - Fee Related
- 2003-03-03 AU AU2003230592A patent/AU2003230592A1/en not_active Abandoned
- 2003-03-03 KR KR10-2004-7013618A patent/KR20050004788A/ko active Application Filing
- 2003-03-03 CN CNB038086883A patent/CN100339153C/zh not_active Expired - Fee Related
- 2003-03-03 WO PCT/US2003/006587 patent/WO2003074152A1/en active Application Filing
- 2003-03-03 US US10/506,135 patent/US7658872B2/en not_active Expired - Fee Related
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US4256108A (en) * | 1977-04-07 | 1981-03-17 | Alza Corporation | Microporous-semipermeable laminated osmotic system |
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CN1158274A (zh) * | 1995-07-05 | 1997-09-03 | 日东电工株式会社 | 高渗透性的反渗透复合膜 |
US6245234B1 (en) * | 1999-06-03 | 2001-06-12 | Saehan Industries Incorporation | Composite polyamide reverse osmosis membrane and method of producing the same |
CN1301586A (zh) * | 1999-12-28 | 2001-07-04 | 世韩工业株式会社 | 聚酰胺反渗透复合膜及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
US7658872B2 (en) | 2010-02-09 |
KR20110086141A (ko) | 2011-07-27 |
JP2005526591A (ja) | 2005-09-08 |
AU2003230592A1 (en) | 2003-09-16 |
US20050103705A1 (en) | 2005-05-19 |
EP1483033A4 (en) | 2005-04-13 |
WO2003074152A1 (en) | 2003-09-12 |
JP4246070B2 (ja) | 2009-04-02 |
CN1646203A (zh) | 2005-07-27 |
EP1483033A1 (en) | 2004-12-08 |
KR20050004788A (ko) | 2005-01-12 |
CA2477427A1 (en) | 2003-09-12 |
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