CN1029824C - 耐氯半透膜 - Google Patents
耐氯半透膜 Download PDFInfo
- Publication number
- CN1029824C CN1029824C CN89102360A CN89102360A CN1029824C CN 1029824 C CN1029824 C CN 1029824C CN 89102360 A CN89102360 A CN 89102360A CN 89102360 A CN89102360 A CN 89102360A CN 1029824 C CN1029824 C CN 1029824C
- Authority
- CN
- China
- Prior art keywords
- chlorine
- film
- semipermeable membranes
- resistant semipermeable
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 40
- 239000000460 chlorine Substances 0.000 title claims abstract description 40
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000768 polyamine Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 8
- 239000011247 coating layer Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 45
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 9
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 8
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical class ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- UQBNGMRDYGPUOO-UHFFFAOYSA-N 1-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CNC1=CC=CC(NC)=C1 UQBNGMRDYGPUOO-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims 2
- YNYCTCUBQDJOIK-UHFFFAOYSA-N ClC1=CC=CC=C1.NCCNCCN Chemical compound ClC1=CC=CC=C1.NCCNCCN YNYCTCUBQDJOIK-UHFFFAOYSA-N 0.000 claims 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims 2
- 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 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000010612 desalination reaction Methods 0.000 abstract description 6
- 239000002253 acid Chemical class 0.000 abstract description 5
- 150000004820 halides Chemical class 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 20
- -1 aromatic tricarboxylic acid Chemical class 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- 238000012805 post-processing Methods 0.000 description 9
- 238000001223 reverse osmosis Methods 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000001262 acyl bromides Chemical class 0.000 description 3
- 150000001267 acyl iodides Chemical class 0.000 description 3
- 150000001502 aryl halides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002328 demineralizing effect Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 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
- 230000003204 osmotic effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002954 polymerization reaction product Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LPDSNGAFAJYVKH-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dichloroaniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C(Cl)=C1Cl LPDSNGAFAJYVKH-UHFFFAOYSA-N 0.000 description 1
- JTDKYHKOMIBNQO-UHFFFAOYSA-N C1=CC=C(C=C1)Br(C=O)C=O Chemical compound C1=CC=C(C=C1)Br(C=O)C=O JTDKYHKOMIBNQO-UHFFFAOYSA-N 0.000 description 1
- YBBGXSZONUAPNA-UHFFFAOYSA-N C1=CC=C(C=C1)I(C=O)C=O Chemical compound C1=CC=C(C=C1)I(C=O)C=O YBBGXSZONUAPNA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 239000005862 Whey Substances 0.000 description 1
- 102000007544 Whey Proteins Human genes 0.000 description 1
- 108010046377 Whey Proteins Proteins 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KRCSBYPKUJAPSQ-UHFFFAOYSA-N benzene formyl chloride Chemical compound C(=O)Cl.C1=CC=CC=C1 KRCSBYPKUJAPSQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001936 parietal 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
- 230000035699 permeability Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B5/00—Anti-hunting arrangements
- G05B5/01—Anti-hunting arrangements electric
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/48—Influencing the pH
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31536—Including interfacial reaction product of adjacent layers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Automation & Control Theory (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
在多孔支持垫衬材料上包含界面聚合反应产物复合材料的耐氯半透膜，可用下法制备：使例如聚砜等多孔支持材料与芳族多胺水溶液相接触，此水溶液含有多羟基化合物及吸酸剂。然后使此有涂层的支持材料与芳香多羧酰卤有机溶剂溶液相接触，接触时间足以使支持材料表面上生成界面聚合反应产物。所得的复合材料然后进行用碱性化合物洗涤、亚硫酸氢钠浸取及用多羟基化合物处理此浸取过的复合物等后处理。所得的膜复合材料可用于例如半咸水或海水的脱盐等分离方法中，此膜能耐水中存在的氯的腐蚀。
Description
液体中或气体中各种成分的分离可用许多方法来实现，应用不对称膜或复合膜的分离技术包括选择渗透、超滤或反渗透。后一类型分离技术的具体例子包括可从海水、污染水、半咸水或盐水中得到可供饮用的或适于其它目的的水的脱盐方法。这个方法对世界上那些找到的水都是半咸水或含盐量太高的水的地区是特别有意义的。为了给工业、农业或家庭生活提供大量饮用水或相对无盐的水，这些水的脱盐是必要的。水的脱盐是令这些水流经反渗透膜，借以使纯化的水通过此膜并回收，同时污物或盐分实际上因被膜阻挡而不能通过此膜，并被作为保留物而被回收。
为此目的所用的反渗透膜必须具有可适用于此方法的某些特性。例如，此膜必须具有很高的盐分排除系数。另外，另一个重要特性及在膜使用时必须指出的问题是膜的抗氯腐蚀的能力。存在于反渗透膜使用中的另一个重要因素是此膜亦应具有高的流通特性，就是说，在较低的压力下此膜通过较大量水的能力。如果膜具有这些所需特性，那么，它就具有工业上适用于脱盐工艺的实用性。
用各种已知的聚合材料可以制备反渗透膜并且已经应用。尽管这些聚合材料中许多具有降低溶质浓度到显示其盐分排除能力超过98%的本领，但某些材料却不具有必要的流通速率，使单位膜表面上由膜生产所需的水体积足以应用此技术。
上文中已有陈述，许多早先的美国专利讨论了适用于脱盐方法的各种膜。例如，美国专利3，567，632、3，600，350、3，710，945、3，878，109、3，904，519、3，920，612、3，951，815、3，993，625及4，048，144描述了各种用聚酰胺制备的半透膜。美国专利3，260，691和3，480，588也同样披露了用芳族伯二胺和芳族三羧酸衍生物的缩合产物制得的一些涂布组合物。
因为脱盐方法所用的半透膜本身应当比较薄以便提供所要求的流通速率，所以在许多情况下反渗透膜必须复合于或叠层于多孔垫衬支持材料上。这多孔支持垫衬材料本身应当具有某些特性，使其适用于这样的用途。例如，这种多孔支持材料应当具有足够大的孔，以便水或渗透物能够穿过这种支持材料而不影响或减小整个复合材料的流通速率。反之，孔也不能太大，否则将使这种薄的复合半透膜倾向于填入或过份凹进孔内，这样，当在高压下进行时，会使这薄膜变形并有破裂的可能，因而使所说的膜在反渗透过程中失去它的效能。
除上述的美国专利外，另一份美国专利4，277，344，披露了一种界面合成的反渗透膜。这种膜是用界面聚合的芳族聚酰胺制得的，而此芳族聚酰胺是从基本上是单体的多酰基卤和基本上是单体的亚芳基多胺制备的。这种复合膜是这样制备的：将含有多胺反应物的水溶液液层涂在支持材料上，使此液层和溶解于液体脂肪族溶剂或液体卤化脂肪族溶剂中的基本上是单体的挥发性多官能团酰卤接触，干燥形成的产物以制成所要的膜。此外，这种膜然后可用氧化剂和氯或释放氯剂处理以改善它的耐氯性能。此专利指出此膜包含多处具有下式的结构：
Ar（CONH-）2COOH
其中Ar代表多官能团芳基卤的芳香核残基。此外，这种膜事实上被认为是轻微交联的，反应是在没有任何表面活性剂及吸酸剂存在的条件下进行的，专利权所有者认为这些化合物似乎没有提供任何本发明范围内的优点，并且认为界面聚合反应最好在没有表面活性剂或吸酸剂存在下进行。
再者，该膜的结构将依赖于水溶液中作为反应剂提供的水，并认为在多官能团芳基卤中芳卤基在和多胺水溶液的反应期间处于竞争状态。专利权拥有者推断芳卤基能与水反应，亦能与伯胺基反应，或者相反地，发生顺序反应：水解反应优先于和胺基的缩合反应。
本发明涉及包括在多孔支持物上的选择渗透壁层的复合膜。具体地说，本发明涉及显示出广泛耐氯及耐氧化剂降解的、优良的溶剂渗透速率和优良的溶质排除性能的膜。
如上所述，使用膜从气体混合物中分离气体、从液体混合物中分离液体、从液体混合物中分离气体或从液体中分离固体，是一个重要的商业课题。特别是在本质上为咸水或盐水，或其中溶解有其它固体和/或有机物质的水的分离的领域中，让水通过分离（选择渗透）膜，可以提供饮用水或适于工业或农业用的水。构成本申请发明特征的这种具体的膜包括由芳族多胺和芳族多羧酰氯反应所得的产物。此膜复合于或是涂布于多孔支持垫衬材料上。把这些膜用于分离（脱盐）方法中，可以在相当长时期内处理水源而无需更换膜，膜的长寿命部分地是由于其耐水源中存在的氯或其它氧化剂引起的降解作用。
因而，本发明的目的是提供一种适用于分离方法和具有所需特性的复合膜。
本发明的进一步的目的是提供一种制备耐氯及其它氧化剂的半透膜的方法，使提供的膜适用于例如氯及其他氧化剂的含量足以降解其它类型膜的水的脱盐分离方法。
一方面，本发明的一种具体方案是按下述方法制备的耐氯半透膜。即将含有多羟基化合物的芳族多胺水溶液流涂在多孔支持垫衬材料上，除去多余的溶液，使有涂层的多孔支持材料和芳族多羧酰卤的有机溶剂溶液相接触，在此多孔支持材料表面上生成界面缩合反应产物，在固化条件下固化所得的复合物形成所说的耐氯半透膜。
本发明的另一具体方案是制备耐氯半透膜的方法，将含有多羟基化合物和吸酸剂的芳族多胺水溶液流涂在多孔支持垫衬材料上，除去多余的溶液，使有涂层的多孔支持材料和芳族多羧酰卤的有机溶剂溶液相接触，在此多孔支持材料表面上生成界面缩合反应产物，在固化条件下固化所得的复合材料，用碱性化合物在提高的温度及pH下洗涤此固化膜，用亚硫酸氢钠在提高的温度下浸出洗涤过的复合材料，用多羟基化合物处理经浸出过的复合材料，回收得到的耐氯半透膜。
本发明的一种特定方案是按下述方法制备的耐氯半透膜：将含有乙二醇和碳酸钠的间-苯二胺的水溶液流涂在聚砜垫衬材料上，除去多余的溶液，使此有涂层的聚砜与苯三甲酰氯的石脑油溶液相接触，在约20°至约150℃温度范围内将所得的复合材料固化约10分钟至约2小时，使此复合材料在约20°至约100℃的温度下及pH在约9至约11的条件下用碳酸钠处理，用亚硫酸氢钠在约20°至约100℃的温度下浸取已处理过的膜。此浸取过的膜可用甘油进一步处理或在20°-100℃进一步加热。
其它的目的及具体方案可在下面对本发明更详细的叙述中找到。
如前所述，本发明涉及耐氯半透膜及这些膜的制备方法。这些膜的制备法如下：将芳族多胺的水溶液流涂在多孔垫衬支持材料上，用撑压、辊压、海绵擦试法、气刀刮试法（air knifing）或其他适当的技术除去多余的溶液，然后使此有涂层的支持材料和芳族多酰卤的有机溶剂溶液接触。用于制备这种芳族多酰卤溶液的有机溶剂是与水溶液不混溶的或不大混溶的，这样就可能在支持材料表面上形成界面缩聚反应产物。所得的复合材料被固化后得到在盐分排除、流通量及耐氯等方面显出良好特性的半透膜。
正如前面讨论过的，这种类型的膜已在美国专利4，277，344中已有陈述。此种膜被认为包含多处有下式的结构：
Ar（CONH-）2COOH
其中Ar代表作为其中一个组分的所用多官能团芳基卤的芳香核残基。现已发现，使用含有多羟基化合物和吸酸剂的芳族多胺水溶液，而且其pH值保持在大约9至约11的条件下，当其与芳族多羧酰卤的有机溶剂溶液相接触时，就会形成这样一种膜，所得的膜在渗透率及分离特性等方面将明显超过按美国专利4，277，344方法（未使用多羟基化合物）所制得膜的优异特性。本发明膜和美国专利4，277，344膜之间另一个不同点是：由于反应介质的高pH值和吸酸剂的应用，所以任何COOH单位都将以羧酸盐的形式而不是以不解离的羧酸形式存在。
在一个具体方案中，本发明的耐氯半透膜可以通过将芳族多胺的水溶液涂布在多孔支持垫衬材料上而制得，此水溶液的组成后面将较详细地叙述。这种多孔支持垫衬材料包括具有一定孔径的聚合物材料，其孔径要大到容许渗透物通过但又不能干扰超薄反渗透膜的桥连作
用。在本发明的优选实施方案中，多孔支持垫衬材料的孔径为约1至5000毫微米，因为孔径超过5000毫微米时，将使这超薄反渗透膜凹陷入孔内，这样就破坏了作为膜所需特性的平坦面的形状。可以用于制备本发明所需膜的复合材料的多孔支持垫衬材料的实例包括这样一些聚合物：例如聚砜、聚碳酸酯、微孔聚丙烯、各种聚酰胺，聚酰亚胺、聚苯醚，各种卤化聚合物（如聚偏氟乙烯）等等。
多孔支持垫衬材料可将单体多胺水溶液或取代的单体多胺水溶液（为提供更耐环境浸蚀的膜）用手涂法或连续操作法涂布。这些单体多胺可以包括例如哌嗪等环多胺;甲基哌嗪、二甲基哌嗪等取代环多胺;间-苯二胺、邻-苯二胺、对-苯二胺等芳族多胺;氯代苯二胺、N，N′-二甲基-1，3-苯二胺等取代芳族多胺;联苯胺等多芳环多胺;3，3′-二甲基联苯胺、3，3′-二氯联苯胺等取代多芳环多胺;或上述各物的混合物，这取决于分离要求和对所得膜的环境稳定性要求。作为芳香多胺载体的溶液包括水和占溶液重量约0.1至5%的芳香多胺。水溶液的另一组份包括如乙二醇、丙二醇、甘油、其它长碳链的二醇即（C4-C12）二醇、聚乙二醇、聚丙二醇、乙二醇与丙二醇的共聚物等多羟基化合物，它们可以单独使用亦可互相混合使用。这水溶液亦也可包含碱性吸酸剂，例如氢氧化钠、氢氧化钾、碳酸钠、碳酸钾等。水溶液中多羟基化合物存在量约为5至90%;而吸酸剂含量较小，约为5至500ppm。再者，此水溶液的pH值保持在较高值，约9至11。
用芳族多胺水溶液涂布多孔支持垫衬材料之后，用上述适当方法除去多余的溶液，然后将此有涂层的支衬材料和芳族多酰卤有机溶剂溶液相接触。可被使用的芳族多酰卤的实例包括如苯三甲酰氯（1，
3，5-三甲酰氯苯）、间苯二甲酰氯、对苯二甲酰氯、苯三甲酰溴（1，3，5-三甲酰溴苯）、间苯二甲酰溴、对苯二甲酰溴、苯三甲酰碘（1，3，5-三甲酰碘）、间苯二甲酰碘、对苯二甲酰碘等二-或三-酰卤，以及二-三酰卤、三-三酰卤的混合物，即苯三甲酰卤以及苯二甲酰卤异构体的混合物。这些二或三酰卤可以被取代，使它们更加耐环境腐蚀。此外，在本发明的优选实施方案中，芳族多酰卤在有机溶剂溶液中的含量约为此溶液重量的0.01至5%。本发明方法中所用的有机溶剂将包括那些不溶于水的、不溶或不太溶解多羟基化合物的溶剂，例如正戊烷、正己烷、正庚烷、环戊烷、环己烷、甲基环戊烷、石脑油等烷烃，或如氟利昂系列的卤化碳氢化合物溶剂或卤化溶剂。应该了解，上面所到的多羟基化合物、吸酸剂、芳族取代或未取代多胺、芳族多酰卤及有机溶剂等，只是可以使用该类化合物的代表而已，本发明没有必要局限于此。
因为芳族多胺的有机溶剂与水溶剂混合物本身是不溶混的或不相容的，因此膜的两个组分的聚合实质上将只在此两个溶剂相的界面处发生，因此包括薄膜的界面聚合反应物将在界面处生成。生成此薄膜所需的接触时间将在约1至约60秒的宽广范围内变动。在多孔支持垫衬材料表面上形成界面聚合反应产物之后，可以固化所得的复合材料，以便除去任何所剩的溶剂及反应物，并牢固地粘贴此薄膜在支持材料的表面上。此复合膜的固化可在一个宽的温度范围进行，所说的温度范围为从室温（20°-25℃）直至约150℃，固化时间约从1分钟至约2小时或更长。时间和温度等操作参数是相关联的，膜固化的主要标准是所说的固化时间足以得到所需的膜而又不影响此薄膜及多孔垫衬支持材料的所需特性。例如，过长的加热或固化时间可能
影响垫衬材料上孔的大小，这将会降低膜的所需流通速率。
随后将对此耐氯膜复合材料进行后处理，即用pH为约9至11的碱性物质水溶液洗涤此膜。此溶液的碱度将由例如氢氧化钠、氢氧化钾、氢氧化锂、碳酸钠、碳酸钾、碳酸锂等碱性化合物所提供。洗涤时的温度从约20°至约100℃，洗涤时间约1至约15分钟。
此膜洗涤之后，将膜进行浸取，使膜上仍可能存在的未反应的芳族多胺得以除去。因为胺可能会氧化膜和使膜变色以及在装置的出口处引起膜的后处理问题，这样多胺的除去是必要的。未反应的芳族多胺的浸取可以用例如亚硫酸氢钠这类物质在温度从约20°至约100℃下处理所说膜约1至5分钟的方法进行。在本发明优选的具体方案中，浸取液中存在的亚硫酸氢钠浓度范围从约0.5至约1%。可以使用的另外的浸取物质包括氨基磺酸等有机酸或硝酸等无机酸。
浸取处理之后，耐氯半透膜用例如甘油等多羟基化合物进一步处理，可以存在的甘油浓度约为从10至50%（体积比），此处理的目的在于保护此薄膜在处理时免遭损坏以及避免此膜变干，后一种情况将导致在分离方法中使用时膜性能的损失。
在本发明的范围内亦考虑了可采用连续操作法制备耐氯半透膜。采用这类型的操作时，使上面已较详细叙述过的多孔支持垫衬材料连续地通过一个含有多羟基化合物和吸酸剂的芳族多胺水溶液液槽。通过液槽之后，垫衬材料被连续地拉出，用适当的方法将可能存在的多余溶液除去。然后使已有涂层的支持材料再连续地通过芳族多酰卤在有机溶剂中的溶液。在和此溶液接触时间内发生界面聚合反应，其后在多孔支持垫衬物材料表面上包含薄膜状界面聚合反应产物的半透膜的复合材料被固化，例如，其方法为使其按一个预先调好的速度通过
一个保持所需固化温度的烘炉，以避免此复合物膜任何可能的损坏。此后，此膜被连续地从固化炉拉出，又连续地通过洗涤、浸取和涂布区作后处理，便得到所要的膜。
所得的耐氯半透膜然后可以用于所需的分离方法中，例如海水脱盐、半咸水脱盐：以及，如硬水的软化等水的其他处理，借此以除掉盐份煮沸所说的处理水，乳清或果汁的浓缩，等等。平片形的膜特别适用于组件或单板设备或多层板并联设备，为此将一片或数片膜卷绕成盘旋状结构。
下面的实例是为了详细说明按照前面叙述的方法制造出来的新型耐氯半透膜，以及作为分离作用物用途而提供的。然而，应该知道，提出这些实例仅仅是为了描述的目的，本发明并不受此所限。
实例Ⅰ
一种耐氯半透膜可按下法制备：使一块多孔聚砜平片通过含有22%（重量）间-苯二胺、70ppm碳酸钠和5%（体积）乙二醇的水溶液。使此聚砜平片接触pH为9.85的此溶液30秒。负载有水溶液混合物的膜在室温下空气干燥约15分钟，然后使其通过含0.15%（重量）苯三甲酰氯的石脑油溶液15秒。接着使此膜状复合材料在21.7℃温度下在空气中干燥23分钟。
此膜的后处理为：在室温下用pH为10.0的碳酸钠溶液洗涤膜5分钟。后处理的浸取步骤是：在40℃温度下用亚硫酸氢钠溶液处理此膜5分钟。最后，在此膜上涂布20%的甘油溶液。此膜记为膜A。
实例Ⅱ
第二个膜的制备方法与前面实例1所述的相似，将聚砜平片通过
含量为2.1%（重量）的间-苯二胺的水溶液，此溶液内含有70ppm的碳酸钠和20%（体积）的乙二醇，溶液的pH值为9.4。使此聚砜平片接触这个溶液30秒，然后将其拉出，多余的溶液用上面所述的相似方法除去。已有涂层的聚砜片然后通过0.1%（重量）的苯三甲酰氯的石脑油溶液15秒钟，然后在21.7℃温度下在流动的气流中干燥20分钟。
所得膜的后处理：室温下用碳酸钠溶液漂洗5分钟，漂洗液的pH值为10.0。之后，残余的间-苯二胺用亚硫酸氢钠溶液在40℃温度下处理5分钟的方法除去，然后涂布甘油溶液。此膜记为膜B。
实例Ⅲ
第三个膜的制备：将聚砜片通过一含多胺为2.1%（重量）的间-苯二胺水溶液，此水溶液含有70ppm的碳酸钠及50%（体积）的乙二醇。此有涂层的聚砜片用上述相似的方法处理，即在相同的条件下使之通过含0.15%（重量）的苯三甲酰氯石脑油溶液。所得膜的后处理亦相似于上面所述的方法，此膜记为膜C。
实例Ⅳ
为比较其结果，除了水溶液中不含乙二醇，即实质上是100%的水溶液外，制备了相似的膜。其余步骤与上面所述相同，经后处理所得的膜记为膜D。
实例Ⅴ
同样为了作比较，按照美国专利4，277，344所述的方法制备了两种膜。第一种膜的制备方法是将聚砜片通过含2.0%（重量）间-苯二胺的水溶液36秒。取出带涂层的聚砜片，除去多余的
溶液，涂层片通过含0.1%（重量/体积）苯三甲酰氯的三氯三氟乙/烷溶液10秒钟。此膜在空气中23.3℃温度下干燥。
第二种膜亦按上段文字所述的方法制备，在空气中干燥以后用含100ppm次氯酸盐的溶液在室温下处理20小时，即得到此膜。在本例中的第一种膜记为膜E，而第二种膜记为膜F。
实例Ⅵ
将按照上面各例的方法制备的各膜放置于渗透池内，使含氯化钠2克/升的配制的半咸水通过膜的表面，流速为5.68升/分，实验时所用的测试条件包括：膜的一面的压力为1516。85Kpa（表压），而另一面保持大气压。在整个实验中温度保持在25℃，而供料水的pH保持为5.5。检测从渗透池中收集的渗透物，测定氯化钠的排除率和流通速率。这些测试结果列于下表。
表
膜 D A B C E F
流通速率 929 1087.9 1344.6 1320.2 884.2 1052.9
（l/m2/d）
排除率（%）98.5 98.6 98.7 95.3 96.3 95.99
从上表可以看到，按本发明的方法在水溶液中使用乙二醇及碳酸钠制备的并如上各例所详述的方式作后处理的膜，与按美国专利4，277，344的方法制备的膜或在水溶液中不加乙二醇时制备的膜相比较，在相近或较大的盐排除率时显示更高的流通速率。
Claims (10)
1、耐氯半透膜，其制备方法为：使含有5-90%(体积)多羟基化合物的芳族多胺或环多胺水溶液流涂在多孔支持垫衬材料上，除去多余溶液，使此有涂层的多孔支持材料和芳族多羧酰囟有机溶剂溶液相接触，在所说的多孔支持材料表面上生成界面缩合反应产物，环境温度下固化所得的复合材料1分钟至2小时，形成所说的耐氯半透膜。
2、权利要求1所述的耐氯半透膜，其中所述芳族多胺包括间苯二胺、邻苯二胺、对苯二胺、4-氯苯二胺、5-氯苯二胺、N，N′-二甲基-1，3-苯二胺、联苯胺、3，3′-二甲基联苯胺、3，3′-二氯联苯胺或其混合物;或者所述环多胺包括环多胺哌嗪、甲基哌嗪、二甲基哌嗪或其混合物。
3、权利要求1所述的耐氯半透膜，其中所述芳族多羧酰囟包括间苯二酰氯、苯三甲酰氯或对苯二酰氯。
4、权利要求1所述的耐氯半透膜，其中所述多羟基化合物包括乙二醇、甘油、丙二醇或聚乙二醇。
5、权利要求1所述的耐氯半透膜，其进一步的特征在于所述水溶液含吸酸剂。
6、权利要求1所述的耐氯半透膜，其中所述水溶液的pH值在9至11范围内。
7、权利要求1所述的耐氯半透膜，其进一步的特征在于所述膜经过碱性化合物处理。
8、权利要求1所述的耐氯半透膜，其进一步的特征在于所述耐氯半透膜在经所述碱性化合物处理之后再经浸取处理。
9、权利要求1所述的耐氯半透膜，其中所述耐氯半透膜在所述浸取处理之后再用多羟基化合物进一步处理，以便在所述膜上形成涂布层。
10、制备耐氯半透膜的方法，此方法包括：将含有5-90%（体积）多羟基化合物及吸酸剂的芳族多胺或环多胺水溶液流涂在多孔支持垫衬材料上，除去多余的溶液，使此有涂层的多孔支持材料和一个芳香多羧酰囟的有机溶剂溶液相接触，在所说的多孔支持材料表面上生成界面缩合反应产物，在固化条件下固化所得复合材料，用碱性化合物在提高的温度及pH下洗涤此固化膜，在提高的温度下用亚硫酸氢钠浸取此洗涤过的复合材料，用多羟基化合物处理此浸取过的复合材料，回收得到的耐氯半透膜。
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/059,295 US4830885A (en) | 1987-06-08 | 1987-06-08 | Chlorine-resistant semipermeable membranes |
| AT89908103T ATE82703T1 (de) | 1987-06-08 | 1989-03-16 | Chlorbestaendige halbdurchlaessige membranen. |
| EP19890908103 EP0462967B1 (en) | 1987-06-08 | 1989-03-16 | Chlorine-resistant semipermeable membranes |
| AU39661/89A AU634717B2 (en) | 1987-06-08 | 1989-03-16 | Chlorine-resistant semipermeable membranes |
| KR1019910701096A KR970006838B1 (ko) | 1987-06-08 | 1989-03-16 | 내염소성 반투막 및 그 제조방법 |
| PCT/US1989/001087 WO1990010494A1 (en) | 1987-06-08 | 1989-03-16 | Chlorine-resistant semipermeable membranes |
| ZA892353A ZA892353B (en) | 1987-06-08 | 1989-03-30 | Chlorine-resistant semipermeable membranes |
| CN89102360A CN1029824C (zh) | 1987-06-08 | 1989-04-17 | 耐氯半透膜 |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/059,295 US4830885A (en) | 1987-06-08 | 1987-06-08 | Chlorine-resistant semipermeable membranes |
| ZA892353A ZA892353B (en) | 1987-06-08 | 1989-03-30 | Chlorine-resistant semipermeable membranes |
| CN89102360A CN1029824C (zh) | 1987-06-08 | 1989-04-17 | 耐氯半透膜 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1046472A CN1046472A (zh) | 1990-10-31 |
| CN1029824C true CN1029824C (zh) | 1995-09-27 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89102360A Expired - Fee Related CN1029824C (zh) | 1987-06-08 | 1989-04-17 | 耐氯半透膜 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4830885A (zh) |
| EP (1) | EP0462967B1 (zh) |
| KR (1) | KR970006838B1 (zh) |
| CN (1) | CN1029824C (zh) |
| AT (1) | ATE82703T1 (zh) |
| AU (1) | AU634717B2 (zh) |
| WO (1) | WO1990010494A1 (zh) |
| ZA (1) | ZA892353B (zh) |
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| US9795928B2 (en) | 2014-06-24 | 2017-10-24 | Nano And Advanced Materials Institute Limited | Stepwise interfacial polymerization technique with different reagent solution designs to prepare hollow fiber nanofiltration membrane composites |
| CN105771700A (zh) * | 2014-12-15 | 2016-07-20 | 华东理工大学 | 采用混合二胺单体的耐氯纳滤膜及其制备方法 |
| US9861940B2 (en) | 2015-08-31 | 2018-01-09 | Lg Baboh2O, Inc. | Additives for salt rejection enhancement of a membrane |
| US9737859B2 (en) | 2016-01-11 | 2017-08-22 | Lg Nanoh2O, Inc. | Process for improved water flux through a TFC membrane |
| US10155203B2 (en) | 2016-03-03 | 2018-12-18 | Lg Nanoh2O, Inc. | Methods of enhancing water flux of a TFC membrane using oxidizing and reducing agents |
| KR102622770B1 (ko) * | 2016-10-26 | 2024-01-10 | 이엠디 밀리포어 코포레이션 | 셀룰로스-함유 필터 재료로부터의 침출물 베타-글루칸 수준의 감소 |
| US10646829B2 (en) | 2017-06-22 | 2020-05-12 | Teledyne Scientific & Imaging, Llc | High flux, chlorine resistant coating for sulfate removal membranes |
| CN109603587A (zh) * | 2018-11-16 | 2019-04-12 | 蓝星（杭州）膜工业有限公司 | 一种抗氧化不变色复合反渗透膜的制备方法 |
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| US3920612A (en) * | 1963-01-21 | 1975-11-18 | Standard Oil Co | Preparation of film forming polymer from carbocyclic aromatic diamine and acyl halide of trimellitic acid anhydride |
| US3260691A (en) * | 1963-05-20 | 1966-07-12 | Monsanto Co | Coating compositions prepared from condensation products of aromatic primary diamines and aromatic tricarboxylic compounds |
| US3480588A (en) * | 1963-08-20 | 1969-11-25 | Monsanto Co | Stable coating composition of a tricarboxylic acid or its partial or full ester and a diamine |
| US4048144A (en) * | 1966-11-25 | 1977-09-13 | Standard Oil Company (Indiana) | Preparation of solid polymers from aromatic primary diamine and acyl halide of trimellitic anhydride |
| US3567632A (en) * | 1968-09-04 | 1971-03-02 | Du Pont | Permselective,aromatic,nitrogen-containing polymeric membranes |
| US3710945A (en) * | 1969-11-26 | 1973-01-16 | Du Pont | Preservation of polyamidic membranes |
| US3600350A (en) * | 1970-04-20 | 1971-08-17 | Du Pont | Poly(p-benzamide) composition,process and product |
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| IL64967A0 (en) * | 1981-03-17 | 1982-04-30 | Aligena Ag | Semipermeable membranes containing modified polysulfones,their manufacture and their use |
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| US4830885A (en) * | 1987-06-08 | 1989-05-16 | Allied-Signal Inc. | Chlorine-resistant semipermeable membranes |
| US4792404A (en) * | 1988-03-28 | 1988-12-20 | Allied-Signal Inc. | Desalination of saline water |
-
1987
- 1987-06-08 US US07/059,295 patent/US4830885A/en not_active Expired - Fee Related
-
1989
- 1989-03-16 KR KR1019910701096A patent/KR970006838B1/ko not_active IP Right Cessation
- 1989-03-16 WO PCT/US1989/001087 patent/WO1990010494A1/en active IP Right Grant
- 1989-03-16 EP EP19890908103 patent/EP0462967B1/en not_active Expired - Lifetime
- 1989-03-16 AT AT89908103T patent/ATE82703T1/de not_active IP Right Cessation
- 1989-03-16 AU AU39661/89A patent/AU634717B2/en not_active Ceased
- 1989-03-30 ZA ZA892353A patent/ZA892353B/xx unknown
- 1989-04-17 CN CN89102360A patent/CN1029824C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ATE82703T1 (de) | 1992-12-15 |
| AU3966189A (en) | 1990-10-09 |
| EP0462967B1 (en) | 1992-11-25 |
| WO1990010494A1 (en) | 1990-09-20 |
| CN1046472A (zh) | 1990-10-31 |
| AU634717B2 (en) | 1993-03-04 |
| KR970006838B1 (ko) | 1997-04-30 |
| US4830885A (en) | 1989-05-16 |
| ZA892353B (en) | 1989-12-27 |
| KR920702824A (ko) | 1992-10-28 |
| EP0462967A1 (en) | 1992-01-02 |
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