GB2352722A - Composite polyamide reverse osmosis membrane - Google Patents
Composite polyamide reverse osmosis membrane Download PDFInfo
- Publication number
- GB2352722A GB2352722A GB9918111A GB9918111A GB2352722A GB 2352722 A GB2352722 A GB 2352722A GB 9918111 A GB9918111 A GB 9918111A GB 9918111 A GB9918111 A GB 9918111A GB 2352722 A GB2352722 A GB 2352722A
- Authority
- GB
- United Kingdom
- Prior art keywords
- amine
- aqueous solution
- polyfunctional
- membrane
- salt
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 102
- 239000004952 Polyamide Substances 0.000 title claims abstract description 41
- 229920002647 polyamide Polymers 0.000 title claims abstract description 41
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 86
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002798 polar solvent Substances 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 48
- 150000001412 amines Chemical class 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 61
- -1 isophthaloyl halide Chemical class 0.000 claims description 49
- 150000003512 tertiary amines Chemical group 0.000 claims description 39
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 34
- 239000000376 reactant Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 150000001266 acyl halides Chemical class 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 16
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- 150000003461 sulfonyl halides Chemical class 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 12
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 claims description 6
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 4
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 claims description 4
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 4
- 125000004427 diamine group Chemical group 0.000 claims 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 abstract description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 37
- 230000004907 flux Effects 0.000 abstract description 23
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 abstract description 19
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 abstract description 9
- 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 abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 abstract 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 13
- 229940098779 methanesulfonic acid Drugs 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 5
- 150000003462 sulfoxides Chemical class 0.000 description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 229940093475 2-ethoxyethanol Drugs 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 125000005270 trialkylamine group Chemical group 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical class C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010406 interfacial reaction Methods 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 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 description 2
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HTXVEEVTGGCUNC-UHFFFAOYSA-N heptane-1,3-diol Chemical compound CCCCC(O)CCO HTXVEEVTGGCUNC-UHFFFAOYSA-N 0.000 description 2
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-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
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZBEPMOZEXLGCTF-UHFFFAOYSA-N O=C(C1CC1)N1CCCC(C1)NC1=NC(=CC=N1)N1C(CC#N)=CN=C1C1=CC2=C(OC=C2)C=C1 Chemical compound O=C(C1CC1)N1CCCC(C1)NC1=NC(=CC=N1)N1C(CC#N)=CN=C1C1=CC2=C(OC=C2)C=C1 ZBEPMOZEXLGCTF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 241000206607 Porphyra umbilicalis Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a composite polyamide reverse osmosis membrane and method of producing the same. In one embodiment, the membrane is made by coating a porous polysulfone for about 40 seconds with an aqueous solution containing (i) a polyfunctional amine in the form of 2 wt % of meta-phenylenediamine (MPD), (ii) a polar solvent in the form of 0.3 wt % 2-ethyl-1,3-hexanediol (EHD), and (iii) an amine salt-forming combination of 2.3 wt % camphorsulfonic acid (CSA) and 1.1 wt % triethylamine (TEA). Next, the excess aqueous solution is removed, and the coated support is dipped for about 1 minute in a 0.1 wt % organic solvent solution of trimesoyl chloride (TMC) in a mixture of alkanes having from 8 to 12 carbon atoms. After draining the organic solvent solution off, the resulting composite membrane is heated at 90{C for about 3.5 minutes and then rinsed in a 0.2% Na<SB>2</SB>CO<SB>3</SB> aqueous solution at room temperature. The resultant membrane exhibits a flux of 47.9 gfd and a salt rejection of 97.6% when used at 225 psi for an aqueous solution containing 2000 ppm of NaCl. In another embodiment, the aqueous solution contains (i) a polyfunctional amine in the form of 2 wt % of MPD, (ii) a combination of polar solvents in the form of 0.3 wt % of EHD and 2 wt % of dimethyl sulfoxide, and (iii) an amine salt-forming combination of 1 wt % of 1,1,3,3-tetramethylguanidine and 1.6 wt % toluene sulfonic acid. The resultant membrane exhibits a flux of 63.7 gfd and a salt rejection of 90.8% when used at 225 psi for an aqueous solution containing 2000 ppm of NaCl.
Description
2352722
COMPOSITE POLYAMEDE REVERSE OSMOSIS MEMBRANE AND METHOD OF PRODUCING THE SAIME BACKGROUND OF THE EVVTINTION
The present invention relates generally to reverse osmosis, membranes and more particularly to a novel composite polyamide reverse osmosis membrane and to a method of producina, the same.
It is known that dissolved substances can be separated from their solvents by the use of various types of selective membranes, examples of such membranes including microfiltration membranes, ultrafiltration membranes and reverse osmosis membranes. One use to which reverse osmosis membranes have previously been put is in the desalination of brackish water or seawater to provide large volumes of relatively non-salty water suitable for industrial, acricultural or home use. What is involved in the desalination of brackish water or seawater using reverse osmosis membranes is literally a filtering out of salts and other dissolved ions or molecules from the salty water by forcing the salty water through a reverse osmosis membrane whereby purified water passes through the membrane while salts and other dissolved ions and molecules do not pass throuah the membrane. Osmotic pressure works against the reverse osmosis process, and the more concentrated the feed water, the greater the osmotic pressure which must be overcome.
A reverse osmosis membrane, in order to be commercially useful in desalinatina brackish water or seawater on a large scale, must possess certain properties. One such property is that the membrane have a high salt rejection coefficient. In fact, for the desalinated water to be suitable for many conunercial applications, the reverse osmosis membrane should have a salt rejection capability of at least about 97%. Another important property of a reverse osmosis 1 membrane is that the membrane possess a high flux characteristic, i.e., the ability to pass a - ZD relatively large amount of water through the membrane at relatively low pressures. Typically, the flux for the membrane should be greater than 10 gallons/ft2-da (-fd) at a pressure of 800 1 t__ y 0 psi for seawater and should be greater than 15 gfd at a pressure of 220 psi for brackish water. More preferably, the flux for the membrane is at least about 22 gfd at brackish water conditions. For certain applications, a rejection rate that is less than would otherwise be desirable may be acceptable in exchange for higher flux and vice versa.
One common type of reverse osmosis membrane is a composite membrane comprisin1c, a porous support and a thin polyamide film formed on the porous support. Typically, the polyamide film is formed by an interfacial polymerization of a polyfunctional amine and a polyfunctional acyl halide.
An example of the aforementioned composite reverse osmosis membrane is disclosed in U.S. Patent No. 4,277,344, inventor Cadotte, which issued July 7, 1981, and which is incorporated herein by reference. The aforementioned patent describes an aromatic polyamide film which is the interfacial reaction product of an aromatic polyamine baving at least two primary amines substituents with an aromatic acyl halide having at least three acyl halide substituents. In the preferred embodiment, a porous polysulfone support is coated with mphenylenediamine in water. After removal of excess m-phenylenediamine solution from the coated support, the coated support is covered with a solution of trimesoyl chloride dissolved in "FREON" TF solvent (trichlorotrifluoroethane). The contact time for the interfacial reaction is 10 seconds, and the reaction is substantially complete in I second. The resulting polysulfone/polyamide composite is then air-dried.
Althouch the Cadotte membrane. described above exhibits good flux and good salt rejection, various approaches have been taken to further improve the flux and salt rejection of composite polyamide reverse osmosis membranes. In addition, other approaches have been taken to improve the resistance of said membranes to chemical degradation and the like. Many of these approaches have involved the use of various types of additives to the solutions used in the interfacial polycondensation reaction.
For example, in U.S. Patent No. 4,872,984, inventor Tomaschke, which issued October 10, 1989, and which is incorporated herein by reference, there is disclosed an aromatic polyamide membrane formed by (a) coating a microporous support with an aqueous solution comprising (i) an essentially monomeric, aromatic, polvarnine reactant having at least two amine functional groups and (ii) an amine salt to form a liquid layer on the microporous support, (b) contacting the liquid layer with an organic solvent solution of an essentially monomeric, ?D aromatic, amine-reactive reactant comprising a polyfunctional acyl halide or mixture thereof, wherein the amine-reactive reactant has, on the avera2e, at least about 2.2 acyl halide groups per reactant molecule, and (c) drying the product of step (b) so as to form a water permeable membrane.
The amine salt of Tomaschke is a monofunctional, monomeric (i.e., polymerizable) amine. Preferably, said amine salt is a water soluble salt of a stroncr acid and a tertiary amine selected from the group consisting of a trialkylamine, such as trimethylamine, triethylamine, tripropylamine; an N-alkylcycloaliphatic amine, such as 1-methylpiperidine; an N,Ndialkylamine, such as N,N-dimethylethylamine and N,N-diethylmethylamine; an NNdialk-yl ethanolamine, such as N,N-dimethylethanolamine; a bicyclic tertiary amine, such as 33- quinuclidinol; and mixtures thereof, or is a quaternary amine selected from at least one member of the group consisting of a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide, tetraethylammoniurn hydroxide and tetrapropylammonium hydroxide; a benzy1trialkylammonium hydroxide, such as benzy1trimethylammonium hydroxide, benzyltriethylammonium hydroxide and be nzy ltrip ropy] arnmo nium hydroxide; and mixtures thereof.
In U.S. Patent No. 4,983,291, inventors Chau et al., which issued January 8, 1991, and which is incorporated herein by reference, there is disclosed a membrane which comprises a polymerized reaction product within and/or on a porous support backing material. According to the Chau et al. patent, said membrane may be prepared by contacting a porous support with an aqueous solution of a polyamine which may, if so desired, contain a polar aprotic solvent not reactive with the amines, a polyhydric compound and an acid acceptor. The polyhydric compound, which may include ethylene glycol, propylene glycol, glycerin and other longer I I Z:1 carbon atom backbone glycols, may be present in the aqueous solution in an amount ranging Z. -D from about 0. 1 to about 50%. The surface of the coated support is freed of excess solution and thereafter contacted with an organic solution of a polyacyl halide for a period of time sufficient Z:
to form a polymerized reaction product within and/or on the support material. The resulting composite is then treated with a h droxypolycarboxylic acid, polyaminoalkylene polycarboxylic y I acid, sulfonic acid, amine salts of acids, amino acid, amino acid salt, polymeric acid and inoraaaic acid, before drying of the membrane.
In U.S. Patent No. 5,576,057, inventors Hirose et al., which issued November 19, 1996, and which is incorporated herein by reference, there is disclosed a composite reverse osmosis 4 membrane comprising a polyamide type skin layer on a potous ZD support, said membrane being formed by coating a solution A containing a compound having at le ast two reactive amino groups on the porous support and, thereafter, contacting a solution B containing a polyfunctional acid halide with the coated layer of solution A, wherein the difference between a solubility parameter of solution A and a solubility parameter of solution B is from 7 to 15 (cal/cm')"'2.
Examples of the solvent for solution A set forth in Hirose et a]. ('057) are a mixed solvent of water and an alcohol such as ethanol, propanol, butanol, butyl alcohol, 1-pentanol, 2-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2 ethylbutanol, 2-ethythexanol, octanol, cyclohexanol, tetrahydrofurftiryl alcohol, neopentyl glycol, t-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3)-methyl-2-butanol, pentyl alcohol, allyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propanediol, I Z) Im butanediol, pentanediol, hexanediol, glycerol, etc.; and a mixed solvent of water and a nitrogen compound such as nitromethane, fon-narnide, methylformamide, acetonitrile, dimethy1formamide, ethy1formamide, etc. As an example of the mixing ratio of water and the other solvent of solution A, Hirose et al. ('Q57) states that the mixing ratio of water/ethanol can be selected in the range of (50 to 90)/(50 to 10), and preferably (60 to 90)/(40 to 10). Hirose et al. ('057) elsewhere states that the amine salts described in JP-A-2-187135 (corresponding to U.S. Patent No. 4,872, 984), such as a salt of a tetraalkylammonium halide or a trialkylarnine and an organic acid can also be suitably used for the solution A to facilitate the film formation, improve the absorption of the amine solution in the support, and accelerate the condensation reaction.
In U.S. Patent No. 5,614,099, inventors Hirose et al., which issued March 25, 1997, and which is incorporated herein by reference, there is disclosed a composite reverse osmosis Cy I membrane having a polyamide type skin layer whose average surface roughness is at east 55 nm. The polyamide type skin layer comprises the reaction product of a compound having amino groups and a polyfunctional acid halide compound having acid halide groups. A polymer film may be formed by contacting a solution containing, for example, m- phenylenediamine with a porous polysulfone supporting film so as to form a la er of the solution on the supporting film, 17 y I= then contacting the film with a solution of trimesic acid chloride and holding the film in a hot air dryer so that a polymer film is formed on the supporting film. The surface of the polyamide type skin layer can also be treated with quaternary ammonium salt and coated with a cross- linked layer of an organic polymer having positively-charged groups.
According to Hirose et al. ('099), the compound having multiple amino groups is preferably present in a solution A, said solution A comprising a compound having a solubility parameter of 8-14 (cal/cml)"', said compound being selected from the group consisting of certain alcohols, ethers, ketones, esters, halogenated hydrocarbons and sulfur-containing compounds. Specific examples of said compound are disclosed in the Hirose et al. ('099) patent. Elsewhere, Hirose et al. ('099) states that the amine salts described in P-A-2-187135, such as a salt of a tetraalkylammonium halide or a trialkylamine and an organic acid can also be suitably used for the solution to facilitate the film formation, improve the absorption of the amine solution in the support, and accelerate the condensation reaction.
Although the membranes described above possess a relatively high degree of water 1 Zz - permeability, it is nonetheless still desirable to further improve the flux of these types of membranes so that they can be operated at lower pressures, such as at 120 psi, in order to conserve energy while still maintaining a high degree of salt rejection.
ZI 6 Other patents of interest include U.S. Patent No. 4,950,404, inventor Chau, issued August 21, 1990; U.S. Patent No. 4,761,234, inventors Uemura et al., which issued August 2, 1988, and U.S. Patent No. 4,769, 148, inventors Fibiger et al., which issued September 6, 1988, all of which are incorporated herein by reference.
7 SUMMARY OF THE F4VENTION it is an object of the present invention to provide a novel polyamide membrane.
According to one aspect of the invention, there is provided a polyamide membrane comprising, a reaction product of (i) an aqueous solution comprising a polyfunctional amine, a salt-containincy compound and one or more polar solvents, said salt-containincy compound comprising at least one amine salt functional group and at least one amine functional group, and (ii) an orcranic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
Preferably, said amine salt functional group is a tertiary amine salt functional group, and said amine functional group is a tertiary amine functional group. Moreover, said salt-containing compound is preferably the reaction product of a strong acid and a polyfunctional tertiary amine. Preferred examples of said strong acid include methanesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, ethanesulfonic acid and benzenesulfonic acid. Preferred examples of said polyfunctional tertiary amine include 1, 4-diazabicyclo [2,2,2] octane, 1,8diazabicyclo[5,4, O]undec-7-ene, N, N, N, N'-tetrame thy 1- 1, 3 -butaned iamine, N, N, N', N' tetramethyl-1,6-hexanediamine, N, N, N', N', N " -pentame thy Id iethy lenetriam ine, 1, 1,31,3tetramethylauanidine, N,N,N,N'tetramethylethylenediamine, substituted imidazoles including 1,2dimethylimidazole and 1-alkyl-substituted imidazoles, and mixtures thereof.
Said one or more polar solvents are preferably selected from the group consisting of 1 4:1 ethylene cylvcol derivatives, propylene glycol derivatives, 1,3- propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives and urea derivatives. Preferred examples of 8 said polar solvents include alkoxyethanols-, such as 2-methoxyethanol, 2- ethoxyethanol, 2propoxyethanol, and 2-butoxyethanol, I-pentanol, 1- butanol, di(ethylene glycol) t-butylmethyl ether, di(ethylene glycol)hexyl ether, propylene glycol butyl ether, propylene glycol propyl ether, 1,3-heptanediol, 2-ethyl-1,3-hexanediol, 1,3-hexanediol, 1,3- pentanediol, dimethyl sulfoxide, tetramethylene sulfoxide, butyl sulfoxide, methylphenyl sulfoxide, tetramethylene sulfone, butyl sulfone, acetonitrile, propionitrile and 1,3-dimethyl-2-i.Tnidazolidinone.
Said one or more polar solvents are also preferably present in said aqueous solution in a total amount constituting about 0.01 to 8%, by weight, of said aqueous solution.
According to another aspect of the invention, there is provided a polyarnide membrane comprising a reaction product of (i) an aqueous solution comprising a polyfunctional amine, a salt-containing, compound and one or more polar solvents, said salt-containing compound being a reaction product of a strong acid and a polyfunctional tertiary amine and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
The aforementioned polyfunctional tertiary amine has n tertiary amine functional groups, n beincr greater than or equal to 2, and said polyfunctional tertiary amine and said strong acid 0 are preferably reacted to-ether in a molar ratio that is greater than or equal to 1: 1, respectively, and is less than I:n, respectively. More preferably, said polyfunctional ter-tiary amine and said strong acid are reacted together in a molar ratio that is less than 1: (0. 95)n, respectively'. Even more preferably, said polyfunctional tertiary amine and said strong acid are reacted together in a molar ratio that is less than 1:(0.9)n, respectively.
9 According to yet another aspect o-f the invention, there is provided a polyamide fun i membrane comprising a reaction product of (i) an aqueous solution comprisi a poly ct ona amine, an amine salt and one or more polar solvents, wherein said one or more polar solvents are selected from the group consisting of 2-ethyl-1,3-hexanediol; a combination of 2-ethyl-1, 3hexanediol and dimethyl sulfoxide; di(ethylene glycol) bexyl ether; a combination of di(ethylene glycol) hexyl ether and dimeth I sulfoxide; di(ethylene glycol) t-butylmethyl ether; a combination y C of an alkoxyethanol and dimethyl sulfoxide; propylene glycol butyl ether; propylene glycol propyl ether; triethylene glycol dimethyl ether; 1,3dimethyl-2-imidazolidinone; a combination of 2-ethyl-1,3-hexanediol and acetonitrile; tetramethylene sulfoxide; butyl sulfoxide; methylphenyl sulfoxide; butyl sulfone; and mixtures thereof, and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
Preferably, said amine salt is selected from the group consisting of a quaternary ammonium salt and a reaction product of a strong acid and a tertiary amine. The tertiary amine m ay be a monofunctional tertiary amine or a polyfunctional tertiary amine.
According to still yet another aspect of the invention, there is provided a polyamide membrane comprising a reaction product of (i) an aqueous solution comprising a polyfunctional amine, an amine salt and one or more polar solvents, wherein said one or more polar solvents are selected from the group consisting of an alkoxyethanol in an amount constituting about 0.05% to about 4%, by weight, of said aqueous solution; dimethyl sulfoxide in an amount constitutins! about 0. 0 1 % to about 8 %, by weight, of said aqueous solution; a combination of an alkoxyethanol in an amount constituting., about 0.05% to about 4%, by weight, of said aqueous solution and dimethyl sulfoxide in ah amount constituting about 0. 0 1 % to about 8 %, by weight, of said aqueous solution; 1-pentanol in an amount constituting about 0.01 % to about 2%, by weight, of said aqueous solution; 1-butanol in an amount constituting about 0.01% to about 3 %, by weight, of said aqueous solution; and tetramethylene sulfone in an amount constituting about 0. 0 1 % to about 4 %, by weight, of said aqueous solution, and (ii) an organic =1 C Z solvent solution comprising an amine-reactive reactant selected from the group consisting, of a polyftinctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
Preferably, said amine salt is selected from the group consisting of a quaternary ammonium salt and a reaction product of a strong acid and a tertiary amine. The tertiary amine may be a monofunctional tertiary amine or a polyfunctional tertiary amine.
The present invention is also directed to a composite reverse osmosis membrane comprising a porous support and a polyamide membrane of the type broadly described above.
It is another object of the present invention to provide a method of producing a composite reverse osmosis membrane.
Consequently, according to a further aspect of the invention, there is provided a method of making a composite reverse osmosis membrane, said method comprising the steps of:
(a) coating a porous support with an aqueous solution comprising a polyfunctional amine, one or more polar solvents and a salt-containincompound, said salt- containing compound being a reaction roduct of a strong acid and a polyfunctional tertiary p amine, so as to form a liquid layer on said porous support; (b) contacting said liquid laver with an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfanctional sulfonyl halide and a polyfunctiorial isocyanate so as to interfacially condense said amine-reactive reactant with said polyfunctional amine, thereby forming a. cross-linked, interfacial polyarnide layer on said porous support; and (c) drying the product of step (b) to form a composite reverse osmosis membrane.
According to yet a further aspect of the invention, there is provided a method of making C> a composite reverse osmosis membrane, said method comprising the steps of:
(a) coating a porous support with a first aqueous solution, said first aqueous solution comprising one or more polar solvents and an amine salt, so as to form a first liquid layer on said porous support; (b) coating the first liquid layer with a second aqueous solution, said second aqueous solution comprising a polyfunctional amine, so as to form a second liquid layer over said first liquid layer; (c) contacting the twice-coated porous support with an organic solvent solution comprising an arnine-reactive reactant selected from the group consisting of a polyfunctional acyl Z C I halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate so as to inter-facially condense said amine-reactive reactant with said polyfunctional amine, thereby forming a crosslinked, interfacial polyamide layer on said porous support; and (d) drying the product of step (c) to form a composite reverse osmosis membrane.
According, to still yet another aspect of the invention, there is provided a method of making a composite reverse osmosis membrane, said method com rising the steps of: p (a) coating a porous support with a first aqueous solution, said first aqueous solution comprising one or more polar solvents, so as to form a first liquid layer on said porous support; (b) coating, the first liquid layer with a second aqueous solution, said second aqueous solution comprising a polyfunctional amine and an amine salt, so as to form a second liquid layer over said first liquid layer; (c) contacting the twice-coated porous support with an organic solvent solution ID comprising an arnine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate' so as to interfacially condense said amine- reactive reactant with said polyfunctional amine, thereby forming, a crosslinked, inter-facial polyamide layer on said porous support; and (d) drying the product of step (c) to form a composite reverse osmosis membrane.
Additional objects, features, aspects and advantages of the present invention will be set forth, in part, in the description which follows and, in part, will be obvious from the description or may be learned by practice of the invention. Certain embodiments of the invention will be described hereafter in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural or other changes may be made without departing from the scope of the invention. The following detailed description is, therefore, not to be taken in a limiting, sense, and the scope of the present invention is best defined by the appended claims.
DETAILED DESCRIPTION OF -PREFERRED EMBOMMENTS
As set forth above, the present invention is directed to a novel composite reverse osmosis membrane. The composite reverse osmosis membrane of the present invention comprises (a) a porous support and (b) a polyamide membrane disposed on said porous support, said polyamide membrane bein- a reaction product of (i) an aqueous solution comprising a polyfunctional amine, an amine salt and one or more polar solvents, the specific amine salt and/or one or more polar solvents used in accordance with the present invention being discussed below and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the aroup consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a ID polyfunctional isocyanate.
The porous support of the present invention is typically a microporous support. The particular microporous support employed in the present invention is not critical thereto but is -generally a polymeric material containing pore sizes which are of sufficient size to permit the passage of permeate therethrough but not large enough so as to interfere with the bridging over I 1- I-) I-D 1 of the ultrathin membrane formed thereon. The pore size of the support will generally range from I to 500 nanometers inasmuch as pores which are larger in diameter than 500 nanometers will permit the ultrathin film to saor into the pores, thus disrupting the flat sheet configuration 0 desired. Examples of microporous supports useful in the present invention include those made of a polysulfone, a polyether sulfone, a polyimide, a polyamide, polypropylene and various halogenated polymers, such as polyvinylidene fluoride. Additional microporous support materials may be found in the patents incorporated herein by reference.
14 The thickness of the microporous 'support is not critical to the present invention. Generally, the thickness of the microporous support is about 25 to 125 Am, preferably about 40 to 75 Ain.
The poIyfunctional amine reactant employed in the present invention is preferably an essentially monomeric amine having, at least two amine functional groups, more preferably 2 to 3 amine functional roups. The arnine functional group, is typically a primary or secondary 9 Z amine functional group, preferably a primary amine functional group. The particular polyarnine employed in the present invention is not critical thereto and may be a single polyamine or a combination thereof. Examples of suitable polyamines include aromatic primary diamines, such as metaphenylenediamine and para-phenylenediamine and substituted derivatives thereof, wherein the substituent includes, e.g., an alkyl group, such as a methyl group or an ethyl group, 4-- C 17 an alkoxy group, such as a methoxy group or an ethoxy group, a hydroxy alk-YI group, a hydroxy group or a halogen atom. Additional examples of suitable polyamines include all-anediamines, such as 1,3-propanediamine and its homologs with or without N-alkyl or aryl substituents, cycloaliphatic primary diamines, such as cyclohexane diamine, cycloaliphatic secondary diamines, such as piperizine and its alkyl derivatives, aromatic secondary amines, such as N,N'-dimethyl-1,3- phenylenediamine, N,N'-diphenylethylene diamine, benzidine, xylylene diamine and derivatives thereof. Other suitable polyamines may be found in the patents incorporated herein by reference. The preferred polyamines of the present invention are aromatic primary diamines, more preferably m- phenylenediamine.
The polyamine is present in an aqueous solution in an amount in the range of from about 0. 1 to 20 %, preferably 0. 5 to 8 %, by weight, of the aqueous solution. The pH of the aqueous solution is in the ran-e of from about 7 to 13. The pH can be adjusted by the addition of a basic acid acceptor in an amount ranging from about 0. 00 1 % to about 5 %, by weight, of the solution. Examples of the aforementioned basic acid acceptor include hydroxides, carboxylates, carbo nates, borates, and phosphates of alkali metals, as well as trialkylamines.
As noted above, in addition to the aforementioned polyamine, the aqueous solution further comprises an amine salt, the amine salt preferably having three or four substituents on the nitrogen atom, examples of such substituents including alkyl, cycloaliphatic, benzyl, alkoxy => C) and/or alkanol aroups. Accordingly, the amine salt is preferably either a quaternary ammonium salt or a reaction product of a strong acid and a tertiary amine.
Examples of quaternary ammonium salts suitable for use in the present invention include tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, tecraethylammonium hydroxide and tetrapropylammonium hydroxide; benzyltrialkyla=onium hydroxides, such as benzy1trimethylammonium hydroxide, benzyltriethylammonium hydroxide and benzyltripropyla=onium hydroxide; and mixtures thereof.
Where the amine salt is the reaction product of a strong acid and a tertiary amine, the tertiary amine may be either a monofunctional tertiary amine or a polyfunctional tertiary amine. Examples of monofunctional tertiary amines suitable for use in the present invention include trialkylamines, such as trimethyl amine, triethyl arnine, and tripropyl amine; Nalkylcycloaliphatic arnines, such as 1-methylpiperldine, N,N-dimethylethylamine and N,Ndiethylmethylamine; and N, N-d ialkyl ethanol amines, such as N,N-dimethylethanolamine.
Examples of strong acids suitable for use in the present invention include methanesulfonic acid (MSA), toluenesulfonic acid (TSA), camphorsulfonicacid (CSA), echanesulfonic acid 16 (ESA), benzenesulfonic acid (BSA), and other aromatic, aliphatic, and cycloaliphatic sulfonic acids, trifluoroacetic acid, nitric acid, hydrochloric acid, sulfuric acid and mixtures thereof, Where the arnine salt is forined using a polyfunctional tertiary amine (said polyfunctional tertiary amine having n tertiary arnine functional groups, n being greater than or equal to 2), said C, 0 Cl polyfunctional tertiary amine and said strong acid are preferably reacted together in a molar ratio that is greater than or equal to 1: 1, respectively, and is less than 1: n, respectively (see U. S. S. N. 09/067, 891, which is incorporated herein by reference). More preferably, said molar ratio of said polyfunctional tertiary amine to said strong acid is greater than or equal to 1: 1 and less than or equal to 1: (0. 95)n and even more preferably is greater than or equal to 1: 1 and less than or equal to 1:(0.9)n.
Still even more preferably, said amine salt that is the reaction product of a polyfunctional tertiary amine and a strong acid comprises at least one tertiary amine salt functional group and In at least one tertiary amine functional group. In this manner, although not wishing to be limited to any particular theory behind the invention, the present inventors believe that the tertiary arnine salt functional group is free to act as a pore former in the polyarnide membrane to thus enhance flux whereas the tertiary amine functional group is free to act as a proton acceptor for acid byproducts produced during the interfacial reaction between the polyfunctional amine (e.0'., metaphenylenediamine) and the amine-reactive reactant (e trimesoyl chloride). The bifunctional character of this type of amine salt appears to improve flux surprisingly more than do amine salts of the type having a single tertiary amine salt functional 2roup and no tertiary amine C C functional groups or amine salts having two or more tertiary arnine salt functional gyro ups and no tertiary arnine functional groups.
17 Examples of polyfunctional tertiary ainines suitable for use in the present invention include 1, 4-diazabicyclo (2,2,2] octane (DABCO), 1,8diazabicyclo[5,4,0]undec-7-ene, N,N,N',N'-tetramethyl-1,3-butanediamine (TMBD), N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N',N"pentamethyldiethylenetriamine, 1,1,3,3-tetramethyl-LYuanidine (TMGU), N,N, N',N'-tetramethylethylenediamine (TMED), substituted imidazoles, such as 1,2dimethylimidazole (DMI), 1 -alk-y I -substituted imidazoles and other substituted imidizoles of the type described in U. S. S. N. 08/99 1, 110 (which application is incorporated here in by reference), and mixtures thereof. Such polyfunctional tertiary amines are essentially nonmonomeric, i.e., not polymerizable.
The amine salt of the present invention is preferably present in the aqueous solution in an amount constitutinc, about 0.3 to 12%, by weiaht, of said aqueous solution, more preferably about 0.6 to 8%, by weight, of said aqueous solution.
As also noted above, in addition to the polyfunctional arnine and the amine salt, the aqueous solution further comprises one or more polar solvents, said one or more polar solvents being selected from the group consisting of ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, selected alcohols, sulfoxide derivatives, sulfone derivatives, rjitrile derivatives, urea derivatives, and mixtures thereof.
Examples of ethylene glycol derivatives suitable for use in the present invention include alkoxyethanols, such as 2-methoxyethanol, 2ethoxyethanol, 2-propoxyethanol and 2butoxyethanol, di(ethylene glycol) tbutylmethyl ether and di(ethylene glycol)hexyl ether.
Examples of propylene glycol derivatives suitable for use in the present invention include propylene glycol butyl ether and propylene glycol propyl ether. Examples of suitable alcohols In 18 for use in the present invention include I-pen(anol and 1-butanol. Examples of 1,3-propanediol derivatives suitable for use in the present in vention include 1,3-heptanediol, 2-ethyl-1,3hexanediol, 1,3-hexanediol and 1,3-pentanediol.
Examples of sulfoxide derivatives suitable for use in the present invention include dimethyl sulfoxide, tetramethylene sulfoxide, butyl sulfoxide and methylphenyl sulfoxide. Examples of sulfone derivatives suitable for use in the present invention include tetramethylene sulfone and butyl sulfone.
Examples of nitrile derivatives suitable for use in the present invention include is selected from the group consisting of acetonitrile and propionitrile. An example of a urea derivative suitable for use in the present invention is 1,3-dimethyl-2-imidazolidinone.
Examples of preferred combinations of two or more polar solvents suitable for use in the present invention include 2-ethyl-1,3-hexanediol and dimethyl sulfoxide; di(ethylene glycol) hexyl ether and dimethyl sulfoxide; an alkoxyethanol (e.g., 2-butoxvethanol) and dimethyl sulfoxide; and 2-ethyl-l,')-hexanediol and acetonitrile.
Said one or more polar solvents of said aqueous solution preferably constitute a combined total of about 0.01 %-8 %, by weight, of said aqueous solution. This combined amount of polar solvents is smaller than that taught or suggested by U.S. Patent Nos. 5,576,057 and 5,614,099, and yet yields equal or better results.
Where di(ethylene glycol) hexyl ether is used as a polar solvent, it preferably constitutes about 0.01 % to about 0.3 %, by weight, of said aqueous solution, more preferably about 0. 1 % to 0. 3 %, by weight, of said aqueous solution. Where 2-ethyl- I,':)- hexanediol is used as a polar solvent, it preferably constitutes about 0.1% to 1.0%, by weight, of said aqueous solution.
19 Where an alkoxyethanol is used as a polar solvent, it preferably constitutes about 0.05 % to about 4%, by weight, of said aqueous solution. Where 1-pentanol is used as a polar solvent, it is preferably present in said aqueous solution in an amount constitutincr about 0.01 % to about 2%, C, by weight, of said aqueous solution. Where 1-butanol is used as a polar solvent, it is preferably present in said aqueous solution in an amount constituting about 0. 0 1 % to about 3 %, by weight, of said aqueous solution. Where the polar solvent is tetramethylene sulfone or methylphenyl sulfoxide, it is present in an amount constituting about 0. 0 1 % to about 4 %, by weight, of said aqueous solution. Where butyl sulfone is used as a polar solvent, it is preferably present in an amount constituting about 0. 01 % to about 0. 5 %, by weight, of said aqueous solution. Where dimethvl sulfoxide is used as a polar solvent, it is preferably present in an amount constituting I n about 0. 1 % to about 7 %, by weight, of said aqueous solution.
Without wishing to be limited to any particular theory behind the invention, the present inventors believe that the combination of the amine salts and the one or more polar solvents described above often has an unexpectedly advantageous effect on improving flux because the amine salts act as a pore former in the membrane while the polar solvents act as catalysts for the pore forming process upon heating of the membrane.
The arnine-reactive reactant employed in the present invention is one or more compounds selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonvl halide and a polyfunctional isocyanate. Preferably, the amine-reactive reactant is an essentially monomeric, aromatic, polyfunctional acyl halide, examples of which include di- or tricarboxylic acid halides, such as trimesoyl chloride (TMC), isophthaloyl chloride (IPC), terephthaloyl chloride (TPC) and mixtures thereof, Examples of other amine-reactive reactants are disclosed in the patents incorporated herein by reference.
The an-dne-reactive reactant is present in an organic solvent solution', the solvent for said organic solvent solution comprising any organic liquid immiscible with water. The aminereactive reactant is present in the organic liquid in an amount in the range of from about 0.005 to 5%, preferably 0.01 to 0.5%, by weight, of the solution. Examples of the aforementioned organic liquid include hexane, cyclohexane, heptane, alkanes having from 8 to 12 carbon atoms, and halogenated hydrocarbons, such as the FREON series. Other examples of the abovedescribed organic liquid may be found in the patents incorporated herein by reference. Preferred org ganic solvents are alkanes having from 8 to 12 carbon atoms and mixtures thereof. ISOPAR1 solvent (Exxon Corp.) is such a mixture of alkanes having from 8 to 12 carbon atoms.
In accordance with the method of the present invention, the abovedescribed porous support is coated with the above-described aqueous solution utilizing either a hand coating or a continuous operation, and the excess solution is removed from the support by rolling, sponging, air knifing or other suitable techniques. Following this, the coated support material is then contacted, for example, by dipping or spraying with the above-described oroanic solvent solution and allowed to remain in place for a period of time in the range of from about 5 seconds to about 10 minutes.
preferably about 20 seconds to 4 minutes. The resulting product is then dried, preferably by heating at SO'C-130'C, more preferably at about 70'C100'C at about 90'Q, for about 1 minute to about 10 minutes (preferably about 2-7 minutes), and then rinsed in a basic aqueous solution for about I to 30 minutes at a temperature between room temperature and about 95'C.
21 The following examples are provided for illustrative purposes only and are in no way I I intended to limit the scope of the present invention:
EXAMPLE 1 A 140 k4m thick microporous polysulfone support including the backing non-woven fabric Z 0 was soaked in an aqueous solution containina, 2 wt % of meta- phenylenediamine (TIVIPID), 2.3 wt % camphorsulfonic acid (CSA), 1.1 wt % triethylamine (TEA) and 2 wt % 2-butoxyethanol (BE) for 40 seconds. The support was drained and nip rolled to remove the excess aqueous solution. Then, the coated support was dipped in 0. 1 wt % solution of trimesoyl chloride (TMC) in Isopar' solvent (Exxon Corp.) for I minute followed by draining the excess organic solution off the support. The resulting composite membrane was heated at 90'C for about 3-5 minutes and then rinsed in 0. 2 % Na2CO3 aqueous solution for 30 minutes at room temperature before performance test. The performance of the reverse osmosis membrane was measured by passing an aqueous solution containing 2000 ppm of NaCl through the membrane at 225 psi. The salt rejection was 99% and the flux was 37 gfd.
EXAMPLES 2-36 and COMPARATIVE EXAMPLES A-W The same procedure as set forth in Example I was carried out for each of Examples 2-36 and Comparative Examples A-W, except that the polar solvents listed in TABLE I were used instead of 2 wt % 2-butoxyethanol (BE).
TABLE I
EXAMPLE POLAR SOLVENT(S) CONCENTRATION FLUX REJECTION (wt %) (GFD) 2 dimethyl sulfoxide 1 40 98.2 (DMSO) 3 2-ethyl-1,3-hexanediol 0.1 35.2 94.5 (EHD) 4 EHD 0.2 42.6 96.0 EHD 0.3 47.9 97.6 6 EHD 0.4 47.5 97.1 7 DMSO and EHD 2 and 0. 3, 75.6 93.5 respectively 8 DTIMSO and EHD 2 and 0.2, 76.8 92.8 respectively 9 DMSO and EHD 0. 5 and 0. 3, 58.4 96.6 respectively DMSO and EHD 5 and 0. ':) 72.4 90.7 11 DMSO and EHD 7 and 0.3 69.5 86.6 12 EHD and acetonitrile 0.2 and 4, 50.7 8 31. 5 respectively 13 DMSO and BE 2 and 2 65.3 93) 2 -3 14 DMSO and BE 0.5 and 2, 46.0 98.0 respectively DMSO and BE 0.1 and 0. 1 44.8 97.9 16 BE 0.1 34.5 98.4 17 BE 4 36.4 96.7 COMP. A BE 6 28.7 94.0 COMP. B BE 8 26.0 91.4 Is 2-propoxyethanol 0.1 22.1 95.1 (PE) 19 PE 43.5 97.0 PE 4 40.6 95.4 21 2-ethoxyethanol 1) 39.2 96.6 22 2-ethoxyethanol 4 45.7 94.3 2 3 2-methoxyethanol 1.38.2 96.6 3 24 2-methoxyethanol 4 '16.7 88.6 COMP. C propylene glycol 23.1 96.9 24 COMP. D ethylene glycol 2 336.3 92.9 dimethyl ether COMP. E ethylene glycol 2 3 1. 4 95,6 diethyl ether di(ethylene glycol) 0.2 36.6 97.7 1 hexyl ether (DEGHE) COMP. F di(ethylene glycol) 2 31.2 95.9 butyl ether COMP. G di(ethylene glycol) 0.1 32.7 93.1 Z butyl ether COMP. H di(ethylene glycol) 2 34.7 96.1 ethyl ether COMP. I di(ethylene glycol) 2 32.5 96.4 methyl ether COMP. J di(ethylene glycol) 2 31.0 95.9 diethyl ether 26 di(ethylene glycol) 1) 38.2 95.6 t-butylmethyl ether 27 propylene glycol 2 39.7 96.9 butyl ether 28 propylene glycol 1 37.3 94.5 propyl ether 29 I-pentanol 1 313. 2 97.3 -110 1 -butanol 3)8.3 97.1 COMP. K I-propanol 32. 4 91.2 CONIP. L isopropanol 3.30. 8 90.7 COMP. m isopropanol 10 34.7 89.4 1,31-dimethyl-2- 1 54.2 92.1 imidazolidinone -3 2 tetramethylene 1 46.6 94.8 sulfoxide 3 burylsulfoxide 1 42.2 95.6 34 methylphenyl sulfoxide 1 -118.0 97.5 COMP. 0 ethyl sulfone 1 29.9 93. 6 tetramethylene sulfone 1 44.6 91.8 (TMSO) 26 36 butyl sulfone 0.5 40.2 98.0 COMP. P N,N- 1 3 5. 9 94.4 di methyl form amide COMP. Q N -methylpyrro lid inone 2 26.9 94.5 COMP. R acetone 2 30.8 96.3:5 COMP. S none 0. 26.0 98.0 COMP. T 1,6-hexanediol 1 37.8 95.6 COMP. U 1,6-hexanediol 0.5 34.4 97.6 COMP. V 1,6-hexanediol 0.25 31.4 97.7 C P. W 1.2-liexandiol 1 29.3 98.0 EXAMPLE -37
The same procedure as set forth in Example 1 was repeated, except that 0. 3 wt % EHD was used instead of 2 wt % BE and that 1 wt % 1,1,3,-I-tetramethyl guanidine (TMGU) and 1.6 wt % toluenesulfonic acid (TSA) were. used instead of TEA and CSA, respectively, The flux and the salt rejection of the resultant membrane were 43.4 gfd and 96.3%, respectively. EXAMPLES 38- 78 and COMPARATIVE EXAMPLES X-Al The same procedure as set forth in Example 37 was carried out for each of Examples 3)8- 78 and Comparative Examples X-Al, except that the polar solvents listed in TABLE 11 were used 27 instead of 0.3 wt % EHD and except that the amine and acid listed in TA13LE 11 were used instead of TMGU and TSA, respectively.
TABLE II
EXAMPLE AM1NE(wt%)/ACID(wt%) POLAR FLUX REJECTION or SOLVENT (wt%) (GFD) (%) QUATERNARY AMMONIUM SALT 38 1,2- EHD(O.-)) 46.1 95.2 dimethylimidazole (DMI) (1)/TSA(l.9) COMP. X TMGU(1)/TSA(1,6) none 22 5.4 93.3 9 TMGU(I)/TSA(l.6) EHD(O.-))/DNISO(2) 63.7 90.8 TMGU(I)/TSA(I.6) DEGHE(0.2)/D,\1S0(2) 59.5 86.9 COMP.Y TMGU(1)/CSA(2.0) none 26.7 97.6 41 TMGU(I)/CSA(2.0) EHD(O. 3) 42.0 97.4 COMP.z DMI(I)/TSA(I.9) none 42.8 91.5 42 DMI(1)/TSA(1.9) EHD(0.33) 46.1 95.2 4 3 DMI(1)/TSA(l.9) EHD(03)/DN1SO(4) 56.6 86.9 4 DMI(I)/TSA(l.9) BE(l) 41.7 97.5 28 DMI(I)/TSA(l.9) - BE(1)/DMSO(4) 49.7 90.1 q2 46 DMI(1)/CSA(2) BE(l)/DMSO(3) 56.9 ' 872 47 DMI(1)/CSA(2) EHD(O.3)/DMSO(4) 46.1 95.2 COMP. AA DMI(I)/CSA(2) none 3 8. 7 89.1 48 DMI(I)/CSA(2) BE(l) 47.4 95.5 49 DMI(1)/CSA(2) EHD(O-3) 52.9 95.5 DMI(I)/CSA(2) triethylene glycol 42.5 92.6 dimethyl ether TEGD(1) COMP. AB TMBD(I)/TSA(l.-I) none 29.1 97.1 51 TMBD(I)/TSA(1.--I) EHD(O.3) 36.7 97.8 52 TMBD(I)/TSA(l.3) EHD(O.3)/DMSO(4) 56.5 86.7 51 T.MBD(1)/TSA(l.3) BE(1) 1 97.8 i 35.5 54 TMBD(I)/TSA(l.-)) BE(1)/DMSO(-D) 55.7 90 ? COMP. AC TMBD(1)/CSA(I.6) none 24.5 97.5 TMBD(1)/CSA(l.6) EHD(O.3) 40.0 97.4 56 TMBD(1)/CSA(I.6) EHD(O.3)/DTvISO(4) 52 93.4 29 COMP. AD TMED(1)/MSA(0.8--I) none 3 2. 5 72.9 57 TMED(1)/MSA(0.83) BE(l) 35.6 89.1 58 TMED(1)/MSA(0.8-)) EHD(O.--I) 318. 7 94.6 59 TMED(l)/MSA(0.83)) DMSO(l) 41.1 90.0 TMED(1)/TSA(I.--I?-) EHD(O.-)) 25.7 95.1 61 TMED(1)/TSA(l.32) EHD(O.3)/DMSO(2) 3 9. 2 92.4 COMP. AE DABCO(1)/MSA(0.85). none 32.3 97.0 62 DABCO(1)/MSA(0.85) BE(I)/DMSO(4) 48.6 88.3 63 DABCO(I)/MSA(0.85) BE(I)/TMSO(4) 24.4 88.5 64 DABCO(2)/MSA(I.7) BE(2) 36.9 96.2 CONIP. AF DABCO(I)/TSA(I.7) none 31.3 95.7 DABCO(I)/TSA(I.7) BE(l) 33.2 96.9 66 DABCO(I)/TSA(I.7) BE(I)/DMSO(4) 48.8 88.8 67 DABCO(I)/TSA(I.7) EHD(O.-)) 30.2 95. 3 68 DABCO(1)/TSA(I.7) EHD(O.3)/DMSO(4) 48.0 88.9 K COMP. AG benzyltrirnethyl- none 30.2 7 ammonium chloride 90.7 (BTAC)(1.5) _071 69 BTAC(1.5) BE(I)/DMSO(-)) 46.5 91.6 BTAC(1.5) EHD(O.3)/DMSO(-)) 48.0 92.3 COMP. AH triethylamine(TEA)(2)/ none 34.1 98.1 TSA(33.4) 71 TEA(2)/TSA(3.4) EHD(O.3) 33 8. 0 9 7. 31 72 TEA(2)/TSA(-"1.4) EHD(O.3)/DMSO(3) 57.1 87.5 73) TEA(--))/TSA(3.4) BE(l) 45.2 97.3 74 TEA(--))/TSA(--1.4) BE(l)/DMSO(3) 5 2. 4 8 3. 3 COMP. AI N,N- none 34.5 97.9 dimethylbenzylamine (DMBA)(l)/TSA(I.4) DMBA(1)/TSA(l.4) EHD(O.)) 96.0 76 DMEA(1)/TSA(l.4) EHD(O.3)/DMSO(3) 47.1 87.2 77 DMBA(1)/TSA(l.4) BE(l) 34.0 97.9 78 DMBA(I)/TSA(l.4) BE(1)/DNISO(3) 56.9 82.8 As can be seen from the above data, the selection of specific polar solvents can have an appreciable effect on the flux and rejection rate of the composite polyamide membrane made in the presence thereof. For example, compare the flux and rejection rates of Examples 1, 16 and 17 for 2%, 0.1 % and 4% 2-butoxyethanol (a.k.a. ethylene glycol monobutyl ether) with that for Comparative Examples D and E for 2 % ethylene glycol dimethyl ether and 2 % ethylene glycol diethyl ether. In addition, compare the flux and rejection rate of Example 25 for 0.2% di(ethylene glycol) hexyl ether with that of Comparative Examples F through I for solvents of similar structure. Other comparisons which exhibit appreciable differences in flux or flux and rejection rate include Example 26 for 2% di(ethylene glycol) t- butylmethyl ether with Comparative Example J for 2 % di(ethylene glycol) diethyl ether; Example 3)5 for tetramethylene sulfone with Comparative Example 0 for ethyl sulfone; and Examples 3 through 6 for 0.1%, 0.2%, 0-3% and 0.4% EHD with Comparative Examples D through J and T through W for ethylene glycol dimethyl ether, ethylene glycol diethyl ether, di(e[hvlene glycol) butyl ether, di(ethylene glycol) ethyl ether, di(ethylene glycol) meihyl ether, di(ethylene glycol) diethyl ether, 1,6-hexanediol and I,21-hexanediol.
Moreover, an unexpected effect appears to exist when certain combinations of polar solvents are used with an amine salt. For instance, the combination of BE and DMSO or the combination of EHD and DMSO appears to result in a significantly higher flux than would be obtained in the presence of the constituent solvents used alone. (Compare Examples 13 (2% DMSO and 2% BE), 14 (0.5% DMSO and 2% BE) and 15 (0.1 % DNISO and 0. 1 % BE) with Example 2 0% DNISO) and Example 1 (2 % BE).) This increase in flux is not apparently the case for all combinations of polar solvents, as indicated by Example 63).
3 2 The embodiments of the present invention recited herein are intended to be merely exemplary and those skilled in the art will be able to make numerous variations and modifications to it without departing from the spirit of the present invention. All such variations and modifications are intended to be within the scope of the present invention as defined by the claims appended hereto.
11 n The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this applic ation and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.
All of the features disclosed in thisspecification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.
Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
The invention is not restricted to the details of the foregoing embodiment (3). The invention extend to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
34
Claims (25)
1. A polyamide membrane comprising a reaction product of (D an aqueous solution comprising a polyfunctional amine, a salt-containing I and one or more polar solvents, ksait-containing compound comp6sing at least one amine salt functional group and at least one amine functional group, and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a p6lyfunctional acyl halide, a polyfunctional sulfonyl halide and a poly-functional isocyanate.
2. The polyamide membrane as claimed in claim I wherein said at least one amine salt functional group is at least one tertiary amine salt functional group and wherein said at least one amine functional group is at least one tertiary amine functional group.
or CIOa-bM Z
3. The polyamide membrane as claimed in claim 11,wherein said polyfunctional amine is at least one member selected from the group consisting of an aromatic primary diamine, a cycloaliphatic secondary diamine, an aromatic secondary diamine and a xylylene diamine.
On praceA;^5 C ta."M
4. The polyarnide mambrane as claimed in k)LRa-4 whefein said polyfunctional arnine is present in said aqueous solution in an amount constituting about 0.1 to 20%, by weight, of said aqueous solution.
5. The polyamide membrane as claimed in wherein said amine-reactive reactant is at least one membrane selected from the group consisting of an isophthaloyl halide, a terephthaloyl halide and a trimesoyl halide.
CR^J
6. The polyamide membrane as claimed in Glab I- wherein said one or more polar solvents are present in said aqueous solution in a total amount constituting about 0.01 to 8%, by weight, of said aqueous solution.
7. A composite reverse osmosis membrane comprising: (a) a porous support; and OL-A 1 3 (b) a Polyamide membrane as claimed in 'Ion said porous support.
8. The composite reverse osmosis membrane as claimed in claim 7 wherein said porous support is made of a material selected from the group consisting of polysulfone, a Polyether sulfone, a polyimide, a polyaniide, polypropylene and polyvinylidene fluoride.
9. A polyamide membrane comprising a reaction product of (i) an aqueous solution comprising a polyfimctional amine, a salt-containing compound and one or more polar solvents, said salt-containing compound being a reaction product of a strong acid and a polyfunctional tertiary amine and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
10. The polyarnide membrane as claimed in claim 9 wherein said polyfunctionaI tertiary amine has n tertiary amine functional groups, n being greater than or equal to 2, wherein said greater than or equal to 1:1, respectively, and is less than I:n, respectively.
11. A composite reverse osmosis membrane comprising:
(a) a porous support; and Or CACLIM ic) (b) a polyamide membrane as claimed in claim 9 Lon said porous support.
12. A polyamide membrane comprising a reaction product of Q) an aqueous solution comprising a polyfunctional arnine, an arnine salt and one or more polar solvents, wherein said one or more polar solvents are selected from the group consisting of 2 -ethyl - 1,3-hexanediol; a combination of 2-ethyl-1,3-hexanediol and dimethyl sulfoxide; di(ethylene glycol) hexyl ether; a combination of di(ethylene glycol) hexyl ether and dimethyl sulfoxide; di(ethylene glycol) t-butylmethyl ether; a combination of an alkoxyethanol and dimethyl suffoxide; propylene glycol butyl ether; propylene glycol propyl ether; triethylene glycol dimethyl ether; 1,3dimethyl-2- imidazohdenone; a combination of 2-ethyl-1,3-hexanediol and acetonitrile; 36 tetramethylene suifoxide; butyl sulfoxide; methylphenyl sulfoxide; butyl sulfone; and mixtures thereof, and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
13. The polyamide membrane as claimed in claim 12 wherein said amine salt is selected from the group consisting of a quaternary ammonium salt and a reaction product of a strong acid and a tertiary amine.
14. A composite reverse osmosis membrane comprising:
(a) a porous support; and 1-3- (b) a polyamide membrane as claimed in claim 12 On said porous support.
15. A polyamide membrane comprising a reaction product of G) an aqueous solution comprising a polyftmctional amine, an arnine salt and one or more polar solvents, wherein said one or more polar solvents are selected from the group consisting of an alkoxyethanol in an amount constituting about 0.05% to about 4%, by weight, of said aqueous solution; dimethyl sulfoxide in an amount constituting about 0.01% to about 8%, by weight, of said aqueous solution; a combination of an alkoxyethanol in an amount constituting about 0.05% to about 4%, by weight, of said aqueous solution and dimethyl suffoxide in an amount constituting about 0.01% to about 8%, by weight, of said aqueous solution; 1-pentanol in an amount constituting about 0.01% to about 2%, by weight, of said aqueous solution; I-butanol in an amount constituting about 0.01% to about 3%, by weight, of said aqueous solution; and tetrarnethylene sulfone in an amount constituting about 0.01% to about 4%, by weight, of said aqueous solution, and Gi) an organic solvent solution comprising an an-Ane-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate.
37
16. The polyamide membrane as claimed in claim 15 wherein said arnine salt is selected from the group consisting of a quaternary ammonium salt and a reaction product of a strong acid and a tertiary arnine.
or cia:m Ir.
17. The polyamide membrane as claimed in claim 15 1wherein said one or more polar solvents are a combination of 2-butoxyethanol in an amount constituting about 0.05% to about 4%, by weight, of said aqueous solution and dimethyl -sulfoxide in an amount constituting about 0.01% to about 8%, by weight, of said aqueous solution.
18. A method of making a composite reverse osmosis membrane, said method comprising the steps of:
(a) coating a porous support with an aqueous solution comprising a polyfunctional amine, one or more polar solvents and a salt-containing compound, said salt-containing compound being a reaction product of a strong acid and a polyfunctional tertiary amine, so as to form a liquid layer on said porous support; (b) contacting said liquid layer with an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfimctional isocyanate so as to interfacially condense s aid amine- reactive reactant with said polyfunctional amine, thereby forming a cross- Enked, interfacial polyarnide layer on said porous support; and (c) drying the product of step (b) to form a composite reverse osmosis membrane.
19. A method of making a composite reverse osmosis membrane, said method comprising the steps of:
(a) coating a porous support with a first aqueous solution, said first aqueous solution comprising one or more polar solvents and an amide salt, so as to form a first liquid layer on said porous support; 38 (b) coating the first liquid layer with a second aqueous solution, said second aqueous solution comprising a polyfunctional amine, so as to form a second liquid layer over said first liquid layer; (c) contacting the twice-coated porous support with an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and' a polyfunctional isocyanate so as to interfacially condense said arnine-reactive reactant with said polyfLinctional arnine, thereby forming a cross-linked, interfacial polyamide layer on said porous suppor- t; and (d) drying the product of step (c) to form a composite reverse osmosis membrane.
20. A method of making a composite reverse osmosis membrane, said method comprising the steps of:
(a) coating a porous support with a first aqueous solution, said first aqueous solution comprising one or more polar solvents, so as to form a first liquid layer on said porous support; (b) coating the first liquid layer with a second aqueous solution, said second aqueous solution comprising a polyfunctional amine and an amine salt, so as to form a second liquid layer over said first liquid layer; (c) contacting the twice-coated porous support with an organic solvent solution comprising an arnine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate so as to interfacially condense said amine-reactive reactant with said polyfunctional amine, thereby forming a cross-linked, interfacial polyamide layer on said porous support; and (d) drying the product of step (c) to form a composite reverse osmosis membrane.
39
21. A polyamide membrane comprising a reaction product of (i) an aqueous solution comprising a polyfunctional amine, a salt-containing compound comprising an amine sa It and/or an amine functional group and one or more polar solvents 1 and (ii)an organic solvent solution comprising an aminereactive reactant.
22. A polyamide membrane according to claim 21 and having any feature of a membrane described in any preceding claim 10 or as described in any statement herein.
23. A polyamide membrane substantially as hereinbefore described with reference to the examples.
24. A reverse osmosis membrane substantially as hereinbefore described with reference to the examples.
25. A method of making a reverse osmosis membrane substantially as hereinbefore described with reference to 20 the examples.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19934737A DE19934737C2 (en) | 1999-07-23 | 1999-07-23 | Polyamide reverse osmosis membrane |
GB9918111A GB2352722B (en) | 1999-07-23 | 1999-08-03 | Composite polyamide reverse osmosis membrane and method of producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19934737A DE19934737C2 (en) | 1999-07-23 | 1999-07-23 | Polyamide reverse osmosis membrane |
GB9918111A GB2352722B (en) | 1999-07-23 | 1999-08-03 | Composite polyamide reverse osmosis membrane and method of producing the same |
Publications (3)
Publication Number | Publication Date |
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GB9918111D0 GB9918111D0 (en) | 1999-10-06 |
GB2352722A true GB2352722A (en) | 2001-02-07 |
GB2352722B GB2352722B (en) | 2004-01-07 |
Family
ID=26054324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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GB9918111A Expired - Lifetime GB2352722B (en) | 1999-07-23 | 1999-08-03 | Composite polyamide reverse osmosis membrane and method of producing the same |
Country Status (2)
Country | Link |
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DE (1) | DE19934737C2 (en) |
GB (1) | GB2352722B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1230971A1 (en) * | 2001-02-12 | 2002-08-14 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method for producing the same |
EP1426098A1 (en) * | 2001-09-10 | 2004-06-09 | Nitto Denko Corporation | Semipermeable composite membrane and process for producing the same |
EP1707255A2 (en) * | 2005-03-30 | 2006-10-04 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010082710A1 (en) * | 2009-01-14 | 2010-07-22 | University-Industry Cooperation Group Of Kyung Hee University | Method for preparing a highly durable reverse osmosis membrane |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50146554A (en) * | 1974-05-17 | 1975-11-25 | ||
US4872984A (en) * | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US4948507A (en) * | 1988-09-28 | 1990-08-14 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US5160619A (en) * | 1990-09-14 | 1992-11-03 | Nitto Denko Corporation | Composite reverse osmosis membrane and production thereof |
US5576057A (en) * | 1993-06-24 | 1996-11-19 | Nitto Denko Corporation | Method of producing high permeable composite reverse osmosis membrane |
US5614099A (en) * | 1994-12-22 | 1997-03-25 | Nitto Denko Corporation | Highly permeable composite reverse osmosis membrane, method of producing the same, and method of using the same |
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 |
US6063278A (en) * | 1998-04-28 | 2000-05-16 | Saehan Industries Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
US4983291A (en) * | 1989-12-14 | 1991-01-08 | Allied-Signal Inc. | Dry high flux semipermeable membranes |
JP3045349B2 (en) * | 1991-11-26 | 2000-05-29 | 株式会社大一商会 | Pachinko machine |
-
1999
- 1999-07-23 DE DE19934737A patent/DE19934737C2/en not_active Expired - Lifetime
- 1999-08-03 GB GB9918111A patent/GB2352722B/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50146554A (en) * | 1974-05-17 | 1975-11-25 | ||
US4872984A (en) * | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US4948507A (en) * | 1988-09-28 | 1990-08-14 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US5160619A (en) * | 1990-09-14 | 1992-11-03 | Nitto Denko Corporation | Composite reverse osmosis membrane and production thereof |
US5576057A (en) * | 1993-06-24 | 1996-11-19 | Nitto Denko Corporation | Method of producing high permeable composite reverse osmosis membrane |
US5614099A (en) * | 1994-12-22 | 1997-03-25 | Nitto Denko Corporation | Highly permeable composite reverse osmosis membrane, method of producing the same, and method of using the same |
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 |
US6063278A (en) * | 1998-04-28 | 2000-05-16 | Saehan Industries Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1230971A1 (en) * | 2001-02-12 | 2002-08-14 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method for producing the same |
EP1426098A1 (en) * | 2001-09-10 | 2004-06-09 | Nitto Denko Corporation | Semipermeable composite membrane and process for producing the same |
EP1426098A4 (en) * | 2001-09-10 | 2005-11-23 | Nitto Denko Corp | Semipermeable composite membrane and process for producing the same |
EP1707255A2 (en) * | 2005-03-30 | 2006-10-04 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
EP1707255A3 (en) * | 2005-03-30 | 2007-05-16 | Saehan Industries, Inc. | Composite polyamide reverse osmosis membrane and method of producing the same |
CN1840230B (en) * | 2005-03-30 | 2012-08-08 | 世韩工业株式会社 | Composite polyamide reverse osmosis membrane and method of producing the same |
Also Published As
Publication number | Publication date |
---|---|
DE19934737C2 (en) | 2001-11-29 |
DE19934737A1 (en) | 2001-03-01 |
GB9918111D0 (en) | 1999-10-06 |
GB2352722B (en) | 2004-01-07 |
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