CN102481525B - 用于硼清除的反渗透复合膜 - Google Patents
用于硼清除的反渗透复合膜 Download PDFInfo
- Publication number
- CN102481525B CN102481525B CN201080039545.3A CN201080039545A CN102481525B CN 102481525 B CN102481525 B CN 102481525B CN 201080039545 A CN201080039545 A CN 201080039545A CN 102481525 B CN102481525 B CN 102481525B
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- CN
- China
- Prior art keywords
- halide
- membrane
- film
- composite membrane
- reverse osmosis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 30
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- -1 aromatic sulfonyl halide Chemical class 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 230000035699 permeability Effects 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000012695 Interfacial polymerization Methods 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 11
- 150000004820 halides Chemical class 0.000 abstract description 10
- 239000013535 sea water Substances 0.000 abstract description 10
- 239000004952 Polyamide Substances 0.000 abstract description 6
- 229920002647 polyamide Polymers 0.000 abstract description 6
- 239000004202 carbamide Substances 0.000 abstract description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 abstract description 5
- 150000002118 epoxides Chemical class 0.000 abstract description 5
- 239000012948 isocyanate Substances 0.000 abstract description 5
- 150000002513 isocyanates Chemical class 0.000 abstract description 5
- 150000003461 sulfonyl halides Chemical class 0.000 abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002715 modification method Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 55
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 6
- 229940018564 m-phenylenediamine Drugs 0.000 description 6
- 238000012805 post-processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JXRGUPLJCCDGKG-UHFFFAOYSA-N 4-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C=C1 JXRGUPLJCCDGKG-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 description 1
- IYBOGQYZTIIPNI-UHFFFAOYSA-N 2-methylhexano-6-lactone Chemical compound CC1CCCCOC1=O IYBOGQYZTIIPNI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- JTMZBRWRXFAITF-UHFFFAOYSA-N azane;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonic acid Chemical compound [NH4+].C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C JTMZBRWRXFAITF-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- ZEXYPISQISIGFV-UHFFFAOYSA-N formyl chloride 1,3,5-trimethylbenzene Chemical compound C(=O)Cl.CC1=CC(=CC(=C1)C)C ZEXYPISQISIGFV-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GCXZDAKFJKCPGK-UHFFFAOYSA-N heptane-1,2-diol Chemical compound CCCCCC(O)CO GCXZDAKFJKCPGK-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/108—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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Abstract
减少海水或淡海水中的硼浓度，同时维持或改善膜的盐挡阻和聚酰胺反渗透(RO)膜流动性能的改良方法，该方法包括使水与复合膜接触，该复合膜包含来自芳族磺酰基卤化物，杂芳族磺酰基卤化物，亚磺酰基卤化物；次磺酰基卤化物；硫酰基卤化物；磷酰基卤化物；膦酰基卤化物；氧膦基卤化物；硫代磷酰基卤化物；硫代膦酰基卤化物，异氰酸酯，尿素，氰酸酯，芳族羰基卤化物，环氧化物或其混合物的部分。
Description
背景
反渗透(RO)膜脱盐使用膜技术将海水和淡海水转换为淡水用于饮用、灌溉和工业应用。此类方法需要的能量实质上小于热脱盐法比如多级闪蒸，因此反渗透膜技术越来越多用于从海水或淡海水制备淡水。
反渗透是通过应用超过渗透压的压力迫使溶剂从高溶质浓度区穿过膜进入低溶质浓度区的过程。这是渗透过程的相反，渗透过程是当不应用外部压力时溶剂从低溶质浓度区穿过膜向高溶质浓度区的自然移动。这里膜是半渗透性，意味着它允许溶剂但非溶质的穿过。用于反渗透的膜具有聚合物基质的致密的阻挡层，在其中发生大多数分离。将膜设计为只允许水穿过该致密层但防止溶质比如盐穿过。反渗透过程需要将高压施加在膜的高浓度侧，通常对于淡水和淡海水是2-17bar(30-250psi)，对于海水是40-70bar(600-1000psi)，所述膜具有必须克服的大约24bar(350psi)的天然渗透压。
多年来，更好的膜技术和能量回收设备使反渗透更为负担得起和有效。但是，RO过程在清除中性污染物比如硼方面不是非常有效，尽管它能够有效地清除至多99.7％离子物种。
海水一般具有4-5mg/L的硼浓度。根据位置和季节效应，硼浓度可达到至多7mg/L，如在波斯湾。人暴露于过量硼的毒理学效应(主要是生殖和发育性)被充分证明。过量硼对植物生长也有害；有害效应包括大范围叶损伤、提早成熟和农作物减产。
在含水环境中，在酸性和中性pH，硼主要作为不解离的硼酸存在。反渗透膜清除带电物种比不带电物种好，因为水合带电物种的表观尺寸较大。不带电的硼酸具有的分子直径和的分子体积，类似于尿素及其它小的非电解质。因此，硼酸明显小于水合钠和氯离子，使硼的清除比氯化钠盐明显更难。
交联芳族聚酰胺RO膜的薄膜典型地由两种类型的孔组成，半径为约的网络孔和半径为约的聚集孔。不带电的硼酸的半径与网络孔接近，实质上小于聚集孔。结果是，RO膜脱盐过程难以实现超过90％的平均硼挡阻，这是制备符合许多应用要求的渗透液典型所需。这导致采用程序比如重复RO膜处理过程2次，或者将处理的水与来自其它来源的低硼浓度水混合。虽然这些另外的处理步骤导致硼浓度减小，但它们实质上增加成本。
近年来，已引入用于硼清除的专用海水反渗透(SWRO)膜。但是，即使使用这些膜，一次通过全尺寸RO过程也难以将硼水平减小至低于0.5mg/L，同时实现所需的系统回收，除非采用另外的处理步骤。例如，在以色列Ashkelon的SWRO工厂，使用4-级级联RO设计以达到＜0.3mg/L的硼规格。转让给TorayIndustriesInc.的US7,279,097公开用脂族胺和脂族酸卤化物处理反渗透膜以改善膜的硼挡阻的方法。所公开的脂族酸卤化物包括“甲磺酰氯，乙酰氯，丙酰氯，丁酰氯，草酰氯，丙二酸二氯，琥珀酸二氯，马来酸二氯，富马酸二氯，氯磺酰乙酰氯，和N，N-二甲基氨基羰基氯”。但是，仍然需要甚至更好的方法，用于制备具有高硼挡阻和盐挡阻性能的新的海水和淡海水膜产品。
简述
本发明涉及用于减小硼浓度和改善聚酰胺反渗透(RO)膜的流动性能，同时维持或改善膜的盐挡阻的改良方法。
简言之，一方面，本发明涉及减小含硼的水中的硼浓度的反渗透方法，该方法包含使水与复合膜接触，所述复合膜包含来自芳族磺酰基卤化物，杂芳族磺酰基卤化物，亚磺酰基卤化物；次磺酰基卤化物；硫酰基卤化物；磷酰基卤化物；膦酰基卤化物；氧膦基卤化物；硫代磷酰基卤化物；硫代膦酰基卤化物，异氰酸酯，尿素，氰酸酯，芳族羰基卤化物，环氧化物或其混合物的部分。
另一方面，本发明涉及制备复合膜的反渗透方法，通过在界面聚合条件下使包含多元酸卤化物的有机溶液与包括多胺的水溶液接触以形成聚酰胺膜。接触步骤在多孔基膜表面上进行，有机溶液进一步包括芳基磺酰基卤化物。这样制备的复合膜可用于减小硼浓度，典型地表现良好的硼挡阻性能。
详述
本发明涉及反渗透方法，用于将含有至少5ppm硼的海水或淡海水中的硼浓度一步减小至少90％，优选一步减小至少95％，更优选一步减小至少96％。水的pH典型地小于或等于约8.5。反渗透过程典型地对于淡水和淡海水在2-17bar(30-250psi)，对于海水在40-70bar(600-1000psi)范围压力操作。
在本发明的反渗透方法中，通过将其与复合膜接触而处理海水或淡海水，所述复合膜包含来自芳族磺酰基卤化物，杂芳族磺酰基卤化物，亚磺酰基卤化物；次磺酰基卤化物；硫酰基卤化物；磷酰基卤化物；膦酰基卤化物；氧膦基卤化物；硫代磷酰基卤化物；硫代膦酰基卤化物，异氰酸酯，尿素，氰酸酯，芳族羰基卤化物，环氧化物或其混合物的部分。在一些实施方案中，所述部分来自芳族磺酰基卤化物，特别是4-硝基苯磺酰氯、1，3-苯二磺酰氯或4-氰基苯磺酰氯。复合膜可另外包括另外的交联亲水聚合物层比如聚乙烯醇(PVA)涂在分离层上。
术语“复合膜”指由在多孔基底膜上形成的分离的功能层组成的薄膜复合(TFC)半透膜。分离的功能层薄，以便使膜通量性能达到最大，并在多孔载体或基底膜上形成以提供机械强度。可用于本发明方法的TFC膜的实例包括，但不限于，由在多孔聚砜载体上形成的聚酰胺分离的功能层组成的反渗透膜、纳米过滤膜及其它薄膜复合膜。
用于本发明反渗透方法的复合膜可通过TFC膜的后处理制备，特别是具备芳族磺酰基卤化物，杂芳族磺酰基卤化物，亚磺酰基卤化物；次磺酰基卤化物；硫酰基卤化物；磷酰基卤化物；膦酰基卤化物；氧膦基卤化物；硫代磷酰基卤化物；硫代膦酰基卤化物，异氰酸酯，尿素，氰酸酯，芳族羰基卤化物，和/或环氧化物的聚酰胺TFC膜。
或者，复合膜可通过界面聚合在膜制造期间通过相同化合物的原位反应制备。因此，另一方面，本发明涉及制备可用于减小硼浓度的方法的复合膜的反渗透方法。使包括多元酸卤化物的有机溶液在界面聚合条件下，在多孔基底膜表面上，与包括多胺的水溶液接触以形成聚酰胺膜。有机溶液进一步包括芳基磺酰基卤化物，杂芳族磺酰基卤化物，亚磺酰基卤化物；次磺酰基卤化物；硫酰基卤化物；磷酰基卤化物；膦酰基卤化物；氧膦基卤化物；硫代磷酰基卤化物；硫代膦酰基卤化物，异氰酸酯，尿素，氰酸酯，芳族羰基卤化物，环氧化物或其混合物，优选芳基磺酰基卤化物，更优选1，3-苯二磺酰氯或1，3，6-萘三磺酰氯。芳基磺酰基卤化物的含量范围可为约0.01％-约2％重量。
有机溶液可另外包括C3-C8环状羰基化合物。C3-C8环状羰基化合物可以是具有3-8个碳原子的环状酮，例如环辛酮、环庚酮、2-甲基环己酮、环己酮、环己烯-3-酮、环戊酮、环丁酮、3-酮四氢呋喃、3-酮四氢噻吩和3-酮氧杂环丁烷；具有3-8个碳原子的环状酯，例如2-甲基己内酯、己内酯、戊内酯、丁内酯、双烯酮和丙内酯；或者C3-C8环状碳酸酯，例如碳酸乙烯酯、碳酸丙烯酯、1，2-丁二醇碳酸酯、1，2-戊二醇碳酸酯、1，2-己二醇碳酸酯和1，2-庚二醇碳酸酯。在一个实施方案中，环状羰基化合物是环己酮。
C3-C8环状羰基化合物的含量可相当于有机溶液总重量约0.1-约3.5重量百分数。在另一个实施方案中，C3-C8环状羰基化合物的含量相当于有机溶液总重量约0.5-约2.5重量百分数。在又一个实施方案中，有机溶液包含相当于有机溶液总重量约1-约1.5重量百分数的C3-C8环状羰基化合物。
合适的多孔基底膜包括由聚砜、聚醚砜、聚酯、聚苯醚、聚苯硫醚、聚氯乙烯、聚丙烯腈、聚偏氟乙烯、聚四氟乙烯、聚碳酸酯、聚酰亚胺、聚醚酰亚胺、聚醚酮和聚醚醚-酮组成的基底膜。许多合适的多孔基底膜可市售获得或者可用本领域普通技术人员已知的技术制备。在一个实施方案中，使用为聚砜膜的多孔基底膜。在另一个实施方案中，多孔基底膜是多孔聚醚砜膜。
界面聚合包括将一种或多种多胺单体的水溶液接触多孔载体膜上；接着涂布有机溶液，一般在脂族溶剂中，含有一种或多种多元酸卤化物单体。在位于多孔载体表面附近的两种溶液层的界面，由亲电和亲核单体的缩聚形成薄膜聚合物，并附着于多孔载体。通过加热或添加催化剂可加速薄膜形成的速率。与多胺单体接触的多元酸卤化物单体在多孔基底膜表面上反应以得到位于多孔载体膜表面上的聚酰胺。合适的多元酸氯化物包括均三苯甲酰氯、对苯二甲酰氯、间苯二甲酰氯、琥珀酸二酰氯、戊二酸二酰氯、己二酸二酰氯、反式-环己烷-1，4-二羧酸二酰氯、顺式-环己烷-1，4-二羧酸二酰氯、Kemp三酸的三酰氯和包含两种或更多种这些多元酸氯化物的混合物。合适的多胺包括对苯二胺(ppd)、间苯二胺(mpd)、4，4’-二氨基联苯、乙二胺、1，3-丙二胺、1，6-己二胺、1，10-癸二胺、4，4’-二氨基联苯砜、1，3，5-三氨基苯、哌嗪、顺式-1，3，5-环己三胺和包含两种或更多种这些多胺的混合物。合适的有机溶剂包括烃溶剂、醇溶剂、酮溶剂、酯溶剂、醚溶剂、酰胺溶剂及其混合物。界面聚合反应可在约5℃-约60℃，优选约10℃-约40℃范围温度下进行。
为了改善渗透性和/或盐挡阻，可将聚酰胺膜用氧化溶液比如次氯酸钠溶液后处理。次氯酸钠在溶液中的浓度可为约10ppm-约4000ppm范围。
实施例
实施例1-11：用4-硝基苯磺酰氯后处理
将聚酰胺RO膜切成6”×12”尺寸，然后夹在两个铝手框(hand-frame)之间，边缘周围用6个夹子密封。将膜用水冲洗约10秒，然后在环境温度用试剂溶液处理指定时间(30-90秒)，该试剂溶液含有如表1列出的甲醇溶液中的4-硝基苯磺酰(nosyl)氯，静置3分钟。将试剂混合物从其给予的同一角从膜倒出。然后将膜在55℃通风式烘箱中干燥10分钟，冷却至环境温度，在冰箱中贮存直至在交叉流动试验台上测试。
比较实施例1-3
对照RO膜如上描述制备，除了不进行后处理。
测试涂布的RO膜的NaCl挡阻和渗透性的方案
将试样切割并用40000ppmNaCl溶液(在DI水中)在800psi于20℃处理1小时。在此之后，将渗透液收集，称重并测量其电导率以获得盐挡阻和膜渗透性。然后在将膜用次氯酸钠溶液(70ppm游离氯在DI水中)在225psi于20℃处理30分钟。在此之后，将膜用DI水冲洗0.5-1.0小时，再次用40000ppmNaCl溶液在800psi于20℃处理1小时。再次将渗透液收集，称重并测量其电导率以获得盐挡阻和膜渗透性。将氯化后的样品还通过ICP(电感耦合等离子体质谱)或偶氮甲碱/UV方法分析用于硼挡阻表征，使用描述于HachDR/2400分光光度计程序手册的方法。
结果显示于表1。在无任何nosyl氯后处理的情况下，对照RO膜具有86.6％-88.6％的硼挡阻率和99.3-99.4％的盐通过率。但是，在nosyl处理后，硼挡阻率增加至91-97％，盐挡阻率增加至99.6-99.9％。
表1：膜渗透性，盐通过率，和硼挡阻性能(通过ICP法表征的硼结果)
实施例12-16用其他试剂后处理
将RO膜用1，3-苯二磺酰氯(BDSC)，4-氰基苯磺酰氯(氰基BSC)，和甲磺酰氯处理。与对照膜相比，膜显示增加的硼挡阻。
实施例17-31用苯二磺酰氯原位处理
实施例17-22：用手框涂布装置制造膜的程序
还用由配对的框组成的手框涂布装置制备复合膜，其中可将多孔基底膜固定，接着用包含C3-C8环状羰基化合物和C1-C8酰胺化合物的聚酰胺涂层涂布。使用以下程序。首先将多孔基底膜浸在去离子水中至少30分钟。将湿的多孔基底膜固定在两个8英寸×11英寸塑料框之间，保持用水覆盖直至进一步加工。从多孔基底膜除去过量的水，将多孔基底膜的一个表面用80克包含间苯二胺(MPD)(2％重量)和三乙基樟脑磺酸铵(TEACSA)(6％重量)的水溶液处理，框架的上部将水溶液限制在多孔基底膜表面上。在120秒时间之后，通过倾斜包含框架和被处理的多孔基底膜的组件而从多孔基底膜表面除去水溶液，直至在被处理的多孔基底膜表面上只可看到水溶液的分离液滴。将被处理的表面通过暴露于轻微空气流进一步处理以除去水溶液的分离液滴。然后将多孔基底膜被处理的表面与150克有机溶液接触，该溶液包含在IsoparG溶剂中的均三苯甲酰氯(0.20％重量)均三甲苯(1.5％重量)、环己酮(6％重量)和苯二磺酰氯(重量％如下表2显示)。然后通过倾斜框架一角除去过量有机溶液并将过量有机溶液收集在合适的收集容器中。然后将被处理的组件置于干燥烘箱中，在60℃温度维持约10分钟时间，接着测试复合膜。
表2手框有机涂层溶液
实施例23-31：用试用涂布机制造膜的程序
用能够涂布12英寸宽网的试用涂布机重复手框程序。将多孔基底膜进料通过由在水中的2.9重量％MPD和6.6重量％TEACSA组成的涂层水浴。使一侧涂有水溶液的多孔基底膜经过橡胶压送辊以除去过量流体。然后将涂布的多孔基底膜进料通过由水不混溶性溶剂、多元酸卤化物和有机添加剂组成的有机涂层浴，如表3显示。在经过有机涂层溶液之后，使多孔基底膜经过干燥机以除去溶剂和水以提供产物复合膜。
表3：试用涂布机有机涂层溶液
用关于实施例1-11描述的方案测试膜。结果显示于表4。
表4：实施例18-32的测试条件和结果
当存在BDSC时，在许多情况下看到在氯化之后％挡阻和A-值显著和同时增加。
虽然本文只说明和描述本发明的某些特征，但本领域技术人员将想到许多修改和变化。因此，应理解附属权利要求旨在覆盖所有此类修改和变化，如同落入本发明的真正精神之内。
Claims (10)
1.一种制备复合膜的方法，其包含在界面聚合条件下使包含均苯三甲酰氯的有机溶液与包含多胺的水溶液接触以形成聚酰胺膜，所述接触在多孔基底膜表面上进行，
所述有机溶液另外包含0.1-3.5重量%的C3-C8环状羰基化合物以及选自1,3-苯二磺酰氯和1,3,6-萘三磺酰氯的芳基磺酰基卤化物，
所述方法包括使聚酰胺膜与次氯酸钠溶液接触以改善膜的渗透性和/或盐挡阻。
2.权利要求1的方法，其中所述有机溶液包含1,3-苯二磺酰氯。
3.权利要求1的方法，其中所述有机溶液包含1,3,6-萘三磺酰氯。
4.权利要求1的方法，其中复合膜另外包含交联亲水聚合物。
5.权利要求4的方法，其中交联亲水聚合物是聚乙烯醇。
6.权利要求1的方法，其中C3-C8环状羰基化合物是环己酮。
7.权利要求1的方法，其中游离氯在次氯酸钠溶液中的浓度范围为10ppm-4000ppm。
8.权利要求1的方法，其中芳基磺酰基卤化物的含量范围为0.01%-2%重量。
9.一种复合膜，其通过权利要求1-8中任一项的方法制备。
10.一种减少含硼的水中硼浓度的反渗透方法，所述反渗透方法包含使水与权利要求9的复合膜接触。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/550,990 US20110049055A1 (en) | 2009-08-31 | 2009-08-31 | Reverse osmosis composite membranes for boron removal |
| US12/550990 | 2009-08-31 | ||
| PCT/US2010/042994 WO2011025607A2 (en) | 2009-08-31 | 2010-07-23 | Reverse osmosis composite membranes for boron removal |
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| CN102481525B true CN102481525B (zh) | 2016-05-11 |
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| US (2) | US20110049055A1 (zh) |
| EP (1) | EP2473261B1 (zh) |
| JP (1) | JP6183945B2 (zh) |
| KR (1) | KR101787122B1 (zh) |
| CN (1) | CN102481525B (zh) |
| AU (1) | AU2010286900B2 (zh) |
| HU (1) | HUE026573T2 (zh) |
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| CN102481525A (zh) | 2012-05-30 |
| WO2011025607A2 (en) | 2011-03-03 |
| EP2473261A2 (en) | 2012-07-11 |
| EP2473261B1 (en) | 2015-12-16 |
| JP2013503034A (ja) | 2013-01-31 |
| US20120255909A1 (en) | 2012-10-11 |
| TWI483770B (zh) | 2015-05-11 |
| US20110049055A1 (en) | 2011-03-03 |
| WO2011025607A3 (en) | 2011-07-07 |
| JP6183945B2 (ja) | 2017-08-23 |
| TW201114476A (en) | 2011-05-01 |
| AU2010286900B2 (en) | 2016-07-28 |
| HUE026573T2 (en) | 2016-06-28 |
| SG178493A1 (en) | 2012-03-29 |
| AU2010286900A1 (en) | 2012-03-15 |
| KR101787122B1 (ko) | 2017-10-18 |
| US8616380B2 (en) | 2013-12-31 |
| KR20120083363A (ko) | 2012-07-25 |
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