CN102380257B - 脱盐过滤材料 - Google Patents
脱盐过滤材料 Download PDFInfo
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- CN102380257B CN102380257B CN201010272136XA CN201010272136A CN102380257B CN 102380257 B CN102380257 B CN 102380257B CN 201010272136X A CN201010272136X A CN 201010272136XA CN 201010272136 A CN201010272136 A CN 201010272136A CN 102380257 B CN102380257 B CN 102380257B
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- filtration material
- desalination
- water
- desalination according
- polymer
- Prior art date
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- 238000010612 desalination reaction Methods 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000001914 filtration Methods 0.000 title claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000012528 membrane Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 30
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 claims description 21
- -1 Kynoar Polymers 0.000 claims description 19
- 239000002121 nanofiber Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 125000003368 amide group Chemical group 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 150000001718 carbodiimides Chemical class 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- PRXAVUGSVPJILE-UHFFFAOYSA-N CC(C(ON)=O)=C.CC1=C(C)C=CC=C1 Chemical compound CC(C(ON)=O)=C.CC1=C(C)C=CC=C1 PRXAVUGSVPJILE-UHFFFAOYSA-N 0.000 claims description 2
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 2
- CDYYAYWJSAKFGA-UHFFFAOYSA-M [Cl-].C(C=C)(=O)OC(C1=CC=CC=C1)([N+](C)(C)C)CC Chemical compound [Cl-].C(C=C)(=O)OC(C1=CC=CC=C1)([N+](C)(C)C)CC CDYYAYWJSAKFGA-UHFFFAOYSA-M 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229950004288 tosilate Drugs 0.000 claims description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 125000004849 alkoxymethyl group Chemical group 0.000 claims 2
- 229920000554 ionomer Polymers 0.000 claims 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- KEJVHMFKDRPSJO-UHFFFAOYSA-N 2-methylpropan-2-amine propyl prop-2-enoate Chemical compound CC(C)(C)N.CCCOC(=O)C=C KEJVHMFKDRPSJO-UHFFFAOYSA-N 0.000 claims 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 238000011033 desalting Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDUFKIIMEWLUSX-UHFFFAOYSA-N C1CN1.C1CN1 Chemical compound C1CN1.C1CN1 KDUFKIIMEWLUSX-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 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 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
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- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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- 238000009987 spinning Methods 0.000 description 2
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- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- FWBDAZIKNUDTFR-UHFFFAOYSA-N 2-ethenyl-1H-imidazole Chemical compound C(=C)C=1NC=CN1.C(=C)C=1NC=CN1 FWBDAZIKNUDTFR-UHFFFAOYSA-N 0.000 description 1
- VXEXDVFIZKWHIB-UHFFFAOYSA-N 2-ethenylpyridine Chemical compound C=CC1=CC=CC=N1.C=CC1=CC=CC=N1 VXEXDVFIZKWHIB-UHFFFAOYSA-N 0.000 description 1
- WNXTZVMMNCCZTP-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate 5-hydroxy-2-methylpent-2-enoic acid Chemical compound OCCC=C(C(=O)O)C.C(C(=C)C)(=O)OCCO WNXTZVMMNCCZTP-UHFFFAOYSA-N 0.000 description 1
- IPGXHRDWHJEWBI-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;4-hydroxy-2-methylidenebutanoic acid Chemical compound OCCOC(=O)C=C.OCCC(=C)C(O)=O IPGXHRDWHJEWBI-UHFFFAOYSA-N 0.000 description 1
- LNGIIXGLYTUUHJ-UHFFFAOYSA-N 2-methylbut-2-enoic acid methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CC=C(C)C(O)=O LNGIIXGLYTUUHJ-UHFFFAOYSA-N 0.000 description 1
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-UHFFFAOYSA-N 0.000 description 1
- BATLMLARMJZTRY-UHFFFAOYSA-N 2-methylprop-2-enenitrile Chemical compound CC(=C)C#N.CC(=C)C#N BATLMLARMJZTRY-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- KPSSXCFHJIIEJQ-UHFFFAOYSA-N 5-hydroxy-2-methylidenepentanoic acid;3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C.OCCCC(=C)C(O)=O KPSSXCFHJIIEJQ-UHFFFAOYSA-N 0.000 description 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
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- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
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- 230000002650 habitual effect Effects 0.000 description 1
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- IQSHMXAZFHORGY-UHFFFAOYSA-N methyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound COC(=O)C=C.CC(=C)C(O)=O IQSHMXAZFHORGY-UHFFFAOYSA-N 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种脱盐过滤材料(filtration material for desalination),其主要结构包括:一载体层(support layer);以及一脱盐层(desalination layer),形成于该载体层上,其中该脱盐层为一复合纤维膜(fiber composite membrane),且该复合纤维膜包括至少一种水可膨润聚合物(water-swellable polymer)。
Description
技术领域
本发明涉及一种脱盐过滤材料,且特别是涉及一种由水可膨润聚合物(water-swellable polymer)所组成的脱盐过滤材料。
背景技术
全世界各大厂积极开发各种应用于海水、工业用水及废水的脱盐过滤材料,除要能高效率处理水中盐类并希望降低操作压力,进而因低耗能可以降低净水处理成本。
美国专利US 4828700提出利用聚甲基丙烯甲酯系列的聚合物进行交联反应,制备出具有在2000ppm盐水中脱盐条件为压力250psi、通量9.1GFD与脱盐率97.9%的海水淡化薄膜。
美国专利US 5464538提出含有正离子的乙烯单体,经过交联反应后制得薄膜,此薄膜同样具有在2500ppm盐水中脱盐条件为压力400psi、3.59GFD通量与91.8%脱盐率。
美国专利US 5755964提出一种过滤材料,其利用胺类化合物处理RO膜表面,以增加薄膜的湿润性,使RO薄膜具有在2000ppm盐水中脱盐条件为压力225psi、48GFD通量达到纳米过滤材料(nanofilteration)的等级。
然而,公知的脱盐过滤材料主要为无孔隙聚合物薄膜(nonporouspolymeric thin film),其需在高压条件下操作,因此,若能提出一种具有亲水性的脱盐过滤材料,则有助于降低操作压力与提高脱盐过滤效果。
发明内容
本发明提供一种脱盐过滤材料(filter medium for desalination),包括:一载体层(support layer);以及一脱盐层(desalination layer),形成于该载体层之上,其中该脱盐层为一复合纤维膜(fiber compositemembrane),且该复合纤维膜包括至少一种水可膨润聚合物(water-swellable polymer)。
为使本发明的上述和其它目的、特征、和优点能更明显易懂,下文特举出较佳实施例,并配合所附图式,作详细说明如下:
具体实施方式
本发明提供一种脱盐过滤材料(filter medium for deslination),其由载体层(support layer)以及形成于载体层之上的脱盐层所组成,其中载体层是用于承载脱盐层,而脱盐层为一复合纤维膜(fiber compositemembrane),且复合纤维膜包括至少一种水可膨润聚合物(water-swellable polymer)。此处所谓的“水可膨润聚合物”意指聚合物本身可藉由吸收水而膨胀,且此聚合物可吸收大量的水分而不会导致其在水中溶解以致于使其结构变形。此水可澎润聚合物为不溶于水的聚合物(not water soluable polymer),其由亲水性单体(hydrophilicmonomers)与疏水性单体(hydrophobic monomers)组成。此外,水可澎润聚合物也可为一溶于水的聚合物(water soluable polymer),其经由适当的交联反应来降低水分解性但是仍保有水可澎润性。
上述的载体层由一或多层多孔性材料组成,其中多孔性材料包括纤维素酯(cellouse ester)、聚砜(polysulfone)、聚丙烯腈(polyacrylonitrile,PAN)、聚偏氟乙烯(polyvinylidene fluoride,PVDF)、聚醚醚酮(polyetheretherketone,PEK)、聚酯(polyester,PET)、聚亚酰胺(polyimide,PI)、氯化聚氯乙烯(chlorinated polyvinyl chloride,PVC)或苯乙烯-丙烯晴共聚物(styrene acrylnitrile,SAN)等,且载体层可自行合成或由市售取得,此外,多孔性材料可以以非织物、织物或开孔(open pores)材料的形式存在。
在一实施例中,脱盐过滤材料是使用两层载体层,底层为聚酯(polyester,PET),上层为聚丙烯腈(polyacrylonitrile,PAN)或聚砜(polysulfone),且载体层可以织物或非织物的形式存在,优选以非织物的形式存在。
水可膨润聚合物(water-swellable polymer)的亲水性单体可以是离子型(ionic)单体或非离子型(non-ionic)单体。
离子型单体包括阳离子型单体(cationic monomer)与阴离子型单体(anionic monomer),阳离子型单体包括丙烯酰氧乙基三甲基氯化铵(acryloxyethyltrimethyl ammonium chloride)、丙烯酰氧乙基三甲基苯甲基氯化铵(acryloxyethyltrimethyl benzyl ammonium chloride)、甲基丙烯酰氧乙基三甲基氯化铵(methacryloxyethyltrimethyl ammoniumchloride)、甲基丙烯酰氧乙基三甲基对甲苯磺酸盐(methacryloxyethyltrimethyl p-toluenesulfonate)、甲基丙烯酰氧乙基二甲基苯甲基氯化铵(methacryloyloxyethyl dimethylbenzyl ammoniumchloride)、丙烯酸二甲胺基乙酯(dimethylaminoethyl acrylate)、叔丁基胺乙基甲基丙烯酸酯(t-butylaminoethyl methacrylate)、乙烯基咪唑(vinylimidazole)或乙烯基吡啶(vinyl pyridine)。
阴离子型单体包括丙烯酸(acrylic acid)、甲基丙烯酸(methacrylicacid)、亚甲基丁二酸(itaconic acid)、β-羧乙基丙烯酸酯(beta-carboxyethyl acrylate)、顺丁烯二酸酐(maleic anhydride)、或上述酸的钠盐,例如丙烯酸钠(sodium acrylate)、1-烯丙氧基-2-羟丙烷磺酸钠(sodium 1-allyloxy-2hydroxypropane sulfonate)、烯丙氧基乙氧基磺酸胺(ammonium allylpolyethoxy sulfate)、苯乙烯磺酸钠(sodium styrenesulfonate)或2-丙烯胺-2-甲基丙基磺酸(2-acrylamido-2-methyl propanesulfonic acid)。
非离子型单体包括甲基丙烯酸羟乙酯(hydroxyethyl methacrylate)、丙烯酸羟乙酯(hydroxyethyl acrylate)、丙烯酸羟丙酯(hydroxypropylacrylate)、丙烯酰胺(acrylamide)、N-羟氧乙基丙烯酰胺(N-hydroxyethylacrylamide)、聚乙烯吡咯烷酮(polyvinylpyrolidone)。
水可澎润聚合物的疏水性单体包括丙烯酸甲酯(methyl acrylate)、丙烯酸乙酯(ethyl acrylate)、丙烯酸丁酯(butyl acrylate)、丙烯酸-2-乙基己酯(2-ethylhexyl acrylate)、甲基丙烯酸甲酯(methyl methacrylate)、甲基丙烯酸叔丁酯(t-butyl methacrylate)、苯乙烯(styrene)或偏氟乙烯(vinylidine fluoride)。另外,虽然丙烯腈(acrylonitrile)与甲基丙烯腈(methacrylonitrile)的单体为水溶性的,但其所组成的聚合物同样可作为疏水性单体。
另外,为了加强复合纤维膜的机械强度,另外可添加一交联剂与水可澎润聚合物进行交联反应(crosslinking reaction),此交联剂可与水可澎润聚合物中的亲水性官能团或疏水性官能团进行反应(优选与亲水性官能团反应),以降低水可澎润聚合物的溶解度(solubility)。交联剂包括酸酐(acid anhydride)、环氧树脂(epoxy)、异氰酸酯(isocyanate)、胺基树酯(甲醛与三聚氰胺、尿素或三聚氰二胺(guanamine)的反应物)、碳二亚胺(carbodiimide)、乙烯亚胺(aziridine)或上述的衍生物。
在一实施例中,马来酸酐(maleic anhydride)是与水可澎润聚合物的亲水性官能团的羟基(hydroxyl)进行交联反应。在另一实施例中,环氧树脂是与水可澎润聚合物的亲水性官能团的羧基(carboxyl)、羟基(hydroxyl)或胺基(amine)进行交联反应。在另一实施例中,异氰酸酯(isocyanate)是与水可澎润聚合物的亲水性官能团的羟基(hydroxyl)进行交联反应。在又一实施例中,三聚氰胺-甲醛树脂(melamine-formaldehyde resins)是与水可澎润聚合物的亲水性官能团的羟基(hydroxyl)、酰胺基(amide)及羧基(carboxyl)进行交联反应。在另一实施例中,碳二亚胺(carbodiimide)或乙烯亚胺(aziridine)是与水可澎润聚合物的亲水性官能团的羧基(carboxyl)进行交联反应。
除以化学键(chemical bond)进行交联反应外,也可用离子键(ionicbond)进行交联聚合(ionic crosslinking),如多氯代烃(multi-chlorinatedhydrocarbon)与胺基反应形成的季铵盐(quaternary ammonium chloride)。在一实施例中,1,6-二氯己烷(1,6-dichlorohexane)是与水可澎润聚合物的亲水性官能团的胺基反应形成季铵盐,以达成盐离子交联作用(quaternization reaction for ionic crosslinking)。
另外,水可澎润聚合物的亲水性官能团也可与一可交联的单体(crosslinkable monomers)进行聚合反应,例如N-异丁氧基甲基丙烯酰胺(N-isobutoxymethyl acrylamide)。
另外,水可澎润聚合物可由一改性聚合物(modified polymer)所组成,例如聚乙烯醇(polyvinyl alcohol)或羟乙基纤维素(hydroxyethylcellulose)或羧甲基纤维素(carboxymethyl cellulose),其中聚乙烯醇为聚醋酸乙烯酯(polyvinylacetate)的水解产物(hydrolysis product),而羟乙氧基纤维素为环氧乙烯(ethylene oxide)与纤维素(cellulose)进行加成反应(addition reaction)的产物。
此外,本发明的复合纤维膜是以一纤维(fiber)搭配一粘合剂(binder)的形式存在,其中可藉由纺丝方法将水可膨润聚合物制成纤维,纺丝方法包括溶液喷纺或静电纺丝法。之后,可利用涂布(coating)或浸渍(dipping)的方法将粘合剂(binder)充满于纤维网孔隙中,经过滚轮(roller)或平板(plate)压合,使结构致密化(dense),即可形成复合纤维膜。
粘合剂(binder)可以是本发明的水可膨润聚合物或其它聚合物,其它聚合物例如聚乙烯醇(polyvinyl alcohol,PVA)、聚苯乙烯(polystyrene,PS)、聚丙烯酰胺(polyacrylamides)、聚甲基丙烯酰胺(polymethacrylamides)、聚甲基丙烯酸酯(polymethacrylates)、聚丙烯酸酯(polyacrylates)、聚酯(polyester)、羟乙基纤维素(hydroxyethyl cellulosic)或羟丙基纤维素(hydroxypropyl cellulose)。
粘合剂(binder)的作用在于增强脱盐过滤材料的机械强度(mechanical stench)以及缩小脱盐层表面的孔洞。
此外,也可添加其它交联剂(crosslinking agents)到粘合剂(binder)中,用以避免复合纤维膜溶解(solubilization)且可增强复合纤维膜的机械强度。举例而言,可添加甲基化三聚氰胺甲醛树脂(methylatedmelamine-formaldehyde resin),例如六甲氧基甲基三聚氰胺(hexamethoxymethylmelamine)至粘合剂中,可与复合纤维膜的羟基(hydroxyl)进行反应,以改变复合纤维膜的溶解度(solubility)。
在一实施例中,先将水可膨润聚合物以静电纺丝法制作成纤维,之后再添加聚丙烯腈(polyacrylonitrile,PAN)作为粘合剂,以制作成复合纤维膜。
在另一实施例中,也可将聚丙烯腈(polyacrylonitrile,PAN)以静电纺丝法制作成纤维,之后再添加水可膨润聚合物作为粘合剂,以制作成复合纤维膜。
在另一优选实施例中,先将水可膨润聚合物以静电纺丝法制作成纤维,之后以另一种水可膨润聚合物作为粘合剂,以制作成复合纤维膜。
本发明的复合纤维膜的纤维包括微米纤维或纳米纤维,微米纤维(microfiber)的直径为约1μm~30μm,或者1μm~15μm,而纳米纤维(nanofiber)的直径为约10nm~1000nm,或者50nm~500nm。
由于公知的RO膜孔径非常小(小于1nm),因此通常需要加压至500psi,甚至高达1000psi以上才能产水,与RO膜相比,本发明最大的优点在于施加压力很小,即可达到与RO膜相近的出水量。将本发明的脱盐过滤材料进行脱盐测试,其出水流量皆大于18L/m2/hr,其压力小于10psi,脱盐效率为约60%~95%。
相较于公知技术,本发明所提供的复合纤维膜(fiber compositemembrane)的开孔(open pores)可作为一有效的脱盐过滤薄膜,因此,也可在低压的条件下达到脱盐效果。此处须注意的是,本发明的脱盐过滤材料仅需一载体层加上一脱盐层即可达成脱盐过滤的效果,而本领域技术人员可依实际应用的需求,另外再加上其它惯用透膜、半透膜或其它聚合物膜。
综上所述,由于本发明的脱盐过滤材料包括复合纤维膜,此复合纤维膜具有多孔性能有效进行脱盐反应,以在低压的情况下,仍具有高通量,因此,可有效提高脱盐效果,使得本发明的脱盐过滤材料能应用于脱盐制程、废水处理、超纯水处理、水质软化或贵重金属回收。
虽然本发明已以数个优选实施例揭露如上,然其并非用以限定本发明,任何所属技术领域中的技术人员,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围应以权利要求书所界定的范围为准。
【实施例】
比较例1
比较例1仅由两层载体层所组成,底层为聚酯(polyester,PET)非织物(购自和友纺织,HO YU TEXTILE CO.,LTD),上层为聚丙烯腈(polyacrylonitrile,PAN),其中PAN购自东华(TONGHWA synthetic fiberCO.Ltd.,分子量为约150,000~300,000)。
比较例2
以比较例1的材料为载体层,以利用静电纺丝方法制备聚丙烯腈纳米纤维(polyacrylonitrile,PAN)棉网:取30g聚丙烯腈(PAN)溶于200gN,N-二甲基乙酰胺(N,N-dimethyl acetamide,DMAc)后,电压39kV、总吐量1000μL/min、空气压力2.8kg/cm2、纺嘴到收料带距离25cm,可制得纳米纤维直径为约280nm-380nm、基重30~60g/m2的纤维网。以3g聚苯乙烯(polystyrene,PS)(购自Aldrich)(粘合剂)溶于27g对二甲苯(p-xylene),涂布于聚丙烯腈纳米纤维棉网,反应温度70℃时间1小时后制成复合纤维膜。
实施例1
制作水可膨润聚合物
取10g苯乙烯磺酸钠、40g 4-乙烯基吡啶、7g苯乙烯、50g去离子水与50g异丙醇,置入反应瓶中,在氮气下加热至70℃。取0.2g过硫酸钾(KPS)作为起始剂溶于10mL去离子水中后,注入反应瓶中后继续搅拌3小时,之后经由沉淀纯化步骤得到产物50.1g,产率为88%。
实施例2
取本发明的聚合物制作成纳米纤维棉网
取36g实施例(1)的聚合物溶于200g N,N-二甲基乙酰胺(N,N-dimethyl acetamide,DMAc)后,利用静电纺丝方法制备纳米纤维棉网:电压39kV、总吐量1200μL/min、空气压力5kg/cm2、纺嘴到收料带距离20cm,可制得直径为约70nm-120mm、棉网基重60~94g/m2的纳米纤维棉网。
实施例3
取市售聚合物制作成纳米纤维棉网
取30g聚丙烯腈(polyacrylonitrile,PAN)聚合物,溶于200g N,N-二甲基乙酰胺(N,N-dimethyl acetamide,DMAc)后,利用静电纺丝方法制备纳米纤维棉网:电压39kV、总吐量1000μL/min、空气压力2.8kg/cm2、纺嘴到收料带距离25cm,可制得纳米纤维直径为约280nm-380nm、基重30~60g/m2的纳米纤维棉网。
实施例4
以比较例1的材料为载体层。
脱盐层制法如下:取3g实施例1聚合物(粘合剂)溶于27g酒精,加入2.1g 1,6-二氯己烷(1,6-Dichlorohexane)(交联剂)制成均匀溶液,涂布于实施例2的纳米纤维棉网,在温度70℃下反应4小时后,以制成复合纤维膜。
实施例5
以比较例1的材料为载体层。
脱盐层制法如下:取0.6g实施例1聚合物(粘合剂)溶于29.4g酒精,加入0.42g 1,6-二氯己烷(1,6-Dichlorohexane)(交联剂)制成均匀溶液,涂布于实施例3的纳米纤维棉网,于温度70℃下反应4小时后,以制成复合纤维膜。
实施例6
以比较例1的材料为载体层。
脱盐层制法如下:取3g市售的PS聚合物(粘合剂)溶于27g对二甲苯(p-xylene),涂布于实施例2的纳米纤维棉网,在温度70℃下反应1小时后,以制成复合纤维膜。
实施例7
以比较例1的材料为载体层。
脱盐层制法如下:取3g实施例1聚合物(粘合剂)溶于27g酒精,加入2.1g 1,6-二氯己烷(1,6-Dichlorohexane)(交联剂)制成均匀溶液,涂布于市售聚丙烯(PP)棉网,在温度70℃下反应4小时后,以制成复合纤维膜。
实施例8
以比较例1的材料为载体层。
脱盐层制法如下:取10g市售聚乙烯醇(polyvinyl alcohol,PVA)(长春,ChangChun Group)(粘合剂)溶于90g水,加入0.01g顺丁烯二酸酐(maleic anhydride,MA)(交联剂)制成均匀溶液,涂布于实施例3的纳米纤维棉网,在温度70℃下反应4小时后,以制成复合纤维膜。
表1显示比较例1~2与实施例4~8的脱盐效率,由表1中可得知,以本发明的水可澎润聚合物制作而成的脱盐过滤材料具有最佳的脱盐效率,脱盐效率50~95%。
表1
Claims (22)
1.一种脱盐过滤材料,包括:
一载体层;以及
一脱盐层,形成于该载体层之上,其中该脱盐层为一复合纤维膜,且该复合纤维膜包括至少一种水可膨润聚合物。
2.根据权利要求1所述的脱盐过滤材料,其中该载体层由一或多层多孔性材料所组成。
3.根据权利要求1所述的脱盐过滤材料,其中该复合纤维膜是以一纤维搭配一粘合剂的形式存在,且该纤维包括微米纤维或纳米纤维。
4.根据权利要求2所述的脱盐过滤材料,其中该多孔性材料包括纤维素酯、聚砜、聚丙烯腈、聚偏氟乙烯、聚醚醚酮、聚酯、聚亚酰胺、氯化聚氯乙烯或苯乙烯-丙烯晴共聚物。
5.根据权利要求1所述的脱盐过滤材料,其中该水可膨润聚合物由亲水性单体与疏水性单体所组成。
6.根据权利要求5所述的脱盐过滤材料,其中亲水性单体包括离子型单体或非离子型单体。
7.根据权利要求6所述的脱盐过滤材料,其中该离子型单体包括阳离子型单体与阴离子型单体。
8.根据权利要求7所述的脱盐过滤材料,其中该阳离子型单体包括丙烯酰氧乙基三甲基氯化铵、丙烯酰氧乙基三甲基苯甲基氯化铵、甲基丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基三甲基对甲苯磺酸盐、甲基丙烯酰氧乙基二甲基苯甲基氯化铵、丙烯酸二甲胺基乙酯、叔丁基胺乙基甲基丙烯酸酯、乙烯基咪唑或乙烯基吡啶。
9.根据权利要求7所述的脱盐过滤材料,其中该阴离子型单体包括丙烯酸、甲基丙烯酸、亚甲基丁二酸、β-羧乙基丙烯酸酯、顺丁烯二酸酐或上述酸的钠盐。
10.根据权利要求6所述的脱盐过滤材料,其中该非离子型单体包括甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酰胺、N-羟氧乙基丙烯酰胺或聚乙烯吡咯烷酮。
11.根据权利要求5所述的脱盐过滤材料,其中该疏水性单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸叔丁酯、苯乙烯或偏氟乙烯。
12.根据权利要求1所述的脱盐过滤材料,其中该水可澎润聚合物还可与一交联剂进行交联反应。
13.根据权利要求12所述的脱盐过滤材料,其中该交联剂包括酸酐、环氧树脂、异氰酸酯、胺基树脂、烷氧基甲基丙烯酰胺、碳二亚胺、乙烯亚胺或上述的衍生物。
14.根据权利要求13所述的脱盐过滤材料,其中该酸酐是与该水可澎润聚合物的羟基进行交联反应。
15.根据权利要求13所述的脱盐过滤材料,其中该环氧树脂是与该水可澎润聚合物的羧基、羟基或胺基进行交联反应。
16.根据权利要求13所述的脱盐过滤材料,其中该异氰酸酯是与该水可澎润聚合物的羟基进行交联反应。
17.根据权利要求13所述的脱盐过滤材料,其中该胺基树酯是与该水可澎润聚合物的羟基、羧基或酰胺基进行交联反应。
18.根据权利要求13所述的脱盐过滤材料,其中该烷氧基甲基丙烯酰胺是与该水可澎润聚合物的羟基进行交联反应。
19.根据权利要求13所述的脱盐过滤材料,其中该碳二亚胺或乙烯亚胺是与该水可澎润聚合物的羧基进行交联反应。
20.根据权利要求12所述的脱盐过滤材料,其中该交联反应包括进行离子交联反应。
21.根据权利要求20所述的脱盐过滤材料,其离子交联反应是由一多氯代烃与该水可澎润聚合物的胺基反应形成季铵盐。
22.根据权利要求1所述的脱盐过滤材料,其中该水可澎润聚合物包括聚乙烯醇、羧甲基纤维素或羟乙基纤维素。
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CN104906969B (zh) * | 2015-05-21 | 2017-03-01 | 浙江大学 | 交联型聚电解质‑表面活性剂复合物的制备方法及用途 |
CN105289331B (zh) * | 2015-12-09 | 2017-11-17 | 苏州科技学院 | 两亲性三嵌段聚合物PSxMAAy‑g‑fPEGz改性PVDF超滤膜及其制备方法 |
CN105664742A (zh) * | 2016-04-13 | 2016-06-15 | 伊美特(上海)环保科技有限公司 | 一种提高聚酰胺反渗透膜水通量及抗污染能力的方法 |
CN112694758B (zh) | 2019-10-23 | 2022-05-24 | 财团法人工业技术研究院 | 离子交换树脂组合物、其制备方法以及其所形成的膜材 |
CN111632580B (zh) * | 2020-05-18 | 2023-04-28 | 宁夏大学 | 一种聚合物刷型磁性氧化石墨烯吸附材料及其制备方法 |
CN112007514B (zh) * | 2020-07-28 | 2022-07-12 | 新长丰实业股份有限公司 | 纳滤复合膜 |
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US11642632B2 (en) | 2020-11-13 | 2023-05-09 | New Micropore, Inc. | Nanofiltration composite membranes |
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CN101039744A (zh) * | 2004-08-13 | 2007-09-19 | 麦克马斯特大学 | 包含非交联的胶凝聚合物的复合材料 |
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