CN103182253B - 脱盐过滤材料 - Google Patents
脱盐过滤材料 Download PDFInfo
- Publication number
- CN103182253B CN103182253B CN201110461177.8A CN201110461177A CN103182253B CN 103182253 B CN103182253 B CN 103182253B CN 201110461177 A CN201110461177 A CN 201110461177A CN 103182253 B CN103182253 B CN 103182253B
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- China
- Prior art keywords
- desalination
- filtration material
- layer
- coating
- nanofibers
- 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.)
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- 238000010612 desalination reaction Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000002121 nanofiber Substances 0.000 claims abstract description 40
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims description 34
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 229920002521 macromolecule Polymers 0.000 claims description 15
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 15
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 14
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 150000001805 chlorine compounds Chemical class 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 238000012695 Interfacial polymerization Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 238000007607 die coating method Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- 150000002118 epoxides Chemical group 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical group CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 238000011033 desalting Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000013535 sea water Substances 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Polymers C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- KDUFKIIMEWLUSX-UHFFFAOYSA-N C1CN1.C1CN1 Chemical compound C1CN1.C1CN1 KDUFKIIMEWLUSX-UHFFFAOYSA-N 0.000 description 1
- XYGKGASSKJWLTN-UHFFFAOYSA-N CCCCCCC.CCCCCCC Chemical compound CCCCCCC.CCCCCCC XYGKGASSKJWLTN-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- DATIMHCCPUZBTD-UHFFFAOYSA-N pentane Chemical compound CCCCC.CCCCC DATIMHCCPUZBTD-UHFFFAOYSA-N 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 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
- 238000003825 pressing Methods 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
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- 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
- B01D69/1216—Three or more layers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
- B01D71/381—Polyvinylalcohol
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/42—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
-
- 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
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Abstract
本发明提供一种脱盐过滤材料，包括：一载体层；一纳米纤维层，形成于该载体层之上；一疏水层，形成于该纳米纤维层之上；以及一亲水层，形成于该疏水层之上。
Description
技术领域
本发明是涉及一种脱盐过滤材料，且特别是涉及一种具有多层结构的脱盐过滤材料。
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 5,464,538提出一种过滤材料，通过乙烯单体经过交联反应制得具有高通量的过滤材料。
美国专利US 5,755,964提出一种过滤材料，其利用胺类化合物处理逆渗透膜(Reverse Osmosis，RO)表面，以增加RO膜的湿润性(wetting)，以提高RO膜的通量。
然而，已知的脱盐过滤材料主要为无孔隙高分子薄膜(nonporous polymericthin film)，其需在高压条件下操作。
因此，业界亟需提出一种脱盐过滤材料，此材料能低操作压力的条件下达到高脱盐过滤效果。
发明内容
本发明的目的在于提供一种能在低操作压力的条件下达到高脱盐过滤效果的脱盐过滤材料。
本发明提供一种脱盐过滤材料，包括：一载体层；一纳米纤维层，形成于该载体层之上；一疏水层，形成于该纳米纤维层之上；以及一亲水层，形成于该疏水层之上。
本发明的优点在于：与现有技术相比，本发明的脱盐过滤材料在施加压力很小时即可达到与RO膜相近的出水量以及高效的脱盐过滤效果。
为让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，作详细说明如下：
附图说明
图1为本发明的脱盐过滤材料的剖面图；其中，主要元件符号说明：
100～脱盐过滤材料 110～载体层
120～纳米纤维层 130～疏水层
140～亲水层。
具体实施方式
请参见图1，此图显示本发明脱盐过滤材料100的剖面图，其中于载体层110之上依序为纳米纤维层120、疏水层130与亲水层140。
上述的载体层110包括一或多层多孔性材料所组成，其中多孔性材料为纤维素酯(cellouse ester)、聚砜(polysulfone)、聚丙烯腈(polyacrylonitrile，PAN)、聚偏氟乙烯(polyvinylidene fluoride，PVDF)、聚醚酮(polyetheretherketone，PEK)、聚酯(polyester，PET)、聚酰亚胺(polyimide，PI)、氯化聚氯乙烯(chlorinatedpolyvinyl chloride，PVC)或苯乙烯-丙烯腈共聚物(styrene acrylnitrile，SAN)等，且载体层可自行合成或由市售取得，此外，该多孔性材料可以以无纺布、织布或开孔(open pores)材料的形式存在。
上述的纳米纤维层120的材料为离子性高分子、聚乙烯醇(polyvinyl alcohol，PVA)、聚丙烯腈(polyacrylonitrile，PAN)、聚醚砜(Polyethersulfone，PES)或聚偏氟乙烯(polyvinglidene fluoride，PVDF)。
离子性高分子具有下述化学式(I)的结构：
化学式(I)
其中R1为苯环磺酸基或烷链磺酸基；
R2为
R3为
以及m、n与q为1～200。离子性高分子的分子量Mn为约5000到160000，其中m、n与q为以Mn理论计算所得。
纳米纤维层120的形成方法包括溶液纺丝法(solution spining)或静电纺丝法(electrospinning)。此外，纳米纤维层120的纤维直径为约20-600nm，较佳为约50-200nm。
另外，为了加强纳米纤维的机械强度，另外可添加一交联剂与离子性高分子进行交联反应(crosslinking reaction)，此交联剂可与离子性高分子中的亲水性官能基或疏水性官能基进行反应(较佳与亲水性官能基反应)，以降低离子性高分子的溶解度(solubility)。所述交联剂为酸酐(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。
疏水层130包括疏水性材料，例如聚丙烯(polypropylene，PP)、聚偏氟乙烯(polyvinglidene fluoride，PVDF)、聚二甲基硅氧烷(Poly-dimethylsiloxane，PDMS)或环氧树脂(epoxy)。
疏水层130的形成方法包括界面聚合法(interfacial polymerization，IP)或涂布方法(coating)。疏水层130的厚度为约50-1000nm，较佳为约100-300nm。界面聚合法(IP)是利用单体在两个不互溶的界面处进行聚合反应，于反应界面形成致密的薄膜。
于一实施例中，疏水层130为聚酰胺膜，其可通过胺基化合物与酰氯化合物两种单体反应而得，反应步骤是先将胺基化合物溶于醇类与水中，先形成水溶液，将载体层110/纳米纤维层120浸入水溶液中，之后取出去除表面多余的水分，再将纳米纤维层120浸入酰氯化合物的有机溶剂中，以进行界面聚合反应，而得到疏水层130。
在胺基化合物的水溶液中，胺基化合物的添加量为占所述胺基化合物的水溶液的约0.1-30重量％，例如双二甲胺(piperazine，PIP)或间苯二胺(M-phenylene diamine，MPD)，醇类例如甲醇、乙醇、异丙醇或正丁醇。
在酰氯化合物的有机溶剂中，酰氯化合物的添加量为占所述酰氯化合物的有机溶剂的约0.1-1重量％，例如苯三甲基酰氯(trimesoyl chloride，TMC)或对苯二酰氯(telephthalloyl chloride，TPC)。有机溶剂例如正己烷(hexane)、三氯三氟乙烷(1，1，2-Trichloro-1，2，2-trifluoroethane)、戊烷(pentane)或庚烷(heptane)。
涂布法(coating)包括旋转涂布(spin coating)、刷涂(brush coating)、刮刀涂布(knife coating)、喷洒式涂布(spraying)、浸沾式涂布(dip coating)、狭缝模具涂布(slot die coating)或印刷(printing)。进行涂布法时，疏水性材料占整体涂布液的含量为约1-10重量％。
亲水层140为离子性高分子或聚乙烯醇(polyvinyl alcohol，PVA)。为了加强亲水层140的机械强度，可另外加入交联剂与亲水层交联，离子性高分子可与交联剂交联(所述交联剂例如环氧化物(epoxy)或卤烷化物(alkyl halides)，添加量为占所述离子高分子的重量的约10-30重量％进行交联反应。聚乙烯醇(polyvinyl alcohol，PVA)可与交联剂(所述交联剂例如戊二醇(propanediol)、马来酸(Maleic acid)或马来酸酐(Maleic acid anhydrides)，添加量为占所述聚乙烯醇(polyvinyl alcohol，PVA)的重量的约1-10重量％进行交联反应。
已知脱盐过滤材料主要包括载体层、多孔层与表面活化层，多孔层为直通孔结构(孔隙大小约为0.01～1μm)，而表面活化层几乎是致密且无孔洞，因此需要较高压力才能使水通过。
须注意的是，本发明的脱盐过滤材料为一复合层，主要通过多层结构达到高通量与高脱盐效果，其中最上层的亲水层140与水之间具有较高亲和力(affinity)，且亲水层140具有离子特性，可以与水中的盐类形成静电作用力，而达到阻隔离子的效果。中间的疏水层130形成无阻力(no resistance)通道，可以让水快速通过。而纳米纤维层120具有网状多孔性(较传统多孔膜孔隙率较高)，可有效提升通量，且通过纳米纤维层120与疏水层130之间的界面毛细驱动力，以及疏水层130与亲水层140之间的界面毛细驱动力，会加速扩散现象(diffusion)，提供向下的作用力，使水分子加速通过多层结构，达到低压出水与增加通量的效果。
已知的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，其过膜压力(trans-membrane pressure，TMP)小于5kg/cm2，且通量皆大于5mL/hr，脱盐效率可达约95％～99％。
此外，本领域人士可依实际应用的需求，另外再加上其它惯用的透膜、半透膜或其它高分子膜于本发明的脱盐过滤材料上。
综上所述，本发明的脱盐过滤材料包括多层结构，每一层结构具有特殊功效，以于低压的情况下，仍具有高通量，使得本发明的脱盐过滤材料能应用于脱盐制程、海水处理、超纯水处理、水质软化或贵重金属回收。
【制备例】
制备例1制作聚丙烯腈(PAN)纳米纤维
取30g聚丙烯腈(polyacrylonitrile，PAN)高分子，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。
制备例2制备离子高分子纳米纤维(离子高分子简称poly E)
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，于氮气下加热至70℃。取0.2g过硫酸钾(KPS)作为引发剂溶于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50.1g离子高分子(poly E)，产率为88％。
之后，将离子高分子溶于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-120nm、棉网基重60～94g/m2的纳米纤维棉网。
【实施例】
实施例1
将制备例1的PAN纳米纤维/PET置于水相(间苯二胺(MPD)/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(苯三甲基酰氯(TMC)/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，以形成疏水层于纳米纤维层之上。
之后，将制备例2的PolyE溶于乙醇溶液(5wt％)进行涂布在此复合材料，然后置于烘箱70℃20分钟进行30000ppm NaCl脱盐测试。
实施例2
将制备例2的PolyE溶于乙醇溶液(5wt％)涂布在PolyE纳米纤维/PET然后置于烘箱70℃20分钟。
之后，将此复合材料置于水相(MPD/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，进行30000ppm NaCl脱盐测试。经GPC测试，所得的polyE的Mn约136784。
实施例3
将制备例2的纳米纤维/PET置于水相(MPD/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，以形成疏水层。
之后，将聚乙烯醇(PVA)溶于水溶液(5w％)并加入0.1wt％戊二醛(glutaraldehyde，GA)涂布在此复合材料，然后置于烘箱70℃20分钟进行400ppm CaCl2脱盐测试。
实施例4
将制备例2的纳米纤维/PET置于水相(双二甲胺(piperazine，PIP)/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，以形成疏水层。
之后，将制备例2的PolyE溶于乙醇溶液(5wt％)涂布在此复合材料，然后置于烘箱70℃20分钟进行30000ppm NaCl脱盐测试。
实施例5
将制备例2的纳米纤维/PET置于水相(PIP/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，进行400ppm CaCl2脱盐测试。
实施例6
将制备例2的纳米纤维/PET置于水相(MPD/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，进行400ppm CaCl2脱盐测试。
实施例7
将5％聚丙烯(Polypropylene)溶液涂布于制备例2的纳米纤维/PET上，置于烘箱70℃20分钟，以形成疏水层。
之后，将制备例2离子高分子的乙醇溶液(5wt％)涂布于制备例2的纳米纤维/PET/PP上进入烘箱70℃10分钟，进行400ppm CaCl2脱盐测试。
实施例8
将聚偏氟乙烯(polyvinglidene fluoride，PVDF)溶于丙酮溶液(5wt％)喷洒式涂布(spraying)于制备例2的纳米纤维/PET上，置于烘箱70℃20分钟，以形成疏水层。
之后，将制备例2离子高分子的乙醇溶液(5wt％)涂布于PVDF/制备例2的纳米纤维/PET上进入烘箱70℃10分钟，进行400ppm CaCl2脱盐测试。
实施例9
将5wt％聚二甲基硅氧烷(Poly-dimethylsiloxane，PDMS)溶液涂布于制备例2的纳米纤维/PET上，置于烘箱70℃20分钟，以形成疏水层。
之后，将制备例2离子高分子的乙醇溶液(5wt％)涂布于PDMS/制备例2的纳米纤维/PET上进入烘箱70℃10分钟，进行400ppm CaCl2脱盐测试。
实施例10
将5wt％环氧树脂(epoxy)溶液并加入0.1％二次乙基三胺(Diethylenetriamine，DETA)涂布于制备例2的纳米纤维/PET上，置于烘箱70℃20分钟，以形成疏水层。
之后，将制备例2离子高分子的乙醇溶液(5wt％)涂布于环氧树脂/制备例2的纳米纤维/PET上进入烘箱70℃10分钟，进行400ppm CaCl2脱盐测试。
比较例1
将PES多孔膜置于水相(MPD/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，进行30000ppm NaCl脱盐测试。
比较例2
将制备例1的PAN纳米纤维/PET置于水相(MPD/水＝2/98(w/w))中3分钟，取出后压吸，置于油相(TMC/己烷＝0.1/100(w/w))中30秒，进入烘箱70℃10分钟，进行30000ppm NaCl脱盐测试。
比较例3
将PVA溶于水溶液(5w％)并加入0.1wt％戊二醛(GA)进行涂布在PES膜上，然后置于烘箱70℃20分钟进行30000ppm NaCl脱盐测试。
比较例4
将5wt％环氧树脂(epoxy)溶液并加入0.1％二次乙基三胺(DETA)进行涂布于PES膜上，然后置于烘箱70℃20分钟进行30000ppm NaCl脱盐测试。
比较例5
将5wt％硅树脂(silicon resin)溶液进行涂布于PES膜上，然后置于烘箱70℃20分钟进行30000ppm NaCl脱盐测试。
比较例6
比较例6的材料同于比较例1，差别在于比较例6进行400ppm CaCl2脱盐测试。
表1显示实施例1-10与比较例1-5的脱盐效果。由表1可知，本发明实施例1-2与4在过膜压力(trans-membrane pressure，TMP)小于5kg/cm2的情况下进行NaCl脱盐测试，可达到97-99％的脱盐效果，表示此材料未来有潜力应用于海水过滤，实施例3与5-10进行CaCl2脱钙测试，表示本发明的材料未来有潜力应用于水质软化处理。
由表1得知，在过膜压力(trans-membrane pressure，TMP)小于5kg/cm2的情况下，比较例1-5无法达到任何的脱盐效果。由比较例2可知，在缺乏最上层亲水层的情况下，无法达到脱盐效果。
表1
×：表示无法量测
虽然本发明已以数个较佳实施例揭露如上，然其并非用以限定本发明，任何所属技术领域中具有通常知识者，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当视后附的权利要求书所界定的范围为准。
Claims (12)
1.一种脱盐过滤材料，包括：
一载体层；
一纳米纤维层，形成于所述载体层之上；
一疏水层，形成于所述纳米纤维层之上；以及
一亲水层，形成于所述疏水层之上；
其中所述纳米纤维层的材料为离子性高分子、聚乙烯醇、聚丙烯腈、聚醚砜或聚偏氟乙烯；
所述疏水层的材料为聚丙烯、聚偏氟乙烯、聚二甲基硅氧烷或环氧树脂；
所述亲水层的材料为离子性高分子或聚乙烯醇。
2.如权利要求1所述的脱盐过滤材料，其中所述载体层包括一或多层多孔性材料。
3.如权利要求2所述的脱盐过滤材料，其中所述多孔性材料为纤维素酯、聚砜、聚丙烯腈、聚偏氟乙烯、聚醚酮、聚酯、聚酰亚胺、氯化聚氯乙烯或苯乙烯-丙烯腈共聚物。
4.如权利要求1所述的脱盐过滤材料，其中所述离子性高分子具有下述化学式(I)的结构：
其中R1为苯环磺酸基或烷链磺酸基；
R2为
R3为以及
m、n与q为1～200。
5.如权利要求1所述的脱盐过滤材料，其中所述纳米纤维层的形成方法为溶液纺丝法或静电纺丝法。
6.如权利要求1所述的脱盐过滤材料，其中所述疏水层的形成方法为界面聚合法或涂布法。
7.如权利要求6所述的脱盐过滤材料，其中所述界面聚合法利用单体进行聚合，单体包括胺基化合物与酰氯化合物。
8.如权利要求7所述的脱盐过滤材料，其中所述胺基化合物为双二甲胺或间苯二胺。
9.如权利要求7所述的脱盐过滤材料，其中所述酰氯化合物为苯三甲基酰氯或对苯二酰氯。
10.如权利要求6所述的脱盐过滤材料，其中所述涂布法为旋转涂布、刷涂、刮刀涂布、喷洒式涂布、浸沾式涂布、狭缝模具涂布或印刷。
11.如权利要求1所述的脱盐过滤材料，其中所述离子性高分子还包括与交联剂交联，所述交联剂为环氧化物或卤烷化物。
12.如权利要求11所述的脱盐过滤材料，其中所述聚乙烯醇还包括与交联剂交联，其中所述交联剂为戊二醇、马来酸或马来酸酐。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| TW100149118A TWI453062B (zh) | 2011-12-28 | 2011-12-28 | 脫鹽過濾材料 |
| TW100149118 | 2011-12-28 |
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| Publication Number | Publication Date |
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| CN103182253A CN103182253A (zh) | 2013-07-03 |
| CN103182253B true CN103182253B (zh) | 2015-02-04 |
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| US (1) | US20130168312A1 (zh) |
| CN (1) | CN103182253B (zh) |
| TW (1) | TWI453062B (zh) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104117288B (zh) * | 2013-04-25 | 2017-07-18 | 财团法人工业技术研究院 | 过滤材料及其制造方法 |
| CN103752183B (zh) * | 2014-01-21 | 2015-10-21 | 清华大学 | 一种聚二甲基硅氧烷多层复合分离膜及其制备方法 |
| JP2017529994A (ja) * | 2014-07-07 | 2017-10-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | 濾過膜 |
| CN106925032B (zh) * | 2015-12-31 | 2019-12-10 | 财团法人工业技术研究院 | 过滤材料 |
| TWI568491B (zh) | 2015-12-31 | 2017-02-01 | 財團法人工業技術研究院 | 過濾材料 |
| CN106823856B (zh) * | 2017-03-21 | 2020-10-30 | 亚美滤膜（南通）有限公司 | 亲水性多孔聚烯烃材料及其亲水性改性处理方法 |
| CN108905647B (zh) * | 2018-06-19 | 2021-07-09 | 杭州安诺过滤器材有限公司 | 一种亲水性聚偏二氟乙烯微滤膜的制备方法 |
| TWI674142B (zh) * | 2018-11-12 | 2019-10-11 | 國立臺灣大學 | 一種全疏薄膜及其製造方法 |
| CN110917895B (zh) * | 2019-12-30 | 2022-01-25 | 南京公诚节能新材料研究院有限公司 | 一种含石墨烯微片的直饮水处理膜及其制备方法 |
| CN111850725B (zh) * | 2020-06-19 | 2022-09-02 | 浙江工商大学 | 聚丙烯腈基-1-甲基哌嗪显色纤维及其合成方法和应用 |
| CN113401960B (zh) * | 2021-05-19 | 2022-08-30 | 大连理工大学 | 一种高效稳定且具有自清洁功能的新型光热水蒸发材料及其制备方法 |
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| JP2008515668A (ja) * | 2004-10-06 | 2008-05-15 | ザ リサーチ ファウンデーション オブ ステイト ユニバーシティー オブ ニューヨーク | 高流量かつ低付着の濾過媒体 |
| WO2008118228A2 (en) * | 2006-12-05 | 2008-10-02 | Stonybrook Water Purification | Articles comprising a fibrous support |
| JP4980154B2 (ja) * | 2007-06-28 | 2012-07-18 | 株式会社クラレ | 濾材およびその製造方法 |
| JP5177506B2 (ja) * | 2008-02-28 | 2013-04-03 | 栗田工業株式会社 | フィルタ及び液処理方法 |
| JP5262668B2 (ja) * | 2008-12-15 | 2013-08-14 | 東レ株式会社 | 複合ナノろ過膜 |
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| CN101642683B (zh) * | 2009-09-10 | 2012-05-02 | 苏州信望膜技术有限公司 | 双层复合中空纤维纳滤膜及其制备方法和专用工具 |
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| Publication number | Publication date |
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| TW201325703A (zh) | 2013-07-01 |
| CN103182253A (zh) | 2013-07-03 |
| TWI453062B (zh) | 2014-09-21 |
| US20130168312A1 (en) | 2013-07-04 |
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