CN111632502A - Non-woven fabric substrate supported polyethylene nanofiltration membrane - Google Patents
Non-woven fabric substrate supported polyethylene nanofiltration membrane Download PDFInfo
- Publication number
- CN111632502A CN111632502A CN202010504909.6A CN202010504909A CN111632502A CN 111632502 A CN111632502 A CN 111632502A CN 202010504909 A CN202010504909 A CN 202010504909A CN 111632502 A CN111632502 A CN 111632502A
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- CN
- China
- Prior art keywords
- woven fabric
- nanofiltration membrane
- membrane
- polyethylene
- fabric substrate
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 102
- -1 polyethylene Polymers 0.000 title claims abstract description 100
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 85
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 85
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 75
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 72
- 239000000758 substrate Substances 0.000 title claims abstract description 66
- 239000012982 microporous membrane Substances 0.000 claims abstract description 42
- 239000011148 porous material Substances 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 230000004907 flux Effects 0.000 abstract description 24
- 239000000178 monomer Substances 0.000 abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 7
- 229920000768 polyamine Polymers 0.000 abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 6
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005374 membrane filtration Methods 0.000 abstract description 3
- 210000004379 membrane Anatomy 0.000 description 29
- 239000000243 solution Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-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
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- WHKWMTXTYKVFLK-UHFFFAOYSA-N 1-propan-2-ylpiperazine Chemical compound CC(C)N1CCNCC1 WHKWMTXTYKVFLK-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- GNIZQCLFRCBEGE-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(Cl)=O GNIZQCLFRCBEGE-UHFFFAOYSA-N 0.000 description 1
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JTWJCOYICMHNCF-UHFFFAOYSA-N CO.N1C=NC(C1)=O Chemical compound CO.N1C=NC(C1)=O JTWJCOYICMHNCF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- PBWUKDMYLKXAIP-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCCC1(C(Cl)=O)C(Cl)=O PBWUKDMYLKXAIP-UHFFFAOYSA-N 0.000 description 1
- JREFGECMMPJUHM-UHFFFAOYSA-N cyclopentane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCC1(C(Cl)=O)C(Cl)=O JREFGECMMPJUHM-UHFFFAOYSA-N 0.000 description 1
- CRMQURWQJQPUMY-UHFFFAOYSA-N cyclopropane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CC1(C(Cl)=O)C(Cl)=O CRMQURWQJQPUMY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- 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
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0292—Polyurethane fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyethylene nanofiltration membrane supported on a non-woven fabric substrate, which comprises a non-woven fabric substrate, a polyethylene microporous membrane and a nanofiltration membrane skin layer; the polyethylene microporous membrane is supported on the non-woven fabric substrate to obtain a non-woven fabric supported polyethylene microporous membrane; the non-woven fabric supported polyethylene microporous membrane forms the nanofiltration membrane skin layer through interfacial polymerization of polyamine water phase monomers and polyacyl chloride oil phase monomers. Compared with a polyethylene microporous nanofiltration membrane without a non-woven fabric as a substrate for supporting, the microporous nanofiltration membrane has the advantages of higher inorganic salt rejection rate, better and stable membrane filtration performance and longer service life; compared with the existing commercial polysulfone-based nanofiltration membrane, the nano-filtration membrane has higher flux and better comprehensive performance on the basis of reaching the same level of rejection rate and service life.
Description
Technical Field
The invention relates to the technical field of nanofiltration membranes, and particularly relates to a non-woven fabric substrate supported polyethylene nanofiltration membrane.
Background
After the 21 st century, the problems of environmental damage and resource shortage are becoming more prominent, and the problem of shortage of fresh water resources is very serious. Fresh water is recycled from river and lake water, underground brackish water, seawater and even sewage and wastewater by a membrane separation method, so that the water resource crisis can be effectively relieved, and the method becomes an important ring for sustainable development in the future. The functional nanofiltration membrane can effectively reduce the hardness, turbidity, chromaticity, bacteria, fungi and other microorganisms of water, can obtain higher water yield under low pressure, and has been widely applied to foreign industrial manufacturing industry and household life.
In the existing commercial nanofiltration membrane, after the polysulfone is formed into a membrane, the thickness of finger-shaped holes and skin layers is high, the aperture is small, the permeation resistance is large, and the flux is at a low level; the polyethylene microporous membrane formed by thermally induced phase separation and stretching pore formation has no compact skin layer, the whole membrane is loose rib-shaped fiber, the permeation resistance is small, and the flux is greatly improved compared with the traditional polysulfone membrane. However, the polyethylene material is too thin, which has the defect of poor mechanical strength, especially compressive property.
Therefore, there is a strong need in the art for a nanofiltration membrane with high mechanical strength, high flux, high inorganic salt rejection rate, stable performance and long service life.
Disclosure of Invention
In view of the above, the invention is expected to provide a non-woven fabric substrate supported polyethylene nanofiltration membrane, so as to improve the flux of the nanofiltration membrane, improve the rejection rate of inorganic salts, prolong the service life and stabilize the performance on the premise of ensuring good mechanical strength.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention provides a non-woven fabric substrate supported polyethylene nanofiltration membrane, which is characterized in that: comprises a non-woven fabric substrate, a polyethylene microporous membrane and a nanofiltration membrane skin layer; the polyethylene microporous membrane is supported on the non-woven fabric substrate; and the nanofiltration membrane skin layer is positioned on the polyethylene microporous membrane.
Furthermore, the material of the non-woven fabric substrate is one or a combination of several of polyethylene terephthalate, polyethylene, polypropylene, polyamide and polyurethane.
Further, the thickness of the non-woven fabric substrate is 70-110 μm, and the mass per unit area is 10-150 g/m2。
Furthermore, the thickness of the non-woven fabric substrate is 90 to 100 μm, and the mass per unit area is 50 to 100g/m2。
Further, the thickness of the polyethylene microporous membrane is between 5 and 25 mu m, and the average pore diameter is between 0.01 and 0.2 mu m.
Furthermore, the thickness of the polyethylene microporous membrane is between 9 and 20 μm, and the average pore diameter is between 0.02 and 0.06 μm.
The invention has the following beneficial effects:
1) compared with the existing commercial nanofiltration membrane, the ultrathin loose membrane main body structure of the polyethylene nanofiltration membrane supported by the non-woven fabric substrate can obtain better pure water permeability, obtain higher flux and keep the same inorganic salt interception level;
2) compared with the existing commercial nanofiltration membrane, the non-woven fabric substrate supported polyethylene nanofiltration membrane provided by the invention can save the cost by more than 40%, has strong continuous industrial production capacity, and has considerable economic benefits;
3) the invention provides a non-woven fabric substrate supported polyethylene nanofiltration membrane, which overcomes the problems of damaged desalting layer and performance attenuation caused by over-thin polyethylene microporous membrane, and prolongs the time for keeping the membrane filtration performance stable, thereby effectively prolonging the service life of the membrane.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a non-woven fabric substrate supported polyethylene nanofiltration membrane provided by the invention;
FIG. 2 is a schematic structural diagram of a non-woven fabric substrate supported polyethylene nanofiltration membrane according to the invention;
description of the element reference numerals
1 nanofiltration Membrane cortex
2 polyethylene microporous membrane
3 non-woven fabric substrate
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The specific embodiment of the invention provides a non-woven fabric substrate supported polyethylene nanofiltration membrane, which comprises a non-woven fabric substrate 3, a polyethylene microporous membrane 2 and a nanofiltration membrane skin layer 1; the polyethylene microporous membrane 2 is supported on the non-woven fabric substrate 3 to obtain a non-woven fabric supported polyethylene microporous membrane; the non-woven fabric supported polyethylene microporous membrane is formed by interfacial polymerization of polyamine water phase monomers and polyacyl chloride oil phase monomers to form the nanofiltration membrane skin layer 1.
Preferably, the material of the non-woven fabric substrate 3 is one or a combination of several of polyethylene terephthalate, polyethylene, polypropylene, polyamide and polyurethane.
Preferably, the thickness of the non-woven fabric substrate 3 is 70-110 μm, and the mass per unit area is 10-150 g/m2。
Specifically, the thickness of the non-woven fabric substrate 3 is 90 to 100 μm, and the mass per unit area is 50 to 100g/m2。
Preferably, the thickness of the polyethylene microporous membrane 2 is between 5 and 25 μm, and the average pore diameter is between 0.01 and 0.2 μm.
Specifically, the thickness of the polyethylene microporous membrane 2 is between 9 and 20 micrometers, and the average pore diameter is between 0.02 and 0.06 micrometer.
Preferably, the polyethylene nanofiltration membrane carried on the non-woven fabric substrate has pure water flux of 60-90L/m under 0.48MPa2h, the rejection rate of monovalent salt is more than 35%, and the rejection rate of divalent salt is more than 98%.
The invention also provides a method for preparing the non-woven fabric substrate supported polyethylene nanofiltration membrane, which comprises the following steps:
dedusting the polyethylene microporous membrane 2, soaking the polyethylene microporous membrane with an organic solvent, and then washing the polyethylene microporous membrane with deionized water;
laying a non-woven fabric under the polyethylene microporous membrane 2, flattening, and compacting and fixing the periphery to obtain a non-woven fabric supported polyethylene microporous membrane;
immersing the non-woven fabric loaded polyethylene microporous membrane in an aqueous phase solution containing polyamine; the polyamine aqueous phase solution comprises the following components: a polyfunctional amine monomer, an acid acceptor and a monomer diffusion promoter; the mass fraction of the polyfunctional amine monomer in the aqueous phase solution is 0.5-3.5%, the mass fraction of the acid acceptor in the aqueous phase solution is 0.1-5%, and the mass fraction of the monomer diffusion promoter in the aqueous phase solution is 0.01-1%; the immersion time is 5-150 seconds;
taking out the membrane from the water phase, removing the redundant water phase solution, then immersing the membrane into an oil phase solution containing a polyacyl chloride monomer, and taking out the membrane after a period of interfacial polymerization reaction to obtain a primary membrane; the mass fraction of the polybasic acyl chloride monomer in the oil phase solvent is 0.01-1%, and the immersion time is 5-120 seconds;
and (3) carrying out heat treatment on the primary membrane obtained in the step for 0.5-20 minutes at 30-100 ℃, and then airing to obtain the non-woven fabric substrate supported polyethylene nanofiltration membrane.
Preferably, the polyfunctional amine monomer is a combination of one or more of piperazine, homopiperazine, N-methylpiperazine, N-isopropylpiperazine, 1-amino-4-methylpiperazine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, ethylenediamine, propylenediamine and tris (2-diaminoethyl) amine.
Preferably, the acid acceptor is one or more of triethylamine, sodium acetate, N-diisopropylethylamine, pyridine and potassium carbonate.
Preferably, the monomer diffusion promoter is one or more of tetrahydrofuran, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, ethoxylated nonylphenol, polyoxyalkylene ether, polyoxyethylene alkyl ether, octylphenol ethoxylate, poloxamer, alkylpolyglucoside, cetyl or oleyl alcohol, polyoxyethylene (20) oleyl ether, imidazolinone carbinol.
Preferably, the polybasic acyl chloride monomer is one of trimesoyl chloride, paraphthaloyl chloride, isophthaloyl chloride, phthalic acid chloride, biphenyl dicarboxylic acid chloride, naphthalene dicarboxylic acid chloride, cyclopropane tricarboxylic acid chloride, cyclopentane tricarboxylic acid chloride and cyclohexane tricarboxylic acid chloride.
Preferably, the oil phase solvent is one of n-hexane, cyclohexane, heptane, Isopar G, Isopar E, Isopar L.
Preferably, the organic solvent includes methanol, ethanol, isopropanol, N-N dimethylformamide, N-N dimethylacetamide, and N-methylpyrrolidone.
Preferably, the mass fraction of the polyacyl chloride monomer in the oil phase solvent is 0.05-0.5%.
Preferably, the time for immersing the non-woven fabric-supported polyethylene microporous membrane in the aqueous solution containing the polyamine is 30-100 seconds.
Preferably, the immersion time in the oil phase solution containing the polybasic acyl chloride monomer is 15 to 60 seconds.
Preferably, the heat treatment temperature of the primary film is 50-80 ℃, and the heat treatment time is 3-10 minutes.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the performance parameters were determined as follows:
(1) thickness: the thickness of the plastic film and the sheet is measured by using a German Mark film thickness gauge C1216 according to the measuring method of GB/T6672-2001, the same sample is tested for 5 times, and the average value is taken as the thickness.
(2) Average pore diameter and porosity: the average pore size and porosity of the polyethylene separation membrane were obtained by testing with a fully automatic water press of type AAQ-3K-a-1, manufactured by american Porous Materials inc. The water pressure of the full-automatic water pressure instrument is controlled at 1500psi of 100 and 1500psi, the surface tension of water is 72dyn/cm, and the contact angle between water and the polyethylene separation membrane is 115 degrees.
(3) Pure water flux and rejection:
pure water flux: and (3) measuring by adopting a nanofiltration tester (self-made).
Retention rate: measured using a conductivity meter (HQ30d, hash, usa).
Flux and rejection: pure water flux is an important parameter for representing the water permeability of the separation membrane, and the membrane is pre-pressed for 1 hour by using deionized water as feed liquid under the pressure of 0.48MPa to ensure that the effluent is stable; then, a pure water flux test was carried out, and the effective membrane area of the test apparatus was 32cm2. The calculation formula is as follows:
wherein Q is the volume (L) of pure water passing therethrough, Δ t is the time (h) of passing therethrough, and A is the effective area (cm) of the permeable membrane2)。
Retention performance: the retention rate (R) is two indexes. After the membrane pre-compaction is finished, the MgSO with 2000mg/L of MgSO4And 500mg/L NaCl solution to be tested at room temperature of 2The test was carried out at 5 ℃. The calculation formula is as follows:
CPand CFThe permeate and feed concentrations (mg/L), respectively, are generally considered to be linearly related to the salt concentration, and thus the salt cut-off R can be calculated using conductivity instead of concentration.
Example 1
The polyethylene microporous membrane 2 (thickness 9 μm, average pore diameter 0.046 μm) was soaked in an isopropanol solution of 50% by mass, and then washed with deionized water. Then placing on a polyethylene terephthalate non-woven fabric substrate 3 (thickness 90 μm, unit area mass 76 g/m)2) And (5) leveling and fixing.
Immersing a non-woven fabric supported polyethylene microporous membrane into a polyamine aqueous phase solution, wherein a polyfunctional amine monomer is piperazine (with the mass concentration of 3%), an acid acceptor is triethylamine (with the mass concentration of 0.5%), a monomer diffusion promoter is sodium dodecyl sulfate (with the mass concentration of 0.1%), and the immersion time is 30 seconds; taking out the membrane from the water phase, removing redundant liquid, immersing the membrane into a polyacyl chloride oil phase solution, wherein a polyacyl chloride monomer is trimesoyl chloride (the mass concentration is 0.1 percent), a used solvent is n-hexane, immersing the membrane for 30 seconds, and taking out the membrane; and (3) carrying out heat treatment at 80 ℃ for 5 minutes to obtain the non-woven fabric substrate supported polyethylene nanofiltration membrane.
Example 2
The polyethylene microporous membrane 2 was replaced with a polyethylene terephthalate nonwoven fabric substrate 3 having a thickness of 70 μm and an average pore diameter of 0.051 μm, and the polyethylene nanofiltration membrane supported on the nonwoven fabric substrate was obtained under the same conditions as in example 1.
Example 3
Polyethylene terephthalate nonwoven fabric substrate 3 having a thickness of 100 μm was used for supporting, and the conditions were otherwise the same as in example 1, to obtain a polyethylene nanofiltration membrane supported on a nonwoven fabric substrate.
Example 4
The polyethylene microporous membrane 2 was replaced with a polyethylene nanofiltration membrane supported on a nonwoven fabric substrate having a thickness of 20 μm and an average pore diameter of 0.041 μm under the same conditions as in example 1.
Example 5
The polyethylene terephthalate non-woven fabric substrate 3 was replaced with a polypropylene non-woven fabric substrate 3 (thickness 90 μm, mass per unit area 81 g/m)2) And the other conditions were the same as in example 1, to obtain a nonwoven fabric-based polyethylene nanofiltration membrane.
Example 6
The mass concentration of the aqueous phase polyamine monomer piperazine in example 1 is adjusted to 2%, the mass concentration of triethylamine is 1%, the mass concentration of the monomer diffusion promoter is isopropanol with the mass concentration of 5%, the temperature of the post-heat treatment is adjusted to 60 ℃, and other conditions are not changed, so that the non-woven fabric substrate supported polyethylene nanofiltration membrane is obtained.
Example 7
The polyethylene microporous membrane 2 of example 1 was replaced with a microporous membrane of 25 μm thickness and an average pore diameter of 0.036 μm and having a thickness of 110 μm and a mass per unit area of 93g/m2The polyethylene terephthalate nonwoven fabric substrate 3 was supported, and other conditions were kept unchanged. And obtaining the non-woven fabric substrate supported polyethylene nanofiltration membrane.
Comparative example 1
Soaking a polyethylene microporous membrane 2 (with the thickness of 9 microns and the average pore diameter of 0.046 microns) in an isopropanol solution with the mass fraction of 50%, and then washing with deionized water; carrying without adding non-woven fabrics.
And (3) carrying out an interfacial polymerization process, wherein the steps and reagents are consistent with those in example 1, so as to obtain the polyethylene microporous nanofiltration membrane.
Comparative example 2
And (3) removing the non-woven fabric substrate 3 in the example 4, and then preparing a nanofiltration membrane, wherein the steps and the conditions are consistent with those in the example 4, so as to obtain the polyethylene microporous nanofiltration membrane.
Comparative example 3
The substrate in the example 1 is replaced by a commercial polysulfone ultrafiltration membrane (the thickness of the non-woven fabric is 90 μm, and the thickness of the skin layer of the polysulfone membrane is 40 μm), and the polysulfone substrate nanofiltration membrane is prepared under the same conditions.
Examples 1-7 and comparative examples 1-3 were tested for pure water flux and inorganic salt rejection and the results are given in the following table:
table 1 test results of pure water flux and inorganic salt rejection in examples and comparative examples
As can be seen from table 1:
in the comparative example 1, because no non-woven fabric is used as a substrate to provide support, the polyethylene microporous membrane has too thin thickness and uneven distribution of water phase monomers, so that the prepared nanofiltration membrane has more defects, high flux during performance test and low interception; after the washing for 18h, the polyethylene support body is partially destroyed, the MgSO4 rejection rate is reduced to 90%, the rejection loss rate reaches 15.2% after 100h, and the service life of the membrane is poor;
compared with the comparative example 2, after the thicker polyvinyl base film is used, the interception can be kept above 90% after 100h, the interception loss is relieved, but still 6.3%;
comparative example 3 using commercial ultrafiltration membrane as substrate, high rejection, good long-term stability, low rejection loss rate of 0.8%, but the disadvantage is low flux, only 45L/m2.h；
In the embodiment 1, the rejection rate is higher after the nanofiltration membrane is prepared under the support of the non-woven fabric, the rejection rate is still over 98 percent after 100h test, the rejection loss rate is as low as 1.1 percent, and the performance of the membrane after the whole membrane is pressed can still be kept stable;
example 2 replacement of ultra-thin polyethylene microporous membrane with thinner nonwoven support yielded 85L/m2H, high flux, good salt interception performance, but insufficient mechanical strength due to the fact that the basement membrane and the support are both too thin, and high interception loss after long-time operation, wherein the interception loss rate is about 2.1%;
example 3 with a thicker nonwoven substrate, the problem of poor impact strength can be effectively alleviated, the entrapment loss rate is effectively reduced to 1.4%, and the flux is 77L/m2H, still maintained at a higher level;
example 4 selects thickening the polyethylene microporous membrane 2, and finds that although the flux is slightly lower, the interception is more stable, the interception loss rate is only 0.9%, and the performance is close to that of a commercial membrane;
in example 5, after the polypropylene non-woven fabric 3 is used, the hydrophobicity is stronger than that of the polyester material, so that the pure water permeation resistance is higher, the flux is reduced, the interception performance is poorer than that of example 2, and the interception loss rate is increased to 1.7%;
after the formula and the process parameters are adjusted in the embodiment 6, the flux is obviously improved, the corresponding interception is reduced to 98.2 percent, the performance is kept good after 100h test, and the interception loss rate is about 1.0 percent;
example 7 replacement with a thicker nonwoven 3, the flux decreased to 63L/m2H, the interception level is higher and can reach 99.4%, meanwhile, the interception loss rate is only 0.8%, and the interception loss rate is equivalent to the level of a nano-filtration membrane prepared by a commercial ultrafiltration membrane, but the flux is obviously higher than the level of the commercial ultrafiltration membrane;
therefore, compared with the polyethylene microporous nanofiltration membrane without the support provided by the non-woven fabric as the substrate 3, the non-woven fabric substrate supported polyethylene nanofiltration membrane provided by the invention has the advantages of higher inorganic salt rejection rate, better and stable membrane filtration performance and longer service life; compared with the existing commercial polysulfone-based nanofiltration membrane, the invention has higher flux and better comprehensive performance on the basis of reaching the same level of rejection rate and service life.
The above matters related to the common general knowledge are not described in detail and can be understood by those skilled in the art.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The utility model provides a non-woven fabrics substrate carries polyethylene nanofiltration membrane which characterized in that: comprises a non-woven fabric substrate, a polyethylene microporous membrane and a nanofiltration membrane skin layer; the polyethylene microporous membrane is supported on the non-woven fabric substrate; and the nanofiltration membrane skin layer is positioned on the polyethylene microporous membrane.
2. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises: the non-woven fabric substrate is made of one or a combination of polyethylene terephthalate, polyethylene, polypropylene, polyamide and polyurethane.
3. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises: the thickness of the non-woven fabric substrate is 70-110 mu m.
4. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises: the mass per unit area of the non-woven fabric substrate is 10-150 g/m2。
5. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 3, wherein the nanofiltration membrane comprises: the thickness of the non-woven fabric substrate is 90-100 mu m.
6. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 4, wherein the nanofiltration membrane comprises: the mass per unit area of the non-woven fabric substrate is 50-100 g/m2。
7. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises: the thickness of the polyethylene microporous membrane is between 5 and 25 mu m.
8. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises: the average pore diameter of the polyethylene microporous membrane is between 0.01 and 0.2 mu m.
9. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 7, wherein the nanofiltration membrane comprises: the thickness of the polyethylene microporous membrane is between 9 and 20 mu m.
10. The non-woven fabric substrate supported polyethylene nanofiltration membrane according to claim 8, wherein the nanofiltration membrane comprises: the average pore diameter of the polyethylene microporous membrane is between 0.02 and 0.06 mu m.
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