CN105536574A - Filter membrane as well as preparation method and application - Google Patents
Filter membrane as well as preparation method and application Download PDFInfo
- Publication number
- CN105536574A CN105536574A CN201510934863.0A CN201510934863A CN105536574A CN 105536574 A CN105536574 A CN 105536574A CN 201510934863 A CN201510934863 A CN 201510934863A CN 105536574 A CN105536574 A CN 105536574A
- Authority
- CN
- China
- Prior art keywords
- metal
- filter membrane
- organic framework
- framework materials
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 108
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 91
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000001914 filtration Methods 0.000 claims abstract description 54
- 238000009987 spinning Methods 0.000 claims abstract description 51
- 238000003618 dip coating Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 44
- 239000013110 organic ligand Substances 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 15
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000013384 organic framework Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229920005594 polymer fiber Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 229940015043 glyoxal Drugs 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 abstract 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000009423 ventilation Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 238000000634 powder X-ray diffraction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000004745 nonwoven fabric Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 9
- 239000002121 nanofiber Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- DVNYTAVYBRSTGK-UHFFFAOYSA-N 5-aminoimidazole-4-carboxamide Chemical compound NC(=O)C=1N=CNC=1N DVNYTAVYBRSTGK-UHFFFAOYSA-N 0.000 description 2
- 206010013975 Dyspnoeas Diseases 0.000 description 2
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- URJFKQPLLWGDEI-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=[C]N1CC1=CC=CC=C1 URJFKQPLLWGDEI-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- IAJLTMBBAVVMQO-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanol Chemical compound C1=CC=C2NC(CO)=NC2=C1 IAJLTMBBAVVMQO-UHFFFAOYSA-N 0.000 description 1
- QMQZIXCNLUPEIN-UHFFFAOYSA-N 1h-imidazole-2-carbonitrile Chemical compound N#CC1=NC=CN1 QMQZIXCNLUPEIN-UHFFFAOYSA-N 0.000 description 1
- XGDRLCRGKUCBQL-UHFFFAOYSA-N 1h-imidazole-4,5-dicarbonitrile Chemical compound N#CC=1N=CNC=1C#N XGDRLCRGKUCBQL-UHFFFAOYSA-N 0.000 description 1
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- JUNAPQMUUHSYOV-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)acetic acid Chemical compound OC(=O)CC=1N=NNN=1 JUNAPQMUUHSYOV-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- JVSMPWHQUPKRNV-UHFFFAOYSA-N 2h-tetrazol-5-amine;hydrate Chemical compound O.NC=1N=NNN=1 JVSMPWHQUPKRNV-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- COYPLDIXZODDDL-UHFFFAOYSA-N 3h-benzimidazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2N=CNC2=C1 COYPLDIXZODDDL-UHFFFAOYSA-N 0.000 description 1
- CVWDKBHAUIZWAY-UHFFFAOYSA-N 4-(4-carboxy-2-hydroxyphenyl)-3-hydroxybenzoic acid Chemical compound OC1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1O CVWDKBHAUIZWAY-UHFFFAOYSA-N 0.000 description 1
- HRGSKQRXBGCEAZ-UHFFFAOYSA-N 4-(4-carboxy-2-nitrophenyl)-3-nitrobenzoic acid Chemical compound [O-][N+](=O)C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1[N+]([O-])=O HRGSKQRXBGCEAZ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical compound C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 description 1
- QURGMSIQFRADOZ-UHFFFAOYSA-N 5-(3,5-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 QURGMSIQFRADOZ-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- KUEFXPHXHHANKS-UHFFFAOYSA-N 5-nitro-1h-1,2,4-triazole Chemical compound [O-][N+](=O)C1=NC=NN1 KUEFXPHXHHANKS-UHFFFAOYSA-N 0.000 description 1
- VYDWQPKRHOGLPA-UHFFFAOYSA-N 5-nitroimidazole Chemical compound [O-][N+](=O)C1=CN=CN1 VYDWQPKRHOGLPA-UHFFFAOYSA-N 0.000 description 1
- NBDAHKQJXVLAID-UHFFFAOYSA-N 5-nitroisophthalic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC([N+]([O-])=O)=C1 NBDAHKQJXVLAID-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 description 1
- BDTOTMBOHYUNSQ-UHFFFAOYSA-N triazole-1-carboxylic acid Chemical compound OC(=O)N1C=CN=N1 BDTOTMBOHYUNSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- 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
- B01D71/28—Polymers of vinyl aromatic compounds
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- 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
- B01D71/30—Polyalkenyl halides
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
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- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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- 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
- B01D71/50—Polycarbonates
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Abstract
The invention relates to a filter membrane, which is formed by a metal organic framework material and a polymer. The invention also provides a method for preparing the filter membrane which is formed by the metal organic framework material and the polymer. The method comprises the following steps: the metal organic framework material and the polymer are contacted, and the filter membrane is formed by spinning or dip-coating. The invention also relates to an application of the filter membrane to filtering of PM2.5 and volatile organic compounds. The filter membrane has the advantages of high specific surface area, abundant surface function groups, high amount of porosity, light transmission, ventilation, etc., and the filter membrane is used for realizing high-efficiency filtering of PM2.5 and volatile organic compounds.
Description
Technical field
The present invention relates to applied chemistry field, particularly, relate to a kind of filter membrane formed by metal-organic framework materials and polymer, prepare the method for described filter membrane, the purposes of described filter membrane in filtering PM2.5 and VOC.
Background technology
Metallic organic framework is a polyporous materials, one dimension, two dimension or three-dimensional reticulated channel structure is formed by metal cluster, metal oxide or slaine and organic ligand effect, have that porosity is high, functional group be abundant, duct in order, the many merits such as various structures, gas storage be separated, catalysis, film, sensing, the field such as biomedical imaging play an important role.
In the last few years, environmental problem was on the rise, and brought high risks to social development, people's lives, ecological safety, was subject to the great attention of government and the extensive concern of broad masses of the people, especially PM2.5 and the VOC such as benzene homologues, formaldehyde.PM2.5 can be detained for a long time in the environment, and very easily in entering human body, brings very large threat to healthy, the life security of people; Volatile organic contaminant is then main " arch-criminal " that cause environmental pollution, damage health, and it participates in atmospheric photochemical reaction, and directly results in the formation of PM2.5 in air; VOC also has very adverse influence to the healthy of people, can carcinogenic, poison central nervous system, cause air hunger, cause expiratory dyspnea even dead.Therefore in the urgent need to finding a kind of new material, method by its rapidly and efficiently filtering.
At present, can either not be used for removing the method that PM2.5 can be used in again removing VOC, all need to use different materials to be processed separately.Such as, be conventionally used to the material of filtering PM2.5, comprise the existing HEPA screen pack can used in the air purifier of filtering PM2.5 commercially sold, main is meltblown fibers, glass fibre and spun-bonded fibre.In addition, PM2.5 is removed by electrostatic precipitator technology in addition.And for the filtering aspect of VOC, the technical method in living and material can be widely used at present.In the industrial production to the filtering of VOC, method conventional at present has absorption method, absorption process, combustion method, condensation method, biological treatment etc.
Summary of the invention
The invention provides a kind of filter membrane, formed by metal-organic framework materials and polymer, described metal-organic framework materials forms the metallic organic framework part in described filter membrane, described polymer forms the polymer fiber part in described filter membrane, and wherein said metal-organic framework materials is formed by source metal and organic ligand effect.
Wherein, described source metal comprises at least one in metal cluster, slaine or metal oxide.
Preferably, the metallic element in described source metal comprises at least one in Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
Preferred, described metallic element comprises at least one in Zn, Zr, Cu or Mg.
In filter membrane of the present invention, described organic ligand is
,
,
,
,
,
,
or
in one, or comprise following co-ordinating functionality :-CO
2h ,-NO
2,-OH ,-NH
2,-CN ,-SO
3h ,-SH, CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2or-C (CN)
3in at least one, wherein, the R in co-ordinating functionality represents the alkylene comprising 1 to 5 phenyl ring independently of one another.
Preferably, described organic ligand is
or comprise-CO
2h ,-NH
2or the organic ligand of at least one co-ordinating functionality in-OH.
In filter membrane of the present invention, described polymer comprises at least one in polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, PMA, polyethylene glycol, Merlon.
Preferably, described polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in filter membrane of the present invention is zirconium chloride, organic ligand is the amino terephthalic acid (TPA) of 2-, and described polymer is polyacrylonitrile.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in filter membrane of the present invention is Schweinfurt green, organic ligand is trimesic acid, and described polymer is polystyrene.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in filter membrane of the present invention is zinc nitrate, organic ligand is glyoxal ethyline, and described polymer is polyacrylonitrile.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in filter membrane of the present invention is magnesium nitrate, organic ligand is 2,5-Dihydroxyterephthalic acid, and described polymer is polyvinylpyrrolidone.
Filter membrane of the present invention, the described metal-organic framework materials wherein relative to 1 gram, the consumption of described polymer is 0.1-10 gram.
Present invention also offers a kind of method preparing above-mentioned filter membrane, the method comprises: by metal-organic framework materials and polymer contact, described metal-organic framework materials forms the metallic organic framework part in described filter membrane, described polymer forms the polymer fiber part in described filter membrane, and wherein said metal-organic framework materials is formed by source metal and organic ligand effect.
Wherein, described source metal comprises at least one in metal cluster, slaine or metal oxide.
Preferably, the metallic element in described source metal comprises at least one in Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
Described metallic element comprises at least one in Zn, Zr, Cu or Mg.
In method of the present invention, described organic ligand is
,
,
,
,
,
,
or
in one, or comprise following co-ordinating functionality :-CO
2h ,-NO
2,-OH ,-NH
2,-CN ,-SO
3h ,-SH ,-CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2or-C (CN)
3in at least one, wherein, the R in co-ordinating functionality represents the alkylene comprising 1 to 5 phenyl ring independently of one another.
Preferably, described organic ligand is
or comprise-CO
2h ,-NH
2or the organic ligand of at least one co-ordinating functionality in-OH.
In method of the present invention, described polymer comprises at least one in polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, PMA, polyethylene glycol, Merlon.
Preferably, described polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in method of the present invention is zirconium chloride, organic ligand is the amino terephthalic acid (TPA) of 2-, and described polymer is polyacrylonitrile.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in method of the present invention is Schweinfurt green, organic ligand is trimesic acid, and described polymer is polystyrene.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in method of the present invention is zinc nitrate, organic ligand is glyoxal ethyline, and described polymer is polyacrylonitrile.
As the preferred embodiment of one of the present invention, the source metal of metal-organic framework materials described in filter membrane of the present invention is magnesium nitrate, organic ligand is 2,5-Dihydroxyterephthalic acid, and described polymer is polyvinylpyrrolidone.
In method of the present invention, the described metal-organic framework materials relative to 1 gram, the consumption of described polymer is 0.1-10 gram.
Method of the present invention, the contact of described metal-organic framework materials and polymer is carried out in a solvent, the metal-organic framework materials of relative 1 gram, and the consumption of solvent is 10-100 milliliter, prepares described filter membrane by spinning or dip-coating method.
Preferably, described solvent comprises at least one in water, methyl alcohol, ethanol, dimethyl formamide, dimethylacetylamide, DEF.
Present invention also offers the purposes of filter membrane of the present invention in filtering PM2.5.
Present invention also offers the purposes of institute's filter membrane of the present invention in filtering VOC.
Filter membrane strainability of the present invention is very outstanding, can rapidly and efficiently filtering PM2.5 and VOC, and within 30 minutes, rejection rate can reach more than 80%.
Filter membrane raw material of the present invention is simple and easy to get, without harmfulness; Preparation technology is fast easy, within about 10 minutes, can obtain product, can realize industrialization and produce; Can simultaneously filtering PM2.5 and VOC, and all there is efficient filtering efficiency, within 30 minutes, rejection rate can reach more than 80%; Described filter membrane purity is high, printing opacity, ventilative, ultralow vapour lock; Described filter membrane has certain flexibility and machinability, can be used for the preparation of multiple protective materials; The specific area of filter membrane is high, surface functional group abundant, porosity is high, effectively facilitates the filtering to PM2.5 and VOC.
Do not have in prior art can either high-efficient filter except PM2.5 again can high-efficient filter except the material of VOC, all need to use different materials to give filtering separately.
Be conventionally used to the material of filtering PM2.5, comprise the existing HEPA screen pack can used in the air purifier of filtering PM2.5 commercially sold, main is meltblown fibers, glass fibre and spun-bonded fibre, these materials are fibrous by micron order, fibre diameter is larger, filter effect is low, simultaneously, its filtration result realizes by the Fan get Hua power effect between PM2.5 and fibrous material, widely different to the particle filtration result of different-diameter, have a strong impact on the filtration result to PM2.5 on the whole.
And for the filtering aspect of VOC, the technical method in living and material can be widely used at present.In the industrial production to the filtering of VOC, method conventional at present has absorption method, absorption process, combustion method, condensation method, biological treatment etc., but these methods all also exist respective deficiency again, complex process, vapour lock are large, technology energy consumption is too high, operation cost is high, filtering efficiency is low.
Filter membrane of the present invention, can simultaneously filtering PM2.5 and VOC, by the functional group that filter membrane surface is abundant, with pollutant effect, can realize removing the high-efficient filter of different-grain diameter, variety classes pollutant, and filter membrane of the present invention has very high porosity, vapour lock is extremely low, printing opacity, ventilative, Non-energy-consumption, greatly reduce production run cost, simultaneously, production method is simple and quick, can be widely applied in productive life.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.
Fig. 1 is the X-ray powder diffraction figure of the filter membrane that embodiment 1 obtains.
Fig. 2 is the scanning electron microscope (SEM) photograph of the filter membrane that embodiment 1 obtains.
Fig. 3 is the X-ray powder diffraction figure of the filter membrane that embodiment 2 obtains.
Fig. 4 is the scanning electron microscope (SEM) photograph of the filter membrane that embodiment 2 obtains.
Fig. 5 is the X-ray powder diffraction figure of the filter membrane that embodiment 3 obtains.
Fig. 6 is the scanning electron microscope (SEM) photograph of the filter membrane that embodiment 3 obtains.
Fig. 7 is the X-ray powder diffraction figure of the filter membrane that embodiment 4 obtains.
Fig. 8 is the scanning electron microscope (SEM) photograph of the filter membrane that embodiment 4 obtains.
Fig. 9 is the PM2.5 filtration result figure of the filter membrane that embodiment 1 obtains.
Figure 10 is the X-ray powder diffraction figure of the filter membrane that embodiment 11 obtains.
Figure 11 is the scanning electron microscope (SEM) photograph of the filter membrane that embodiment 11 obtains.
Figure 12 is the X-ray powder diffraction figure of the filter membrane that embodiment 12 obtains.
Figure 13 is the scanning electron microscope (SEM) photograph of the filter membrane that embodiment 12 obtains.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, when not doing contrary explanation, the liquid of use or the volumetric quantities of gas are all 20 DEG C, the numerical value of 1 normal atmosphere pressure.
metal-organic framework materials
Metallic organic framework part from metal organic framework material in filter membrane of the present invention is formed, described metal-organic framework materials refers to and to be formed by source metal and organic ligand effect, has the new material of one dimension, two dimension or three-dimensional repeatably reticulated channel structure.Wherein, source metal comprises at least one in metal cluster, slaine or metal oxide.
Metallic element in described source metal can be at least one in Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
Wherein, preferably, the metallic element in the source metal of described metal-organic framework materials is Zn, Zr, Cu or Mg.
Described organic ligand is
,
,
,
,
,
,
or
in one, or comprise following co-ordinating functionality :-CO
2h ,-NO
2,-OH ,-NH
2,-CN ,-SO
3h ,-SH ,-CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2or C (CN)
3in at least one, wherein, the R in co-ordinating functionality represents the alkylene comprising 1 to 5 phenyl ring independently of one another.Wherein, preferred organic ligand is
or comprise-CO
2h ,-NH
2or the organic ligand of at least one co-ordinating functionality in-OH.
Described organic ligand comprises terephthalic acid (TPA), trimesic acid, 2-nitroterephthalic, 2-hydroxyterephthalic acid, 2,5-Dihydroxyterephthalic acid, the amino terephthalic acid (TPA) of 2-, 2-sulfonic group terephthalic acid (TPA) list sodium, 5-amino isophthalic acid, 5-nitroisophthalic acid, 4 hydroxyisophthalic acid, 5-sulfonic group M-phthalic acid list sodium salt, benzoic acid, 4,4 '-biphenyl dicarboxylic acid, 2,2 '-dinitro-4,4 '-biphenyl dicarboxylic acid, 2,2 '-diaminourea-4,4 '-biphenyl dicarboxylic acid, 2,2 '-dihydroxy-4,4 '-biphenyl dicarboxylic acid, 3,3 ', 5,5 '-bibenzene tetracarboxylic, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic, NDA, naphthalene-Isosorbide-5-Nitrae-dioctyl phthalate, 3-mercaptopropionic acid, 3-amino-5-sulfydryl-1,2,4-triazole, DMSA, 5-methoxyl group-2-mercaptobenzimidazole, 1-methyl-5-mercapto tetrazole, imidazoles, benzimidazole, 2-mercaptobenzimidazole, N, N-carbonyl dimidazoles, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-methylimidazole, glyoxal ethyline, 4-methylimidazole, 2-nitroimidazole, 2-cyanoimidazole, 1,2-methylimidazole, imidazole-4,5-dicarboxylic acid, 4-amino-5-Imidazole carboxamide, 2-methylol-1H-benzimidazole, 2-tolimidazole, 5,6-dimethylbenzimidazole, 4,5-dicyano imidazole, benzimidazole-5-formic acid, 1H-imidazoles-4-formic acid, 2 isopropyl imidazole, 1 benzyl 2 methyl imidazole, 4-nitroimidazole, 5-aminotetrazole monohydrate, tetrazoleacetic acid, 1,2,4-triazole, 1-methyl isophthalic acid, 2,4-triazole, 1-methyl isophthalic acid, 2,3,4-tetrazole, triazole-3-carboxylic acid, 4-amino-4H-1,2,4-triazole, 3-nitro-1,2,4-triazole.
Metal-organic framework materials used in the present invention can be prepared by method of the prior art, and the preparation method of the metal-organic framework materials used in the present invention is as follows:
Method 1:
The zirconium chloride of 0.1250 gram is dissolved in 5 milliliters of N, in dinethylformamide (DMF), amino for 0.1340 gram of 2-terephthalic acid (TPA) is dissolved in 10 milliliters of DMF, then two kinds of solution are mixed, react 12 hours under 80oC, the powder DMF that centrifugation obtains washs 3 times, and soaks 3 days in ethanol, and products therefrom 150oC is dried.
Method 2:
0.60 gram of Schweinfurt green and 0.42 gram of trimesic acid are put into ball grinder, adds 1 milliliter of ethanol, mechanical ball milling 30 minutes, take out blue solid, wash several times with ethanolic solution, until filtrate clarification, then 60 DEG C of oven dry, obtain product.
Method 3:
Be dissolved in 50 ml methanol by 0.6454 gram of zinc nitrate and 0.8106 gram of glyoxal ethyline, at room temperature leave standstill 24 hours, centrifugation obtains white powder, uses methanol wash several times, and products therefrom 150oC is dried.
Method 4:
By 1.4 grams of magnesium nitrates and 0.337 gram 2,5-dihydric para-phthalic acid is dissolved into 135 milliliters of N, in the mixed solvent of dinethylformamide (DMF), 9 milliliters of ethanol and 9 ml waters, react 26 hours under 125oC, the product with methylalcohol washing obtained, and in methyl alcohol soak 3 days, afterwards filter products therefrom and under vacuum 250oC dry 6 hours.
polymer
Polymer of the present invention can be the various chemical substance preparing membrane material that can be used for, and comprises at least one in polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, PMA, polyethylene glycol, Merlon.The preferred polymer of the present invention is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
the preparation of filter membrane
The contact of metal-organic framework materials of the present invention and polymer is carried out in a solvent.
Described solvent comprises at least one in water, methyl alcohol, ethanol, dimethyl formamide, dimethylacetylamide, DEF.The present inventor finds to select dimethyl formamide as solvent, and the film purity obtained is higher, and filtration result is better.
Relative to the metal-organic framework materials of 1 gram, the consumption of described polymer can be 0.1-10 gram, is more preferably 1-8 gram, and the consumption of solvent is 10-100 milliliter, is more preferably 15-80 milliliter.
Filter membrane of the present invention is prepared by spinning process.
By metal-organic framework materials and polymer spun on non-woven fabrics, the two growth thus obtain metallic organic framework/polymer filtration film of jointly interweaving.Specifically, first according to following optimum configurations spinning-drawing machine: spinning feeding rate is that 0.1-10 milliliter is per hour, preferably 0.5-5 milliliter is per hour, spinning voltage is 8-13 kilovolt, spinning distance is 10-50 centimetre, is preferably 15-30 centimetre, the spinning time is 1-30 minute, is preferably 3-20 minute, and needle sizes is 20G.Spinning solution metal-organic framework materials of the present invention and polymer being contacted in a solvent formation afterwards injects sample introduction needle, and non-woven fabrics is positioned over negative electrode for receiving the spinning solution of ejection as reception base material.Starting device, according to certain rate of feed, is ejected into spinning solution on non-woven fabrics, obtains filter membrane of the present invention.
Also the method by dip-coating prepares filter membrane of the present invention.
Specifically, metal-organic framework materials of the present invention is contacted formation mixed solution in a solvent with polymer, mixed solution is placed in controllable temperature oil bath pan, temperature controls constant in normal temperature 25 degrees Celsius, continuous stirring, immerse in mixed solution afterwards as receiving the non-woven fabrics of base material, after each dip-coating 30 seconds to 5 minutes, dip-coating 1-10 time, namely taking-up non-woven fabrics obtains filter membrane of the present invention in an oven 75 degrees Celsius of dry half an hour.
the filtering test of PM2.5
In the present invention, following equipment is used to the test of PM2.5, title: four-in-one corpuscular counter, model: DT-9881M, manufacturer: Shenzhen Huashengchang Machinary Industry Co., Ltd.This equipment is used can directly to test PM2.5 change in concentration.
Wherein, described filtering PM2.5 measure of merit condition is: test 30min under normal temperature and pressure.
the filtering test of VOC
The method of testing of VOC is: first the formaldehyde of certain volume concentration X1ppm or toluene vapor are passed through airtight film filter, device exhaust end access quadrupole rod mass spectrometer (producer: Beijing Ying Gehaide analytical technology Co., Ltd) is carried out test of quantitative analysis, obtains target object volume concentrations X2ppm.Through computing formula (X1-X2)/X1*100%, obtain filtering efficiency.
Wherein, described filtering VOC measure of merit condition is: input concentration 115ppm, gas flow rate 150sccm, and vacuum condition scans 5 minutes.
Further describe the present invention by the following examples.
Embodiment 1
Metal-organic framework materials (source metal is zirconium chloride, organic ligand is the amino terephthalic acid (TPA) of 2-) is dispersed in solvent dimethylformamide, then adds polyacrylonitrile, mix, obtain spinning solution.Wherein, relative to the metal-organic framework materials of 1 gram, the consumption of polymer is 5 grams, and the consumption of solvent is 50 milliliters, and mixing temperature is room temperature, and incorporation time is 8 hours.
Above-mentioned spinning solution is carried out spinning, receives fiber with non-woven fabrics, obtain filter membrane; Wherein, spinning parameter is that spinning feeding rate 3 milliliters is per hour, and spinning voltage is 13 kilovolts, and spinning distance is 20 centimetres, and the spinning time is 10 minutes, and syringe needle model is 20G.
X-ray powder diffraction and scanning electron microscope analysis are carried out to this filter membrane.X-ray powder diffraction, model: BrukerD8Advance, 4-50 between test section
0, sweep speed 4
0per minute; ESEM model HitachiS4800, sweep parameter: 1, Fig. 2 A, accelerating potential 5 kilovolts, operating distance 9.3 millimeters, multiplication factor 4.5 ten thousand times, length scales 10 microns; 2, Fig. 2 B, accelerating potential 5 kilovolts, operating distance 9.3 millimeters, multiplication factor 450,000 times, length scales 1 micron.Result display metal-organic framework materials can keep original structure, and success and polymer spinning obtain filter membrane.As shown in Figure 1, scanning electron microscope (SEM) photograph as shown in Figure 2 A and 2 B for the X-ray powder diffraction figure of this filter membrane.
In Fig. 1, the nanofiber obtained after the metal-organic framework materials synthesized, metal-organic framework materials and mixed with polymers and the monocrystalline simulation curve of metal-organic framework materials fit like a glove, illustrate that successfully synthesis obtains corresponding metallo-organic framework, and the metal-organic framework materials on filter membrane maintains original structure, is not destroyed; In Fig. 2 A and Fig. 2 B, be the scanning electron microscope (SEM) photograph that gained filter membrane is done, by Electronic Speculum figure, can see that metal-organic framework materials and polymer spinning successfully obtain nanofiber, and on non-woven fabrics, form netted intertexture, obtain filter membrane.Wherein, the line of intertexture is polymer fiber, and the projection on line is metal-organic framework materials.
Embodiment 2
Metal-organic framework materials (source metal be Schweinfurt green, organic ligand be trimesic acid) is dispersed in dimethyl formamide, then adds polystyrene, mix, obtain spinning solution.Wherein, relative to the metal-organic framework materials of 1 gram, the consumption of polymer is 8 grams, and the consumption of solvent is 80 milliliters, and mixing temperature is room temperature, and incorporation time is 8 hours.
Above-mentioned spinning solution is carried out spinning, receives fiber with non-woven fabrics, obtain filter membrane; Wherein, spinning parameter is that spinning feeding rate 5 milliliters is per hour, and spinning voltage is 10 kilovolts, and spinning distance is 15 centimetres, and the spinning time is 5 minutes, and syringe needle model is 20G.
Carry out X-ray powder diffraction and scanning electron microscope analysis to this filter membrane, method of testing and test condition are with embodiment 1, and result display metal-organic framework materials can keep original structure, and success and polymer spinning obtain filter membrane.As shown in Figure 3, scanning electron microscope (SEM) photograph as shown in Figure 4 A and 4 B shown in FIG. for the X-ray powder diffraction figure of this filter membrane.In Fig. 3, the nanofiber obtained after the metal-organic framework materials synthesized, metal-organic framework materials and mixed with polymers and the monocrystalline simulation curve of metal-organic framework materials fit like a glove, illustrate that successfully synthesis obtains corresponding metallo-organic framework, and the metal-organic framework materials on filter membrane maintains original structure, is not destroyed; In Fig. 4 A and Fig. 4 B, be the scanning electron microscope (SEM) photograph that gained filter membrane is done, by Electronic Speculum figure, can see that metal-organic framework materials and polymer spinning successfully obtain nanofiber, and on non-woven fabrics, form netted intertexture, obtain filter membrane.Wherein, the line of intertexture is polymer fiber, and the projection on line is metal-organic framework materials.
Embodiment 3
Metal-organic framework materials (source metal is zinc nitrate, and organic ligand is glyoxal ethyline) is dispersed in dimethyl formamide, then adds polyacrylonitrile, mix, obtain spinning solution.Wherein, relative to the metal-organic framework materials of 1 gram, the consumption of polymer is 3 grams, and the consumption of solvent is 35 milliliters, and mixing temperature is room temperature, and incorporation time is 8 hours.
Above-mentioned spinning solution is carried out spinning, receives fiber with non-woven fabrics, obtain filter membrane; Wherein, spinning parameter is that spinning feeding rate 2 milliliters is per hour, and spinning voltage is 12 kilovolts, and spinning distance is 30 centimetres, and the spinning time is 3 minutes, and syringe needle model is 20G.
Carry out X-ray powder diffraction and scanning electron microscope analysis to this filter membrane, method of testing and test condition are with embodiment 1, and result display metal-organic framework materials can keep original structure, and success and polymer spinning obtain filter membrane.As shown in Figure 5, scanning electron microscope (SEM) photograph as shown in Figure 6 A and 6 B for the X-ray powder diffraction figure of this filter membrane.In Fig. 5, the nanofiber obtained after the metal-organic framework materials synthesized, metal-organic framework materials and mixed with polymers and the monocrystalline simulation curve of metal-organic framework materials fit like a glove, illustrate that successfully synthesis obtains corresponding metallo-organic framework, and the metal-organic framework materials on filter membrane maintains original structure, is not destroyed; In Fig. 6 A and Fig. 6 B, be the scanning electron microscope (SEM) photograph that gained filter membrane is done, by Electronic Speculum figure, can see that metal-organic framework materials and polymer spinning successfully obtain nanofiber, and on non-woven fabrics, form netted intertexture, obtain filter membrane.Wherein, the line of intertexture is polymer fiber, and the projection on line is metal-organic framework materials.
Embodiment 4
Metal-organic framework materials (source metal is magnesium nitrate, and organic ligand is 2,5-Dihydroxyterephthalic acid) is dispersed in dimethyl formamide, then adds polyvinylpyrrolidone, mix, obtain spinning solution.Wherein, relative to the metal-organic framework materials of 1 gram, the consumption of polymer is 5 grams, and the consumption of solvent is 50 milliliters, and mixing temperature is room temperature, and incorporation time is 8 hours.
Above-mentioned spinning solution is carried out spinning, receives fiber with non-woven fabrics, obtain filter membrane; Wherein, spinning parameter is that spinning feeding rate 0.5 milliliter is per hour, and spinning voltage is 8 kilovolts, and spinning distance is 15 centimetres, and the spinning time is 20 minutes, and syringe needle model is 20G.
Carry out X-ray powder diffraction and scanning electron microscope analysis to this filter membrane, method of testing and test condition are with embodiment 1, and result display metal-organic framework materials can keep original structure, and success and polymer spinning obtain filter membrane.As shown in Figure 7, scanning electron microscope (SEM) photograph as shown in Figure 8 A and 8 B for the X-ray powder diffraction figure of this filter membrane.In Fig. 7, the nanofiber obtained after the metal-organic framework materials synthesized, metal-organic framework materials and mixed with polymers and the monocrystalline simulation curve of metal-organic framework materials fit like a glove, illustrate that successfully synthesis obtains corresponding metallo-organic framework, and the metal-organic framework materials on filter membrane maintains original structure, is not destroyed; In Fig. 8 A and Fig. 8 B, be the scanning electron microscope (SEM) photograph that gained filter membrane is done, by Electronic Speculum figure, can see that metal-organic framework materials and polymer spinning successfully obtain nanofiber, and on non-woven fabrics, form netted intertexture, obtain filter membrane.Wherein, the line of intertexture is polymer fiber, and the projection on line is metal-organic framework materials.
Embodiment 5-10
Prepare filter membrane according to the method for embodiment 1,2,3 and 4, design parameter and raw material are recorded in Table 1.
Embodiment 11
Metal-organic framework materials (source metal is zinc nitrate, and organic ligand is glyoxal ethyline) is dispersed in dimethyl formamide, then adds polyacrylonitrile, mix, obtain mixed solution.Wherein, relative to the metal-organic framework materials of 1 gram, the consumption of polymer is 3 grams, and the consumption of solvent is 35 milliliters.Non-woven fabrics is inserted in mixed solution as reception base material, after each dip-coating 30 seconds, dip-coating 10 times, takes out, puts into baking oven and obtain filter membrane 75 degrees Celsius of dry half an hour.Carry out X-ray powder diffraction and scanning electron microscope analysis to this filter membrane, method of testing and test condition are with embodiment 3, and gained test result is shown in Figure 10-11.Test by the method for the filtering test of the aforesaid PM2.5 of description of the present invention and VOC the filter membrane that the present embodiment obtains, result is PM2.5 filtering efficiency is 89.7%, and the filtering efficiency of formaldehyde is 89.3%, and the filtering efficiency of toluene is 87.1%.
Embodiment 12
Metal-organic framework materials (source metal is magnesium nitrate, and organic ligand is 2,5-Dihydroxyterephthalic acid) is dispersed in dimethyl formamide, then adds polyvinylpyrrolidone, mix, obtain mixed solution.Wherein, relative to the metal-organic framework materials of 1 gram, the consumption of polymer is 5 grams, and the consumption of solvent is 50 milliliters.Non-woven fabrics is inserted in mixed solution as reception base material, puts into baking oven and obtain filter membrane 75 degrees Celsius of dry half an hour after each dip-coating 5 minutes, dip-coating 1 time.X-ray powder diffraction and scanning electron microscope analysis are carried out to this filter membrane, method of testing and test condition are with embodiment 4, test result is shown in Figure 12-13, the filter membrane that the present embodiment obtains is tested by the method for the filtering test of the aforesaid PM2.5 of description of the present invention and VOC, result is the filtering efficiency of PM2.5 is 92.2%, the filtering efficiency of formaldehyde is 91.5%, and the filtering efficiency of toluene is 89.9%.
Test case 1
The filtering PM2.5 performance of the filter membrane that the method testing example 1-10 tested by the filtering of the aforesaid PM2.5 of description of the present invention obtains, concrete filtering efficiency data is see table 1.
In Fig. 9, polymer fiber has a large amount of significantly projection, these projections are the PM2.5 that polymer fiber is caught.
Test case 2
The performance of the filtering formaldehyde of the filter membrane that the method testing example 1-10 tested by the filtering of the aforesaid VOC of description of the present invention obtains, concrete filtering efficiency data is see table 1.
Test case 3
The performance of the filtering toluene of the filter membrane that the method testing example 1-10 tested by the filtering of the aforesaid VOC of description of the present invention obtains, concrete filtering efficiency data is see table 1.
The filtering efficiency of the parameter of table 1 embodiment 1-10 and PM2.5, formaldehyde and toluene
Visible according to the data of Fig. 1-13, process of the present invention successfully can obtain filter membrane; Visible by the filtering efficiency data of embodiment 1-12, the filter membrane that method of the present invention prepares can filtering PM2.5 rapidly and efficiently and VOC.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (30)
1. a filter membrane, formed by metal-organic framework materials and polymer, described metal-organic framework materials forms the metallic organic framework part in described filter membrane, described polymer forms the polymer fiber part in described filter membrane, and wherein said metal-organic framework materials is formed by source metal and organic ligand effect.
2. filter membrane according to claim 1, is characterized in that, described source metal comprises at least one in metal cluster, slaine or metal oxide.
3. filter membrane according to claim 2, is characterized in that, the metallic element in described source metal comprises at least one in Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
4. filter membrane according to claim 3, is characterized in that, described metallic element comprises at least one in Zn, Zr, Cu or Mg.
5. filter membrane according to claim 1, is characterized in that, described organic ligand is
,
,
,
,
,
,
or
in one, or comprise following co-ordinating functionality :-CO
2h ,-NO
2,-OH ,-NH
2,-CN ,-SO
3h ,-SH ,-CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2or-C (CN)
3in at least one, wherein, the R in co-ordinating functionality represents the alkylene comprising 1 to 5 phenyl ring independently of one another.
6. filter membrane according to claim 5, is characterized in that, described organic ligand is
or comprise-CO
2h ,-NH
2or the organic ligand of at least one co-ordinating functionality in-OH.
7. filter membrane according to claim 1, it is characterized in that, described polymer comprises at least one in polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, PMA, polyethylene glycol, Merlon.
8. filter membrane according to claim 7, is characterized in that, described polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
9. filter membrane according to claim 1, is characterized in that, the source metal of described metal-organic framework materials is zirconium chloride, organic ligand is the amino terephthalic acid (TPA) of 2-, and described polymer is polyacrylonitrile.
10. filter membrane according to claim 1, is characterized in that, the source metal of described metal-organic framework materials is Schweinfurt green, organic ligand is trimesic acid, and described polymer is polystyrene.
11. filter membranes according to claim 1, is characterized in that, the source metal of described metal-organic framework materials is zinc nitrate, organic ligand is glyoxal ethyline, and described polymer is polyacrylonitrile.
12. filter membranes according to claim 1, is characterized in that, the source metal of described metal-organic framework materials is magnesium nitrate, organic ligand is 2,5-Dihydroxyterephthalic acid, and described polymer is polyvinylpyrrolidone.
Filter membrane in 13. claim 1-12 described in arbitrary claim, is characterized in that, the described metal-organic framework materials relative to 1 gram, and the consumption of described polymer is 0.1-10 gram.
14. 1 kinds of methods preparing filter membrane, the method comprises: by metal-organic framework materials and polymer contact, described metal-organic framework materials forms the metallic organic framework part in described filter membrane, described polymer forms the polymer fiber part in described filter membrane, and wherein said metal-organic framework materials is formed by source metal and organic ligand effect.
15. methods according to claim 14, is characterized in that: described source metal comprises at least one in metal cluster, slaine or metal oxide.
16. methods according to claim 15, is characterized in that: the metallic element in described source metal comprises at least one in Mg, Ca, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ge.
17. methods according to claim 16, is characterized in that, described metallic element comprises at least one in Zn, Zr, Cu or Mg.
18. methods according to claim 14, is characterized in that: described organic ligand is
,
,
,
,
,
,
or
in one, or comprise following co-ordinating functionality :-CO
2h ,-NO
2,-OH ,-NH
2,-CN ,-SO
3h ,-SH ,-CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2or-C (CN)
3in at least one, wherein, the R in co-ordinating functionality represents the alkylene comprising 1 to 5 phenyl ring independently of one another.
19. methods according to claim 18, is characterized in that, described organic ligand is
or comprise-CO
2h ,-OH or-NH
2in the organic ligand of at least one co-ordinating functionality.
20. methods according to claim 14, is characterized in that: described polymer comprises at least one in polytetrafluoroethylene (PTFE), polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene, polyacrylonitrile, PMA, polyethylene glycol, Merlon.
21. methods according to claim 20, is characterized in that, described polymer is polyacrylonitrile, polystyrene or polyvinylpyrrolidone.
22. methods according to claim 14, is characterized in that, the source metal of described metal-organic framework materials is zirconium chloride, organic ligand is the amino terephthalic acid (TPA) of 2-, and described polymer is polyacrylonitrile.
23. methods according to claim 14, is characterized in that, the source metal of described metal-organic framework materials is Schweinfurt green, organic ligand is trimesic acid, and described polymer is polystyrene.
24. methods according to claim 14, is characterized in that, the source metal of described metal-organic framework materials is zinc nitrate, organic ligand is glyoxal ethyline, and described polymer is polyacrylonitrile.
25. methods according to claim 14, is characterized in that, the source metal of described metal-organic framework materials is magnesium nitrate, organic ligand is 2,5-Dihydroxyterephthalic acid, and described polymer is polyvinylpyrrolidone.
26. methods according to claim arbitrary in claim 14-25, it is characterized in that: the described metal-organic framework materials relative to 1 gram, the consumption of described polymer is 0.1-10 gram.
27. methods according to claim 14, it is characterized in that: the contact of described metal-organic framework materials and polymer is carried out in a solvent, the metal-organic framework materials of relative 1 gram, the consumption of solvent is 10-100 milliliter, prepares described filter membrane by spinning or dip-coating method.
28. methods according to claim 27, is characterized in that: described solvent comprises at least one in water, methyl alcohol, ethanol, dimethyl formamide, dimethylacetylamide, DEF.
The purposes of the filter membrane prepared by method in filtering PM2.5 in filter membrane described in 29. claim 1-12 any one claims or claim 14-25,27-28 described in any one claim.
The purposes of the filter membrane prepared by method in filtering VOC in filter membrane described in 30. claim 1-12 any one claims or claim 14-25,27-28 described in any one claim.
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Effective date of registration: 20210114 Address after: 102400 80712, 7th floor, education practice building, 11 Xueyuan North Street, Gongchen sub district office, Fangshan District, Beijing Patentee after: Science and technology Qingke (Beijing) Technology Co.,Ltd. Address before: 100139 room 4347, 4th floor, building 3, yard 29, Dongbeiwang South Road, Haidian District, Beijing Patentee before: KETAI(BEIJING)TECHNOLOGY Co.,Ltd. |
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Application publication date: 20160504 Assignee: Qingke (Chongqing) Advanced Materials Research Institute Co.,Ltd. Assignor: Science and technology Qingke (Beijing) Technology Co.,Ltd. Contract record no.: X2024980001958 Denomination of invention: Filter membrane and its preparation method and application Granted publication date: 20191203 License type: Common License Record date: 20240204 |