CN118204121A - Polyvinylidene fluoride catalytic membrane and preparation method and application thereof - Google Patents
Polyvinylidene fluoride catalytic membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN118204121A CN118204121A CN202410169463.4A CN202410169463A CN118204121A CN 118204121 A CN118204121 A CN 118204121A CN 202410169463 A CN202410169463 A CN 202410169463A CN 118204121 A CN118204121 A CN 118204121A
- Authority
- CN
- China
- Prior art keywords
- film
- catalytic
- polyvinylidene fluoride
- preparation
- casting solution
- 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.)
- Pending
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 140
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 69
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012528 membrane Substances 0.000 title abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 47
- 238000005266 casting Methods 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 33
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 9
- 239000004745 nonwoven fabric Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 230000004907 flux Effects 0.000 abstract description 21
- 238000011065 in-situ storage Methods 0.000 abstract description 13
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 5
- 238000000614 phase inversion technique Methods 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 10
- 229960001180 norfloxacin Drugs 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000009295 crossflow filtration Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229960005404 sulfamethoxazole Drugs 0.000 description 3
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 108010059993 Vancomycin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 1
- 229960000623 carbamazepine Drugs 0.000 description 1
- 229960001229 ciprofloxacin hydrochloride Drugs 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229960001572 vancomycin hydrochloride Drugs 0.000 description 1
- LCTORFDMHNKUSG-XTTLPDOESA-N vancomycin monohydrochloride Chemical compound Cl.O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 LCTORFDMHNKUSG-XTTLPDOESA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyvinylidene fluoride catalytic membrane and a preparation method and application thereof. The catalytic film is prepared by an in-situ growth synchronous phase inversion method, and comprises the following steps: dissolving polyvinylidene fluoride, a pore-forming agent and hydrated hydrochloride in an organic solvent to obtain a casting solution; and (3) after standing and defoaming, coating the casting solution on a support body to form a film, immersing the support body in a potassium hexacyanocobaltate aqueous solution to perform phase inversion to form a film, and simultaneously growing Prussian blue analogue catalyst particles in situ in the film to obtain the polyvinylidene fluoride catalytic film. The preparation method of the polyvinylidene fluoride catalytic film provided by the invention is simple, energy-saving, mild and controllable, and the prepared catalytic film has high permeation flux and excellent mechanical property, shows high-efficiency catalytic efficiency, and is mainly applied to catalyzing persulfate to oxidize and degrade organic pollutants in water.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a polyvinylidene fluoride catalytic membrane, and a preparation method and application thereof.
Background
At present, a large amount of organic pollutants in water body are generated due to the production and use of medical medicaments, the abuse of pesticides, the discharge of personal care products into domestic wastewater and the discharge of industrial wastes, so that fresh water storage is seriously threatened, and the traditional treatment modes of organic pollutant wastewater such as adsorption sedimentation, coagulation flocculation, biological treatment and the like have the defects of high manufacturing cost, high industrialization cost, complex technology, low energy utilization rate and many practical application aspects. Advanced Oxidation Processes (AOPs) based on nano-catalyst activated persulfate catalytic oxidative degradation of organic pollutants can be applied to water pollution remediation processes by generating reactive oxygen radicals with strong oxidizing properties to oxidatively degrade the organic pollutants, and particularly Fenton-like reactions based on Peroxomonosulfate (PMS) are considered as an effective measure for treating organic pollutant wastewater. Prussian Blue Analogues (PBAs) are used as an ancient synthetic cyanide coordination polymer, have a high specific surface area, a three-dimensional open metal framework structure and polydisperse metal active sites, and the adjustability of the structure also enables the PBAs to have a bimetal synergistic effect, so that the PBAs can be used as an effective peroxymonosulfate activator for catalyzing, oxidizing and degrading organic pollutants. However, this method is still limited in practical use due to low activation efficiency and low radical utilization.
As an innovative water treatment technology, the membrane separation technology has the advantages of low energy consumption, small occupied area, large treatment capacity, no secondary pollution and the like. In recent years, the design of catalytic membranes with the functions of catalytic degradation of organic matters and separation has been attracting attention, and how to develop high-performance catalytic membrane systems to effectively remove pollutants in water has been receiving extensive attention from students at home and abroad. Catalytic reactions occur in nanoscale spaces, electron movement is constrained and limited by the space, and such confinement effects will alter electron movement characteristics, resulting in a change in the electronic structure of the system, thereby increasing the rate of catalytic reactions. The continuous multistage high-efficiency catalytic degradation of organic pollutants in water under the nanoscale can be realized by coupling the finite field catalysis and the membrane separation process. At present, the preparation of the catalytic membrane mostly adopts the following three methods: (1) Firstly, phase-converting into a film, and then loading prepared catalytic particles into the film; (2) Firstly preparing a catalyst, then adding the catalyst into a casting solution, and forming a film through phase inversion; (3) The phase is converted into a film, and then catalyst particles are grown in situ in the film. However, the preparation methods of the catalytic films have a plurality of defects, such as stepwise preparation processes of the catalytic films, complicated steps and complex preparation methods; the catalyst cannot be uniformly dispersed, and the membrane has poor catalytic performance due to fewer exposed active sites; the catalyst is very easy to run off due to the fact that the catalyst and the membrane matrix cannot be firmly combined.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyvinylidene fluoride catalytic film, and a preparation method and application thereof. The catalytic membrane is prepared by in-situ growth and synchronous phase inversion method, and metal salt is added into the membrane casting solution and ligand salt is added into the water solidifying bath in the membrane preparation process, so that Prussian blue analogue catalyst particles grow in situ in the phase inversion process to synthesize the catalytic membrane in one step, the preparation method is simple, and the prepared catalytic membrane has high permeation flux, excellent mechanical property and high catalytic efficiency.
The technical scheme of the invention is as follows:
The first aspect of the invention provides a preparation method of a polyvinylidene fluoride catalytic film, which comprises the following steps:
(1) Dissolving polyvinylidene fluoride, a pore-forming agent and hydrated hydrochloride in an organic solvent to obtain a casting solution;
(2) Coating the casting solution on a support body to form a film, and immersing the film in a potassium hexacyanocobaltate aqueous solution to obtain a polyvinylidene fluoride catalytic film containing Prussian blue analog particles;
the hydrated hydrochloride comprises one of ferrous chloride tetrahydrate, cobalt chloride hexahydrate, nickel chloride hexahydrate, copper chloride dihydrate, stannous chloride dihydrate and manganese chloride tetrahydrate.
The Prussian blue analogues include Fe3[Co(CN)6]2、Co3[Co(CN)6]2、Ni3[Co(CN)6]2、Cu3[Co(CN)6]2、Sn3[Co(CN)6]2 or Mn 3[Co(CN)6]2.
Preferably, in the step (1), the mass fraction of polyvinylidene fluoride in the casting solution is 16%, the mass fraction of the pore-forming agent is 4%, and the mass fraction of the hydrated hydrochloride is 0.32-1.92%.
Preferably, in the step (1), the pore-forming agent comprises at least one of polyethylene glycol and polyvinylpyrrolidone, including but not limited to polyethylene glycol 400, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 10000, polyethylene glycol 20000 and polyvinylpyrrolidone; the organic solvent comprises N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.
Preferably, in the step (2), the film thickness of the coating film is 150-250 μm, and the film thickness of the polyvinylidene fluoride catalytic film is 150-250 μm.
Preferably, in the step (2), the concentration of the potassium hexacyanocobaltate aqueous solution is 1-5 mmol/L; the molar ratio of the hydrated hydrochloride to the potassium hexacyanocobaltate is 4.0:5.0-0.6:5.0.
Preferably, the Prussian blue analog particles have a particle size of 20 to 200nm.
Preferably, in the step (2), the support comprises a glass plate, a polypropylene nonwoven fabric, a polyester nonwoven fabric.
Preferably, in the step (2), the soaking temperature is 25-50 ℃ and the soaking time is 8-24 h.
In a second aspect, the invention provides a polyvinylidene fluoride catalytic film prepared by the preparation method in the first aspect, wherein the content of the Prussian blue analogues in the catalytic film is 1.6-10wt%, and the content is theoretical content.
A third aspect of the present invention provides a polyvinylidene fluoride catalytic film prepared by the preparation method of the first aspect or the application of the polyvinylidene fluoride catalytic film of the second aspect, wherein the catalytic film is used for water treatment; the water treatment includes catalytic degradation of organic pollutant wastewater.
The beneficial technical effects of the invention are as follows:
According to the invention, metal salt is added into the casting solution in the film preparation process, and ligand salt is added into the water solidifying bath, so that Prussian blue analog catalyst particles are grown in situ in the phase conversion process, the catalytic film is synthesized in one step, the preparation method of the catalytic film is simple and energy-saving, the process is mild, the controllability and the variability are high, the catalyst particles grown in situ in the film are uniformly and firmly dispersed, catalyst agglomeration and embedding caused by a method of loading other catalysts on a film substrate are avoided, and rich active sites in the catalytic process are ensured.
The catalytic membrane provided by the invention has stable catalytic performance, can efficiently and rapidly activate persulfate to generate active oxygen free radicals, can rapidly remove organic pollutants under a wider applicable pH range, has good catalytic reusability, and has wide application prospect in the water treatment industry and considerable economic benefit.
The catalytic membrane provided by the invention can maintain relatively long-term stable flux under a lower operating pressure of 0.1MPa, is excellent in mechanical strength and has certain reusability.
Drawings
FIG. 1 is an infrared spectrum of a polyvinylidene fluoride catalytic film prepared in example 2 of the present invention and a polyvinylidene fluoride film of comparative example 1.
FIG. 2 is an electron microscopic image of a polyvinylidene fluoride catalytic film prepared in example 2 of the present invention.
FIG. 3 shows the removal rate of norfloxacin from a polyvinylidene fluoride catalytic film prepared in example 2 of the present invention at different pH values.
FIG. 4 shows the removal rate of norfloxacin from a polyvinylidene fluoride catalytic film prepared in example 2 of the present invention after 4 cycles.
FIG. 5 is a graph showing the flux change of the polyvinylidene fluoride catalytic film prepared in example 3 of the present invention in 90 minutes of operation time.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
The catalytic membrane provided by the invention degrades organic pollutants in water by activating persulfate, wherein the organic pollutants are methylene blue, rhodamine B, congo red, methyl orange, tetracycline hydrochloride, sulfamethoxazole, norfloxacin, ciprofloxacin, carbamazepine or vancomycin hydrochloride.
In the invention, the casting solution is coated on a support body to form a film, and immersed in a potassium hexacyanocobaltate aqueous solution to carry out phase inversion to form a film, and meanwhile, prussian blue analogue catalyst particles grow in situ in the film to obtain the polyvinylidene fluoride catalytic film. M Ⅱ in the resulting prussian blue analogues reacts as a reactive site with persulfates to produce reactive intermediates (ROS) such as SO 4 ·-, OH and 1O2 that participate in the removal of organic contaminants, such that the contaminant molecules are oxidatively decomposed and eventually mineralized into CO 2 and H 2 O. The polyvinylidene fluoride catalytic membrane has rich nanoscale porous structures, the structures can promote the adsorption process of the catalytic membrane on organic pollutants, in addition, the structures can limit the active intermediates and pollutant molecules in the nano space, and the electron movement in the reaction process is limited and restricted by the nano space, so that the catalytic reaction efficiency can be improved, and the removal performance of the organic pollutants is further improved.
The first aspect of the invention provides a preparation method of a polyvinylidene fluoride catalytic film, which comprises the following steps:
(1) Dissolving polyvinylidene fluoride, a pore-forming agent and hydrated hydrochloride in an organic solvent to obtain a casting solution;
(2) Coating the casting solution on a support body to form a film, and immersing the film in a potassium hexacyanocobaltate aqueous solution to obtain a polyvinylidene fluoride catalytic film containing Prussian blue analog particles;
the hydrated hydrochloride comprises one of ferrous chloride tetrahydrate, cobalt chloride hexahydrate, nickel chloride hexahydrate, copper chloride dihydrate, stannous chloride dihydrate and manganese chloride tetrahydrate.
The Prussian blue analog particles include Fe3[Co(CN)6]2、Co3[Co(CN)6]2、Ni3[Co(CN)6]2、Cu3[Co(CN)6]2、Sn3[Co(CN)6]2 or Mn 3[Co(CN)6]2.
Preferably, in the step (1), the mass fraction of polyvinylidene fluoride in the casting solution is 16%, the mass fraction of the pore-forming agent is 4%, the mass fraction of hydrated hydrochloride is 0.32-1.92%, and the mass fraction of the hydrated hydrochloride includes, but is not limited to, 0.32%, 0.5%, 1.12%, 1.5%, 1.8%, and 1.92%.
Preferably, in the step (1), the pore-forming agent comprises at least one of polyethylene glycol and polyvinylpyrrolidone, including but not limited to polyethylene glycol 400, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 10000, polyethylene glycol 20000 and polyvinylpyrrolidone; the organic solvent comprises N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.
Preferably, in step (2), the film thickness of the coating film is 150 to 250 μm, including but not limited to 150 μm, 180 μm, 200 μm, 220 μm, 240 μm, 250 μm, preferably 200 μm.
Preferably, in the step (2), the concentration of the potassium hexacyanocobaltate aqueous solution is 1-5 mmol/L, including but not limited to 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L and 5mmol/L; the molar ratio of the hydrated hydrochloride to the potassium hexacyanocobaltate is 4.0:5.0-0.6:5.0, including but not limited to 4:0.6, 4:5, 4:2, 4.5:0.6, 4.5:2, 4.5:5, 5:0.6, 5:1, 5:5.
Preferably, the Prussian blue analog particles have a particle size of 20 to 200nm.
Preferably, in the step (2), the support comprises a glass plate, a polypropylene nonwoven fabric, a polyester nonwoven fabric.
Preferably, in the step (2), the soaking temperature is 25-50 ℃, including but not limited to 25 ℃,30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, and the soaking time is 8-24 hours, including but not limited to 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours.
Preferably, the polyvinylidene fluoride catalytic film containing Prussian blue analog particles has a film thickness of 150 to 250 μm.
In a second aspect, the present invention provides a polyvinylidene fluoride catalytic film prepared by the preparation method according to the first aspect, wherein the content of the Prussian blue analogues in the catalytic film is 1.6-10wt%, including but not limited to 1.6wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, where the content is theoretical content.
The theoretical content of Prussian blue analog particles is the mass obtained by carrying out coordination reaction according to the maximum coordination number of hydrated hydrochloride and potassium hexacyanocobaltate, specifically, the mass of the hydrated hydrochloride is converted into the mass of hydrated hydrochloride (the potassium hexacyanocobaltate is excessive), the mass of PBAs is obtained according to the maximum coordination number of a general formula M Ⅱ 3[Co(CN)6]2 after the coordination of the hydrated hydrochloride and the potassium hexacyanocobaltate, the mass is converted into the mass according to the relative molecular mass of M Ⅱ 3[Co(CN)6]2, and the percentage of the mass of the Prussian blue analog particles generated in theory to the mass of polyvinylidene fluoride is calculated, namely the theoretical content of the Prussian blue analog particles.
A third aspect of the present invention provides a polyvinylidene fluoride catalytic film prepared by the preparation method of the first aspect or the application of the polyvinylidene fluoride catalytic film of the second aspect, wherein the catalytic film is used for water treatment; the water treatment includes catalytic degradation of organic pollutant wastewater.
The performance test of the catalytic membrane is carried out by the cross-flow filter device in all the examples, the pump flow rate is 1.7L/min, the effective filtering area of the membrane is 0.001256m 2, and the water flux and the pollutant removal rate of all the membranes are tested under the conditions that the operating pressure is 0.1MPa and the operating temperature is 25 ℃.
The water flux is calculated according to the following formula:
Wherein J is water flux, L.m -2·h-1.bar; v is the sampling volume, 0.005L; s is the effective filtration area of the membrane, 0.001256m 2; t is sampling time, h; Δp is the transmembrane pressure difference, bar.
The catalytic performance test of the catalytic film was determined using an ultraviolet-visible spectrophotometer (UV-Vis, TU-1901). And (3) measuring the absorbance of the filtrate at intervals of 5min under the maximum absorption wavelength corresponding to the pollutant, wherein the total measurement time is 60min, calculating the concentration of the solution according to the absorbance, and calculating the pollutant removal rate by the following formula:
Wherein R is the removal rate of pollutants; c 0 and C t were used as initial and t-time concentrations of the solutions, mg/L.
The invention is further illustrated by the following examples and comparative examples.
Example 1
A preparation method of a polyvinylidene fluoride catalytic film comprises the following steps:
S1: dissolving cobalt chloride hexahydrate, polyethylene glycol 20000 and polyvinylidene fluoride in N, N' -dimethylformamide at 70 ℃ to obtain a casting solution, wherein the mass fractions of the polyvinylidene fluoride, the polyethylene glycol 20000, the cobalt chloride hexahydrate and the solvent in the casting solution are respectively 16wt%, 4wt%, 0.32wt% and 79.68wt%.
S2: coating a film casting solution which is insulated at 40 ℃ on a glass plate to form a film, immersing the film casting solution in a potassium hexacyanocobaltate aqueous solution with the concentration of 5mmol/L at 40 ℃ for 24 hours to convert the film into a film, and simultaneously growing Co 3[Co(CN)6]2 particles in situ in the film to obtain a polyvinylidene fluoride catalytic film with the average film thickness of 174 mu m, wherein the molar ratio of cobalt chloride hexahydrate to potassium hexacyanocobaltate is 0.6:5.0, and the theoretical content of Co 3[Co(CN)6]2 particles in the obtained catalytic film is 1.6wt%.
And (3) carrying out the comprehensive performance test of the catalytic membrane by adopting a cross-flow membrane filter device at 25 ℃ and 0.1 MPa. Preparing 20mg/L tetracycline hydrochloride solution as a raw material liquid to be tested, adjusting the initial pH=7 of the raw material liquid to be tested, adding potassium peroxomonosulfate to obtain the raw material liquid to be tested when the test is started, and performing catalytic performance test of the catalytic membrane, wherein the concentration of the potassium peroxomonosulfate is 5mmol/L, and the test duration is 60min. The result shows that the permeation flux of the catalytic membrane is 178.43 L.m -2·h-1.bar, and when the initial pH=7 of the liquid to be detected and the addition amount of the potassium peroxomonosulfate salt is 5mmol/L, the removal rate of the catalytic membrane to 20mg/L tetracycline hydrochloride within 60min is 86.58%.
Example 2
A preparation method of a polyvinylidene fluoride catalytic film comprises the following steps:
S1: dissolving nickel chloride hexahydrate, polyethylene glycol 20000 and polyvinylidene fluoride in N-methyl pyrrolidone at 70 ℃ to obtain a casting solution, wherein the mass fractions of the polyvinylidene fluoride, the polyethylene glycol 20000, the nickel chloride hexahydrate and the solvent in the casting solution are respectively 16wt%, 4wt%, 1.12wt% and 78.88wt%.
S2: coating a film casting solution which is insulated at 40 ℃ on a polypropylene non-woven fabric to form a film, immersing the film casting solution in a potassium hexacyanocobaltate aqueous solution with the concentration of 3mmol/L at 40 ℃ for 24 hours to convert the film into a film, and simultaneously growing Ni 3[Co(CN)6]2 particles in situ in the film to obtain a polyvinylidene fluoride catalytic film, wherein the average film thickness is 205 mu m, the molar ratio of nickel chloride hexahydrate to potassium hexacyanocobaltate is 2.4:3.0, and the theoretical content of Ni 3[Co(CN)6]2 particles in the obtained catalytic film is 6wt%.
And (3) carrying out the comprehensive performance test of the catalytic membrane by adopting a cross-flow membrane filter device at 25 ℃ and 0.1 MPa. Preparing a 20mg/L norfloxacin solution as a raw material liquid to be tested, adjusting the initial pH=7 of the liquid to be tested, adding potassium peroxomonosulfate to obtain the liquid to be tested when the test is started, and testing the catalytic performance of the catalytic membrane, wherein the concentration of the potassium peroxomonosulfate is 5mmol/L, and the test duration is 60min. The result shows that the permeation flux of the catalytic membrane is 650.14 L.m -2·h-1.bar, and when the initial pH=7 of the liquid to be detected and the addition amount of the potassium peroxomonosulfate salt is 5mmol/L, the removal rate of the catalytic membrane to 20mg/L norfloxacin in 60min is 97.88%.
Example 3
A preparation method of a polyvinylidene fluoride catalytic film comprises the following steps:
S1: manganese chloride tetrahydrate, polyvinylpyrrolidone and polyvinylidene fluoride are dissolved in N, N' -dimethylacetamide at 70 ℃ to obtain casting solution, and the mass fractions of the polyvinylidene fluoride, the polyvinylpyrrolidone, the cobalt chloride hexahydrate and the solvent in the casting solution are 16wt%, 4wt%, 0.32wt% and 79.68wt% respectively.
S2: coating a film casting solution which is insulated at 40 ℃ on a glass plate to form a film, immersing the film casting solution in a potassium hexacyanocobaltate aqueous solution with the concentration of 3mmol/L at 40 ℃ for 24 hours to convert the film into a film, and simultaneously growing Mn 3[Co(CN)6]2 particles in situ in the film to obtain a polyvinylidene fluoride catalytic film, wherein the average film thickness is 209 mu m, the molar ratio of manganese chloride tetrahydrate to potassium hexacyanocobaltate is 0.6:3.0, and the theoretical content of Mn 3[Co(CN)6]2 particles in the obtained catalytic film is 3.2wt%.
And (3) carrying out the comprehensive performance test of the catalytic membrane by adopting a cross-flow membrane filter device at 25 ℃ and 0.1 MPa. Preparing a sulfamethoxazole solution with the concentration of 20mg/L as a raw material liquid to be tested, adjusting the initial pH=9 of the raw material liquid to be tested, adding potassium peroxomonosulfate to obtain the raw material liquid to be tested when the test is started, and testing the catalytic performance of the catalytic membrane, wherein the concentration of the potassium peroxomonosulfate is 5mmol/L, and the test duration is 60min. As a result, the permeation flux of the catalyst film was 164.35 L.multidot.m -2·h-1.multidot.bar, and when the initial pH=9 of the solution to be measured and the addition amount of the potassium peroxomonosulfate salt was 5mmol/L, the removal rate of the catalyst film to 20mg/L of sulfamethoxazole in 60min was 91.04%.
Example 4
A preparation method of a polyvinylidene fluoride catalytic film comprises the following steps:
S1: dissolving cobalt chloride hexahydrate, polyethylene glycol 10000 and polyvinylidene fluoride in N-methylpyrrolidone at 70 ℃ to obtain a casting solution, wherein the mass fractions of the polyvinylidene fluoride, the polyethylene glycol 10000, the cobalt chloride hexahydrate and the solvent in the casting solution are respectively 16wt%, 4wt%, 1.92wt% and 78.08wt%.
S2: coating a film casting solution which is insulated at 40 ℃ on a polyester non-woven fabric to form a film, immersing the film casting solution in a potassium hexacyanocobaltate aqueous solution with the concentration of 5mmol/L at 40 ℃ for 24 hours to convert the film into a film, and simultaneously growing Co 3[Co(CN)6]2 particles in situ in the film to obtain a polyvinylidene fluoride catalytic film, wherein the average film thickness is 220 mu m, the molar ratio of cobalt chloride hexahydrate to potassium hexacyanocobaltate is 4.0:5.0, and the theoretical content of Co 3[Co(CN)6]2 particles in the obtained catalytic film is 10wt%.
And (3) carrying out the comprehensive performance test of the catalytic membrane by adopting a cross-flow membrane filter device at 25 ℃ and 0.1 MPa. Preparing 20mg/L tetracycline hydrochloride solution as a raw material liquid to be tested, adjusting the initial pH=7 of the raw material liquid to be tested, adding potassium peroxomonosulfate to obtain the raw material liquid to be tested when the test is started, and testing the catalytic performance of the catalytic membrane, wherein the concentration of the potassium peroxomonosulfate is 5mmol/L, and the test duration is 60min. The result shows that the permeation flux of the catalytic membrane is 1050.28 L.m -2·h-1.bar, and when the initial pH=7 of the liquid to be detected and the addition amount of the potassium peroxomonosulfate salt is 5mmol/L, the removal rate of the catalytic membrane to 20mg/L tetracycline hydrochloride within 60min is 94.62%.
Example 5
A preparation method of a polyvinylidene fluoride catalytic film comprises the following steps:
s1: dissolving nickel chloride hexahydrate, polyvinylpyrrolidone and polyvinylidene fluoride in N, N' -dimethylformamide at 70 ℃ to obtain a casting solution, wherein the mass fractions of the polyvinylidene fluoride, the polyvinylpyrrolidone, the nickel chloride hexahydrate and the solvent are respectively 16wt%, 4wt%, 1.12wt% and 78.88wt%.
S2: coating a film casting solution which is insulated at 40 ℃ on a glass plate to form a film, immersing the film casting solution in a potassium hexacyanocobaltate aqueous solution with the concentration of 4mmol/L at 40 ℃ for 24 hours to convert the film into a film, and simultaneously growing Ni 3[Co(CN)6]2 particles in situ in the film to obtain a polyvinylidene fluoride catalytic film, wherein the average film thickness is 212 mu m, the molar ratio of nickel chloride hexahydrate to potassium hexacyanocobaltate is 2.4:4.0, and the Ni 3[Co(CN)6]2 particles content in the obtained catalytic film is 6wt%.
And (3) carrying out the comprehensive performance test of the catalytic membrane by adopting a cross-flow membrane filter device at 25 ℃ and 0.1 MPa. Respectively preparing 20mg/L methylene blue and rhodamine B base solution as raw material liquid to be tested, adjusting the initial pH=7 of the raw material liquid to be tested, respectively adding potassium peroxomonosulphate to obtain the raw material liquid to be tested when the test is started, and testing the catalytic performance of the catalytic film, wherein the concentration of the potassium peroxomonosulphate is 5mmol/L, and the test duration is 60min. The results show that the permeation flux of the catalytic membrane is 145.14 L.m -2·h-1 bar, and when the initial pH=7 of the liquid to be detected and the addition amount of the potassium peroxomonosulfate salt is 5mmol/L, the removal rates of the catalytic membrane to 20mg/L methylene blue and rhodamine B groups in 60min are 98.62% and 95.96% respectively.
Comparative example 1
A polyvinylidene fluoride film, the preparation process of which comprises the following steps:
Polyethylene glycol 20000 and polyvinylidene fluoride are dissolved in N, N' -dimethylformamide at 70 ℃ to obtain a casting film liquid, wherein the mass fractions of the polyvinylidene fluoride, the polyethylene glycol 20000 and the solvent are respectively 16wt%, 4wt% and 78wt%. The casting solution which is kept at 40 ℃ is coated on a glass plate to form a film, and the film is immersed in deionized water at 25 ℃ for 24 hours to be converted into a film, wherein the average film thickness is 202 mu m.
The comprehensive performance of the catalytic membrane is carried out by adopting a cross-flow membrane filter device at 25 ℃ and 0.1MPa, and the permeation flux of the catalytic membrane is 104.41 L.m -2·h-1.bar; the removal rate of the catalytic film to tetracycline hydrochloride was measured by the method of example, and the result shows that the removal rate of the catalytic film to 20mg/L tetracycline hydrochloride within 60min is 70.20% when the concentration of potassium peroxomonosulfate salt is 5mmol/L and the initial pH of the test solution is=7.
Comparative example 2
A preparation method of a polyvinylidene fluoride catalytic film comprises the following steps:
And dissolving the polyvinylpyrrolidone and the polyvinylidene fluoride in N, N' -dimethylformamide at 70 ℃ to obtain a casting film liquid, wherein the mass fractions of the polyvinylidene fluoride, the polyvinylpyrrolidone and the solvent are respectively 16wt%, 4wt% and 78wt%. Coating the film casting solution which is insulated at 40 ℃ on a polyester non-woven fabric to form a film, immersing the film casting solution in deionized water at 25 ℃ for 24 hours to convert the film into a film, wherein the average film thickness is 210 mu m.
The catalytic membrane comprehensive performance is carried out by adopting a cross-flow membrane filtration device at 25 ℃ and 0.1MPa, and the permeation flux of the catalytic membrane of comparative example 2 is 486.37 L.m -2·h-1.bar; the removal rates of the catalytic film on methylene blue and rhodamine B groups are respectively measured by using the method of the example, and the result shows that the concentration of the potassium peroxymonosulfate is 5mmol/L, and the removal rate of the catalytic film on 20mg/L methylene blue and rhodamine B groups within 60min is 46.20% and 40.39% when the initial pH value of the test solution is=7.
Test example:
(1) Infrared spectrogram
The infrared spectrograms of the catalytic film prepared in example 2 of the present invention and the polyvinylidene fluoride film prepared in comparative example 1 were measured, and the results are shown in fig. 1. From the figure, it can be seen that the polyvinylidene fluoride catalytic film exhibited a characteristic peak at 2166cm -1, which is attributed to the stretching vibration of c≡n in the nickel-cobalt prussian blue analogue.
(2) Film Performance test
By measuring the permeation fluxes of the membranes prepared in examples and comparative examples, the catalytic performances of the catalytic membranes prepared in examples 1 to 5 have higher pure water fluxes and higher catalytic removal rates of organic pollutants than those of the catalytic membranes prepared in comparative examples 1 to 2, and the catalytic membranes have high catalytic performances and higher water fluxes in a catalytic system, so that the catalytic membranes can be used for removing organic pollutants in water.
(3) Testing of removal at different pH
A 20mg/L norfloxacin solution at an initial ph=2, 5, 7, 9, 11 was prepared and the catalytic performance of the catalytic membrane was tested at different pH values using a membrane cross-flow filtration device under the same test conditions as in example 2. As shown in fig. 3, the catalytic film prepared in example 2 showed higher removal rate of norfloxacin at different pH, showing the wide pH applicable range of the catalytic film prepared in example 2.
(4) Repeatability test of catalytic film
The catalytic membrane prepared in example 2 was subjected to catalytic repetition test to prepare norfloxacin solution with a concentration of 20mg/L and an initial ph=7, and the norfloxacin was removed by continuously recycling 4 times of activated PMS under the same conditions using a membrane cross-flow filtration device, and the reaction time per cycle was 60min. As shown in fig. 4, the removal rate of norfloxacin in the catalytic film prepared in example 2 is still above 95% after 4 catalytic cycles, which indicates that the catalytic film prepared in example 2 has better catalytic reusability.
(5) Stability test of catalytic membranes
The continuous stability performance test was performed on example 3, and the stability of the catalytic membrane prepared in example 3 was investigated for a long period of time by examining the pure water flux change of the normal operation of example 3 in 90 minutes using a membrane cross-flow filtration apparatus under the same conditions. As shown in fig. 5, the catalytic film prepared in example 3 maintains a relatively stable flux for a longer operation time of 90 minutes, and a relatively remarkable flux decay does not appear temporarily, which indicates that the catalytic film prepared in example 3 can maintain a long-term stable flux at a lower operation pressure of 0.1MPa, and has good operation stability and relatively excellent mechanical strength.
The above is only a preferred embodiment of the present invention, and the present invention is not limited to the above examples. It is to be understood that other modifications and variations which may be directly derived or contemplated by those skilled in the art without departing from the spirit and concepts of the present invention are deemed to be included within the scope of the present invention.
Claims (10)
1. A method for preparing a polyvinylidene fluoride catalytic film, which is characterized by comprising the following steps:
(1) Dissolving polyvinylidene fluoride, a pore-forming agent and hydrated hydrochloride in an organic solvent to obtain a casting solution;
(2) Coating the casting solution on a support body to form a film, and immersing the film in a potassium hexacyanocobaltate aqueous solution to obtain a polyvinylidene fluoride catalytic film containing Prussian blue analog particles;
the hydrated hydrochloride comprises one of ferrous chloride tetrahydrate, cobalt chloride hexahydrate, nickel chloride hexahydrate, copper chloride dihydrate, stannous chloride dihydrate and manganese chloride tetrahydrate.
The Prussian blue analog particles include Fe3[Co(CN)6]2、Co3[Co(CN)6]2、Ni3[Co(CN)6]2、Cu3[Co(CN)6]2、Sn3[Co(CN)6]2 or Mn 3[Co(CN)6]2.
2. The method according to claim 1, wherein in the step (1), the mass fraction of polyvinylidene fluoride in the casting solution is 16%, the mass fraction of the pore-forming agent is 4%, and the mass fraction of the hydrated hydrochloride is 0.32-1.92%.
3. The method according to claim 1, wherein in the step (1), the pore-forming agent comprises at least one of polyethylene glycol and polyvinylpyrrolidone; the organic solvent comprises N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.
4. The method according to claim 1, wherein in the step (2), the film thickness of the polyvinylidene fluoride catalyst film is 150 to 250. Mu.m.
5. The method according to claim 1, wherein in the step (2), the concentration of the potassium hexacyanocobaltate aqueous solution is 1 to 5mmol/L; the molar ratio of the hydrated hydrochloride to the potassium hexacyanocobaltate is 4.0:5.0-0.6:5.0.
6. The preparation method according to claim 1, wherein the Prussian blue analog particles have a particle diameter of 20 to 200nm.
7. The method according to claim 1, wherein in the step (2), the support comprises a glass plate, a polypropylene nonwoven fabric, a polyester nonwoven fabric.
8. The method according to claim 1, wherein in the step (2), the soaking temperature is 25 to 50 ℃ and the soaking time is 8 to 24 hours.
9. A polyvinylidene fluoride catalytic film prepared by the preparation method of any one of claims 1 to 8, wherein the content of prussian blue analogue particles in the catalytic film is 1.6 to 10wt%.
10. Use of a polyvinylidene fluoride catalytic film prepared by the preparation method according to any one of claims 1 to 8 or a polyvinylidene fluoride catalytic film according to claim 9 for water treatment; the water treatment includes catalytic degradation of organic pollutant wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410169463.4A CN118204121A (en) | 2024-02-06 | 2024-02-06 | Polyvinylidene fluoride catalytic membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410169463.4A CN118204121A (en) | 2024-02-06 | 2024-02-06 | Polyvinylidene fluoride catalytic membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118204121A true CN118204121A (en) | 2024-06-18 |
Family
ID=91445296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410169463.4A Pending CN118204121A (en) | 2024-02-06 | 2024-02-06 | Polyvinylidene fluoride catalytic membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118204121A (en) |
-
2024
- 2024-02-06 CN CN202410169463.4A patent/CN118204121A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Superoxide radical mediated persulfate activation by nitrogen doped bimetallic MOF (FeCo/N-MOF) for efficient tetracycline degradation | |
| Ye et al. | A novel NH2-MIL-88B (Fe)-modified ceramic membrane for the integration of electro-Fenton and filtration processes: A case study on naproxen degradation | |
| CN113333011B (en) | Composite catalyst and preparation method and application thereof | |
| CN107617447B (en) | Ag @ MOFs/TiO2Preparation method and application of photocatalyst | |
| Ahmadi et al. | Foulant layer degradation of dye in Photocatalytic Membrane Reactor (PMR) containing immobilized and suspended NH2-MIL125 (Ti) MOF led to water flux recovery | |
| He et al. | Incorporating metal–organic frameworks into substrates for environmental applications | |
| AU2008327879A1 (en) | Production and use of novel polyanilines for treating water | |
| Li et al. | Highly efficient sunlight-driven self-cleaning electrospun nanofiber membrane NM88B@ HPAN for water treatment | |
| CN114618589B (en) | Preparation method and application of ozone degradation catalyst based on iron-based organic framework | |
| CN111450829B (en) | Copper oxide nano catalytic film for catalyzing persulfate to degrade organic wastewater and preparation method thereof | |
| Zhou et al. | In situ growth of UIO-66-NH2 on thermally stabilized electrospun polyacrylonitrile nanofibers for visible-light driven Cr (VI) photocatalytic reduction | |
| Zhang et al. | Development of polyacrylonitrile/perovskite catalytic membrane with abundant channel-assisted reaction sites for organic pollutant removal | |
| Marchesini et al. | Pd and Pd, In nanoparticles supported on polymer fibres as catalysts for the nitrate and nitrite reduction in aqueous media | |
| Huang et al. | Synthesis of recyclable 3D LC/h-ZIF-8 by Zn (Ⅱ) containing wastewater for photocatalytic degradation of mixed-dye under UV-Vis irradiation | |
| Teng et al. | A green hydrothermal synthesis of polyacrylonitrile@ carbon/MIL-101 (Fe) composite nanofiber membrane for efficient selective removal of tetracycline | |
| CN114950409A (en) | Manganese-based catalytic material and preparation method and application thereof | |
| CN109046029B (en) | Preparation method of modified PVDF ultrafiltration membrane for complex heavy metal wastewater treatment | |
| Hao et al. | Integration of g-C3N4 into cellulose/graphene oxide foams for efficient photocatalytic Cr (VI) reduction | |
| Song et al. | Facile synthesis method of C self-doped g-C3N4 and its performance in photodegradation of sulfamethoxazole | |
| Lin et al. | Engineering ZIF-67 loaded nanofibrous membrane with thermal stabilization treatment for efficient photocatalytic CO2 reduction | |
| CN113731402A (en) | Catalyst and preparation method and application thereof | |
| CN118204121A (en) | Polyvinylidene fluoride catalytic membrane and preparation method and application thereof | |
| CN114887617B (en) | Manganese oxide/carbon composite catalyst rich in oxygen vacancies and surface-functionalized, preparation method thereof and application thereof in formaldehyde removal | |
| Hu et al. | Soft high-loading TiO 2 composite biomaterial film as an efficient and recyclable catalyst for removing methylene blue | |
| CN113044952B (en) | Preparation method of metal organic framework nanofiber membrane and method for activating monoperoxybisulfate to treat organic wastewater by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |