CN109277006A - A kind of preparation method of polyvinylidene fluoride modified composite membrane - Google Patents
A kind of preparation method of polyvinylidene fluoride modified composite membrane Download PDFInfo
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- CN109277006A CN109277006A CN201811162594.0A CN201811162594A CN109277006A CN 109277006 A CN109277006 A CN 109277006A CN 201811162594 A CN201811162594 A CN 201811162594A CN 109277006 A CN109277006 A CN 109277006A
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 64
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- 239000011787 zinc oxide Substances 0.000 claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 claims abstract description 32
- 238000005576 amination reaction Methods 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 230000003647 oxidation Effects 0.000 claims 3
- 238000007254 oxidation reaction Methods 0.000 claims 3
- 235000019441 ethanol Nutrition 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- JQBMTMBJMXRRCJ-UHFFFAOYSA-N zinc;dihydrate Chemical compound O.O.[Zn] JQBMTMBJMXRRCJ-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000004140 cleaning Methods 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 7
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 50
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 238000010792 warming Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BXGTVNLGPMZLAZ-UHFFFAOYSA-N n'-ethylmethanediimine;hydrochloride Chemical compound Cl.CCN=C=N BXGTVNLGPMZLAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HRSADIZPZPRZEI-UHFFFAOYSA-L zinc;diacetate;hydrate Chemical compound O.[Zn+2].CC([O-])=O.CC([O-])=O HRSADIZPZPRZEI-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000005303 weighing 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F2101/36—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
- C02F2305/10—Photocatalysts
Abstract
The present invention provides a kind of preparation method of polyvinylidene fluoride modified composite membrane, include the following steps: a) to prepare graphene oxide using improved Hummer's chemical method；B) amination graphene oxide is prepared；C) amino functional graphene oxide/zinc oxide composite photocatalyst is prepared；D) polyvinylidene fluoride modified composite membrane is prepared.It present invention is mainly applied to the processing of dirty organic pollutants, can either effectively solve the problems, such as that catalyst recycles, and the organic matter of energy pollution degradation PVDF, realize composite membrane self-cleaning function, while catalytic degradation effect is good.
Description
Technical field
The invention belongs to technical field of material, more particularly, to a kind of preparation side of polyvinylidene fluoride modified composite membrane
Method.
Background technique
With the continuous development of printing and dyeing industry, problem brought by dyeing and printing sewage is more serious, especially methylene blue etc.
The use of colored dyes gradually increases, and to river, the ecosystems such as lake and ocean cause various adverse effects, to human health
Constitute grave danger.
Common dirt organic pollutants processing technique includes absorption, UF membrane, condensation etc., mainly removes and holds from water
Long property organic pollutant, however the removal of the pollutant is usually to assemble organic matter difficult to degrade or changed in water
At solid phase, needs to handle secondary pollution and using reproducing adsorbent, increase process costs.In addition to this, photocatalysis in recent years
Dirty organic pollutants of degrading also are widely studied.However, photocatalyst material degradation water pollutant there are catalyst not
Easily recycling, the deficiencies of catalytic degradation effect is bad.Therefore, develop it is a kind of convenient for catalyst recycling catalytic degradation material have weight
The application value wanted.
Summary of the invention
The present invention proposes a kind of preparation method of polyvinylidene fluoride modified composite membrane, to solve in sewage treatment catalyst not
Convenient for recycling, the technical problems such as catalytic degradation effect is bad.
A kind of preparation method of polyvinylidene fluoride modified composite membrane, includes the following steps:
A) graphene oxide is prepared using improved Hummer's chemical method；
B) progress of graphene oxide obtained by step a) is amination modified, obtain amination graphene oxide；
C) amination graphene oxide obtained by step b) being dissolved in dehydrated alcohol, acetic acid dihydrate zinc is added in ultrasonic disperse,
It is warming up to after acetic acid dihydrate zinc is completely dissolved, the ethanol solution of potassium hydroxide is added, then places it in reaction kettle and reacts
Afterwards, it cleans, drying obtains amino functional graphene oxide/zinc oxide composite photocatalyst；
D) polyvinylidene fluoride modified composite membrane is prepared, specifically:
D1) by amino functional graphene oxide/zinc oxide composite photocatalyst ultrasonic disperse obtained by step c) in poly- second
After the dimethyl formamide solution of glycol, PVDF is added, under constant temperature, stirring is completely dissolved rear standing and defoaming to PVDF, obtains
Casting solution；
D2) casting solution is added drop-wise on dry glass plate, knifing, gained film is immersed in pure water coagulating bath, to film
After molding, pure water cleaning obtains polyvinylidene fluoride modified composite membrane.
Further, in step c), concentration of the amination graphene oxide in dehydrated alcohol is 0.1-15mg/ml；Two
Acetate hydrate zinc concentration is 0.1-15mg/ml；The mass ratio of amination graphene oxide and acetic acid dihydrate zinc is 1:1-1:
100。
Further, in step c), reaction temperature is 80-150 DEG C in reaction kettle, reaction time 3-12h.
Further, in step c), the ethanol solution of potassium hydroxide is that the potassium hydroxide ultrasound of 0.5-3g is dissolved in 1-
The dehydrated alcohol of 10ml is made.
Further, step d1) in, amino functional graphene oxide/zinc oxide composite photocatalyst dosage accounts for diformazan
Base formamide solution 0.1-1wt%；Preferably, amino functional graphene oxide/zinc oxide composite photocatalyst dosage accounts for two
Methylformamide solution 0.5wt%.
Further, step d1) in, PVDF dosage accounts for dimethyl formamide solution 2-20wt%；Preferably, PVDF dosage
Account for dimethyl formamide solution 16-20wt%.
Further, step d1) in, amino functional graphene oxide/zinc oxide composite photocatalyst and PVDF mass
Than for 1:1-40.
Further, step d1) in, the temperature of constant temperature is 20-80 DEG C；The standing and defoaming time is 1-24h.
Further, step d1) in, Polyethylene glycol is 2-8wt% in the dimethyl formamide solution of polyethylene glycol.
Further, step d2) in, the temperature of pure water coagulating bath is 10-60 DEG C；Using with a thickness of 100-300 μ in knifing
The knifing stick of m.
A kind of preparation method of polyvinylidene fluoride modified composite membrane proposed by the present invention has the advantage that the preparation method
NGO-ZnO composite photo-catalyst is carried on PVDF carrier, a kind of composite membrane with high catalytic degradation performance is formed, it can
It is enough effectively to solve the problems, such as that catalyst recycles, and the organic matter of energy pollution degradation PVDF, it realizes the automatically cleaning of composite membrane, is catalyzed simultaneously
Degradation effect is good.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Below in conjunction with embodiment, the present invention will be described in detail.
A kind of preparation method of polyvinylidene fluoride modified composite membrane, includes the following steps:
A) graphene oxide (GO) is prepared using improved Hummer's chemical method；
B) amination graphene oxide (NGO) is prepared: the progress of graphene oxide obtained by step a) is amination modified, obtain ammonia
Base graphene oxide；
C) amino functional graphene oxide/zinc oxide (NGO-ZnO) composite photo-catalyst is prepared；By ammonia obtained by step b)
Base graphene oxide is dissolved in dehydrated alcohol, and ultrasonic disperse is added acetic acid dihydrate zinc, it is completely molten to be warming up to acetic acid dihydrate zinc
Xie Hou, is added the ethanol solution of potassium hydroxide, then places it in reaction kettle after reacting, and cleans, and it is multiple to obtain NGO-ZnO for drying
Light combination catalyst；
D) it prepares polyvinylidene fluoride modified composite membrane (PVDF/NGO-ZnO), specific as follows:
D1) by NGO-ZnO composite photo-catalyst ultrasonic disperse obtained by step c) polyethylene glycol (PEG) dimethyl formyl
After amine aqueous solution (DMF), PVDF is added, under constant temperature, stirring to PVDF is completely dissolved rear standing and defoaming, until bubble-free generates,
Obtain casting solution；
D2) casting solution is added drop-wise on dry glass plate, knifing, gained film is immersed in rapidly in pure water coagulating bath,
After film molding, pure water cleaning obtains PVDF/NGO-ZnO composite membrane.
Zinc oxide (ZnO) is as n-type semiconductor oxide for being asked during photocatalytic pollutant degradation there are following
Topic: (1) post-processing for needing catalyst to remove；(2) agglomerate easy to form in the solution reduces effective surface area；(3) it is difficult to
Realize the complete recycling of catalyst；(4) light induced electron and hole are compound in a short time.Nitrogen-doped graphene (NGO) is used as one
Kind excellent carrier and electron transport material, material surface area is big, has excellent electric conductivity and mechanical performance, and NGO is modified
ZnO can effectively inhibit the compound of light induced electron to improve photocatalysis performance relative to zinc oxide itself as photochemical catalyst,
But the problem of being not easily recycled there are still photochemical catalyst.
Kynoar (PVDF) is used as a kind of membrane material, since its chemical stability is good, high mechanical strength, ageing resistance
Can be excellent, it is widely used in organic pollutant processing, but in use process, PVDF is easy also to need PVDF again by organic pollution
Treatment process.
Therefore, the embodiment of the present invention proposes one kind using PVDF as carrier in conjunction with NGO-ZnO composite photo-catalyst
NGO-ZnO composite photo-catalyst is carried on PVDF carrier by the preparation method of PVDF/NGO-ZnO composite membrane, forms a kind of tool
There is the composite membrane of high catalytic degradation performance, can either effectively solve the problems, such as that catalyst recycles, and energy pollution degradation PVDF's is organic
Object realizes the self-cleaning function of composite membrane, while catalytic degradation effect is good.
Further, in step c), concentration of the amination graphene oxide in dehydrated alcohol is 0.1-15mg/ml；Two
Acetate hydrate zinc concentration is 0.1-15mg/ml；The mass ratio of amination graphene oxide and acetic acid dihydrate zinc is 1:1-1:
100。
Further, in step c), reaction temperature is 80-150 DEG C in reaction kettle, reaction time 3-12h.
Further, in step c), the ethanol solution of potassium hydroxide is that the potassium hydroxide ultrasound of 0.5-3g is dissolved in 1-
The dehydrated alcohol of 10ml is made.
In an embodiment of the present invention, step d1) in, amino functional graphene oxide/zinc oxide composite photocatalyst
Dosage accounts for dimethyl formamide solution 0.1-1wt%；Be specifically as follows 0.1wt%, 0.2wt%, 0.4wt%, 0.5wt%,
0.8wt%, 1wt%.Within this range, with the raising of NGO-ZnO composite photo-catalyst dosage, the catalytic degradation energy of composite membrane
Power gradually increases, but NGO-ZnO composite photo-catalyst dosage is excessive, will cause photochemical catalyst aggregation, reduces light utilization efficiency, influences
Catalytic degradation performance, while catalyst is not easily recycled.Preferably, the dosage of NGO-ZnO composite photo-catalyst accounts for dimethyl formyl
Amine aqueous solution 0.5wt%.The catalytic effect of the ratio composite membrane reaches best.
Further, step d1) in, it can be 2-20wt% that the dosage of PVDF, which accounts for dimethyl formamide solution,；Preferably,
The dosage of PVDF accounts for dimethyl formamide solution 16-20wt%, is specifically as follows 16wt%, 18wt%, 20wt%.PVDF dosage
Excessively, the reduction of composite membrane self-cleaning performance can be made.
Further, step d1) in, NGO-ZnO composite photo-catalyst and PVDF mass ratio are 1:1-40.Preferably,
NGO-ZnO composite photo-catalyst and PVDF mass ratio are 1:20-32.The proper ratio of NGO-ZnO composite photo-catalyst and PVDF,
Be conducive to composite photo-catalyst uniform load on PVDF, to improve catalytic performance.
Further, step d1) in, the temperature of constant temperature is 20-80 DEG C；Preferably, the temperature of constant temperature is 55-65 DEG C；More
Preferably, the temperature of constant temperature is 60 DEG C.This temperature range is conducive to PVDF and preferably dissolves, and urges to be conducive to NGO-ZnO light
Agent load.
Further, step d1) in, Polyethylene glycol can be 2-8wt%；Be specifically as follows 2wt%, 4wt%,
6wt%, 8wt% etc..
Further, step d1) in, the standing and defoaming time can be 1-24h.It is specifically as follows 10h, 12h, 15h etc., example
Such as, the standing and defoaming time is 12h.Standing and defoaming is until bubble-free in casting solution generates.
Further, step d2) in, the temperature of coagulating bath can be 10-60 DEG C.It is specifically as follows 20 DEG C, 25 DEG C, 30
DEG C, for example, the temperature of coagulating bath can be 25 DEG C.The temperature of coagulating bath has great influence, temperature to the molding effect of composite membrane
The low or excessively high composite membrane that is unfavorable for is spent to form.
Further, step d2) in, thickness employed in knifing can be 100-300 μm of knifing stick；It is specifically as follows
100 μm, 200 μm, 300 μm etc..
In a preferred embodiment, amino functional graphene oxide/zinc oxide composite photocatalyst dosage accounts for
Dimethyl formamide solution 0.5wt%, PVDF dosage accounts for dimethyl formamide solution 16-20wt%.
In an embodiment of the present invention, step a) prepares graphene oxide (GO) using improved Hummer's chemical method,
It is specifically as follows:
The pretreated powdered graphite of 5-20g and 1-10g sodium nitrate are added to the reaction containing the 100-500ml concentrated sulfuric acid
In device, after stirring 0.5-5h under ice-water bath, it is slowly added to 10-50g potassium permanganate and continues to stir 1-5h；Later by reaction system
It is warming up to 10-50 DEG C, after the reaction was continued 1-5h, 100-500ml deionized water is slowly added to, reaction system is warming up to 50-150
DEG C and stir 5-30min；Backward system in be slow added into 200-1000ml deionized water, 10- is added after stirring 1-10min
50ml 30wt% hydrogen peroxide terminates reaction, and solution colour is glassy yellow by black transitions, is continued after stirring 10-30min, will
After product carries out pickling, it is washed to pH ≈ 7, filters and obtains graphene oxide (GO) after being freeze-dried, for use.
In an embodiment of the present invention, step b) prepares amination graphene oxide (NGO), is specifically as follows:
It weighs GO obtained by 30-50mg step a) and is dispersed in containing N, it is cold in N methyl-formamide (DMF) beaker
But GO solution is to 0 DEG C, then 3-8mmol 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is added into the solution
(EDC) and 3-8mmol N- hydroxysuccinimide (NHS).By mixture after 0 DEG C of activation 0.5-5h, 6- is added into solution
15mmol diethylenetriamine, is stirred overnight at room temperature.Product is centrifugated, respectively three times with acetone and water washing, freeze-drying
After obtain amination graphene oxide (NGO), for use.
In an embodiment of the present invention, step c) prepares amino functional graphene oxide/zinc oxide composite photocatalyst
(NGO-ZnO), it is specifically as follows:
Potassium hydroxide (KOH) ultrasound for weighing 0.5-3g is dissolved in the dehydrated alcohol of 1-10ml, for use.By 1-100mg step
B) resulting amination graphene oxide (NGO) is dissolved in 10-100mL dehydrated alcohol, ultrasonic disperse, and to being added in the solution
10-500mg acetic acid dihydrate zinc is warming up to 50-100 DEG C in oil bath, after acetic acid dihydrate zinc is completely dissolved, rapidly joins 1-
The ethanol solution of 3mlKOH is simultaneously allowed to after reacting 3-10min, and aforesaid liquid is transferred in tetrafluoroethene liner reaction kettle and is heated up
To 80-150 DEG C and keep 3-12h.It is finally cleaned three times with deionized water, dehydrated alcohol is washed once, is dried at 25-80 DEG C.Phase
Close document (Dongdong Zhang, Yiping Zhao, et al. " Fabrication and characterization of
amino-grafted graphene oxide modified ZnO with high photocatalytic activity.”
Applied Surface Science 458 (2018): 638-647.) this is also had been reported that in.
It is next combined with specific embodiments below that the present invention will be described in detail.
Embodiment 1
A) graphene oxide is prepared with improved Hummer's chemical method
The pretreated graphite of 5g and 2.5g sodium nitrate are added in the reactor containing 120ml sulfuric acid, under ice-water bath
After stirring 1h, it is slowly added to 15g potassium permanganate and continues to stir 2h；Reaction system is warming up to 35 DEG C later, the reaction was continued 2h
Afterwards, it is slowly added to 120ml deionized water, reaction system is warming up to 90 DEG C and stirs 15min；Backward system in again slowly plus
Enter 250ml deionized water, the termination reaction of 12ml 30wt% hydrogen peroxide is added after stirring 2min, solution colour is by black transitions
For glassy yellow, continues after stirring 15min, after product is carried out pickling, be washed to pH ≈ 7, filter and obtain oxygen after being freeze-dried
Graphite alkene (GO), for use；
B) amination graphene oxide (NGO) is prepared
30mg GO obtained by step a) is dispersed in 50ml DMF, after 1 hour ultrasonication, cooling GO solution to 0
DEG C, then 5mmol 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC) and 5mmol are added into the solution
Then N- hydroxysuccinimide (NHS) is added 12mmol diethylenetriamine and was stirred at room temperature by mixture in 0 DEG C of stirring 2h
Night.Product is centrifugated, obtains amination graphene oxide (NGO) three times, after freeze-drying with acetone and water washing respectively,
For use；
C) amino functional graphene oxide/zinc oxide composite photocatalyst (NGO-ZnO) is prepared
It weighs the resulting NGO of 70mg step b) to be dissolved in 35mL dehydrated alcohol, ultrasonic disperse, and to being added in the solution
384mg acetic acid dihydrate zinc is warming up to 75 DEG C in oil bath, after acetic acid dihydrate zinc is completely dissolved, rapidly joins 1.5ml KOH
Ethanol solution and be allowed to after reacting 5min, aforesaid liquid is transferred in tetrafluoroethene liner reaction kettle and is warming up to 150 DEG C simultaneously
5h is kept, is finally cleaned three times with deionized water, dehydrated alcohol is washed once, is dried at 60 DEG C, and amino functional graphite oxide is obtained
Alkene/zinc oxide (NGO-ZnO) composite photo-catalyst, for use；
D) polyvinylidene fluoride modified composite membrane (PVDF/NGO-ZnO) is prepared
D1) the photochemical catalyst ultrasonic disperse for preparing the step c) of 0.3wt% is in the DMF solution that PEG concentration is 8wt%
In, the PVDF powder of 10wt% is added to the solution.By the mixed liquor, constant temperature is stirred to PVDF and is completely dissolved at 55 DEG C, and
Standing and defoaming 12h obtains casting solution at a temperature of this.
D2) casting solution is added dropwise on dry glass plate, and with the knifing stick striking plate membrane with a thickness of 300 μm.It will
Primary membrane is immersed in rapidly in 25 DEG C of pure water coagulating bath, is cleaned after film molding with a large amount of pure water, and be stored in pure water,
Obtain polyvinylidene fluoride modified composite membrane.
Embodiment 2
A)-c) with embodiment 1；
D) polyvinylidene fluoride modified composite membrane is prepared
D1) the NGO-ZnO photochemical catalyst ultrasonic disperse for preparing the step c) of 0.5wt% is 8wt%'s in PEG concentration
In DMF solution, the PVDF powder of 16wt% is added to the solution.By the mixed liquor at 60 DEG C constant temperature stir it is completely molten to PVDF
Solution, and standing and defoaming 12h obtains casting solution at this temperature.
D2) casting solution is added dropwise on dry glass plate, and with the knifing stick striking plate membrane with a thickness of 300 μm.It will
Primary membrane is immersed in rapidly in 25 DEG C of pure water coagulating bath, is cleaned after film molding with a large amount of pure water, and be stored in pure water,
Obtain polyvinylidene fluoride modified composite membrane.
Embodiment 3
A)-c) with embodiment 1；
D) polyvinylidene fluoride modified composite membrane is prepared:
D1) the NGO-ZnO photochemical catalyst ultrasonic disperse for preparing the step c) of 1wt% is in the DMF that PEG concentration is 8wt%
In solution, the PVDF powder of 20wt% is added to the solution.By the mixed liquor, constant temperature is stirred to PVDF and is completely dissolved at 65 DEG C,
And standing and defoaming 12h obtains casting solution at this temperature.
D2) casting solution is added dropwise on dry glass plate, and with the knifing stick striking plate membrane with a thickness of 300 μm.It will
Primary membrane is immersed in rapidly in 25 DEG C of pure water coagulating bath, is cleaned after film molding with a large amount of pure water, and be stored in pure water,
Obtain polyvinylidene fluoride modified composite membrane.
Comparative example 1
A)-d) with embodiment 2, the difference is that NGO-ZnO composite photo-catalyst additive amount is 0.
Experimental test is carried out to embodiment performance below.
By taking organic pollutant methylene blue as an example, the catalytic degradation performance of composite membrane of the present invention is tested.
(1) preparation of methylene blue (MB) solution
10mgMB dyestuff is accurately weighed in small beaker, adds water and stirs and makes it dissolve, after be transferred in 1000ml volumetric flask,
Continue to add water constant volume, obtains the MB solution that concentration is 10mg/L.
(2) photocatalysis is tested
By film obtained by embodiment 1-3 and comparative example, it is sequentially placed into the MB solution of 20ml 5mg/L, is protected from light processing, is put into
Room temperature shakes 12h in shaking table.It is taken out after it reaches adsorption equilibrium, is put into progress photocatalysis experiment under simulated solar irradiation.Every
20min takes a sample, and each film takes 6 samples altogether.Using ultraviolet-visible spectrophotometer survey MB concentration, set wavelength as
665nm measures absorbance, then calculates MB removal rate and average removal rate according to Formulas I.
Wherein, A in Formulas I0Refer to that MB solution does not carry out the measured absorbance value of photocatalysis test, AtRefer to that addition is different
Gained film is final that MB removal rate is shown in Table to gained absorbance value after the progress photocatalysis experiment of MB solution after the NGO-ZnO of concentration
1。
(3) self-cleaning ability is tested
The water flux of composite membrane after organic pollutant is measured before not carrying out organic pollutant processing and handled respectively,
Then its automatically cleaning rate is calculated by formula II.
Wherein, J in formula IIfRefer to the pure water flux of composite membrane before not carrying out organic pollutant processing, JwRefer to and has handled
The pure water flux of composite membrane after organic pollutant finally measures automatically cleaning rate and is shown in Table 1.
1 composite membrane of table is to MB removal rate and composite membrane automatically cleaning rate
Can be obtained by embodiment 1-3, PVDF/NGO-ZnO composite membrane can efficiently, energy saving methylene blue in sewage of degrading etc.
Dyestuff.And the organic pollutant for being adsorbed on composite membrane itself can be removed, realize automatically cleaning, be its degradation of organic dyes,
The application in the fields such as dyeing and printing sewage processing is laid a good foundation.It can be obtained by comparative example 1, photocatalyst on PVDF in can obviously mention
High catalytic degradation performance and itself clean rate.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of polyvinylidene fluoride modified composite membrane, includes the following steps:
A) graphene oxide is prepared using improved Hummer's chemical method；
B) progress of graphene oxide obtained by step a) is amination modified, obtain amination graphene oxide；
C) amination graphene oxide obtained by step b) is dissolved in dehydrated alcohol, acetic acid dihydrate zinc, heating is added in ultrasonic disperse
After being completely dissolved to acetic acid dihydrate zinc, the ethanol solution of potassium hydroxide is added, then places it in reaction kettle after reacting, clearly
It washes, dries, obtain amino functional graphene oxide/zinc oxide composite photocatalyst；
D) polyvinylidene fluoride modified composite membrane is prepared, specifically:
D1) by amino functional graphene oxide/zinc oxide composite photocatalyst ultrasonic disperse obtained by step c) in polyethylene glycol
Dimethyl formamide solution after, PVDF is added, under constant temperature, stirring is completely dissolved rear standing and defoaming to PVDF, obtains casting film
Liquid；
D2) casting solution is added drop-wise on dry glass plate, knifing, gained film is immersed in pure water coagulating bath, formed to film
Afterwards, pure water cleans, and obtains polyvinylidene fluoride modified composite membrane.
2. the preparation method of composite membrane according to claim 1, it is characterised in that: in step c), amination graphite oxide
Concentration of the alkene in dehydrated alcohol is 0.1-15mg/ml；Acetic acid dihydrate zinc concentration is 0.1-15mg/ml；Amination oxidation
The mass ratio of graphene and acetic acid dihydrate zinc is 1:1-1:100.
3. the preparation method of composite membrane according to claim 1, it is characterised in that: in step c), temperature is reacted in reaction kettle
Degree is 80-150 DEG C, reaction time 3-12h.
4. the preparation method of composite membrane according to claim 1, it is characterised in that: in step c), the ethyl alcohol of potassium hydroxide
Solution is that the dehydrated alcohol that the potassium hydroxide ultrasound of 0.5-3g is dissolved in 1-10ml is made.
5. the preparation method of composite membrane according to claim 1, it is characterised in that: step d1) in, amino functional oxidation
Graphene/zinc oxide composite photocatalyst dosage accounts for dimethyl formamide solution 0.1-1wt%；Preferably, amino functional oxygen
Graphite alkene/zinc oxide composite photocatalyst dosage accounts for dimethyl formamide solution 0.5wt%.
6. the preparation method of composite membrane according to claim 1, it is characterised in that: step d1) in, PVDF dosage accounts for diformazan
Base formamide solution 2-20wt%；Preferably, PVDF dosage accounts for dimethyl formamide solution 16-20wt%.
7. the preparation method of composite membrane according to claim 1, it is characterised in that: step d1) in, amino functional oxidation
Graphene/zinc oxide composite photocatalyst and PVDF mass ratio are 1:1-40；Preferably, amino functional graphene oxide/oxygen
Change zinc composite photo-catalyst and PVDF mass ratio is 1:20-32.
8. the preparation method of composite membrane according to claim 1, it is characterised in that: step d1) in, the temperature of constant temperature is
20-80℃；The standing and defoaming time is 1-24h.
9. the preparation method of composite membrane according to claim 1, it is characterised in that: step d1) in, the diformazan of polyethylene glycol
Polyethylene glycol is 2-8wt% in base formamide solution.
10. the preparation method of composite membrane according to claim 1, it is characterised in that: step d2) in, pure water coagulating bath
Temperature is 10-60 DEG C；Using the knifing stick with a thickness of 100-300 μm in knifing.
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