CN114405543A - Copper-aluminum bimetal composite polyvinylidene fluoride film and preparation method thereof - Google Patents
Copper-aluminum bimetal composite polyvinylidene fluoride film and preparation method thereof Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 89
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 89
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims 2
- 239000012528 membrane Substances 0.000 abstract description 38
- 239000000835 fiber Substances 0.000 abstract description 25
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001431 copper ion Inorganic materials 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 38
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000005337 ground glass Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 229920000831 ionic polymer Polymers 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- 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
- C02F1/722—Oxidation by peroxides
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- 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
- C02F2101/345—Phenols
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Abstract
The invention relates to a copper-aluminum bimetal composite polyvinylidene fluoride film and a preparation method thereof, and the preparation method comprises the following steps: dissolving crystalline aluminum chloride, copper nitrate trihydrate and urea in water, drying the dissolved liquid to obtain an intermediate, calcining the intermediate to obtain a copper-aluminum bimetallic catalyst, and grinding the prepared copper-aluminum bimetallic catalyst into powder; dissolving polyvinylidene fluoride powder and polyvinylpyrrolidone powder in a solvent, adding a powdery copper-aluminum bimetallic catalyst into a polyvinylidene fluoride solution, and dissolving under a magnetic force condition to obtain polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetallic spinning solution; putting polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetal spinning solution into an electrostatic spinning device to obtain the copper-aluminum bimetal composite polyvinylidene fluoride membrane. The high specific surface area of the PVDF fiber membrane is utilized to increase the contact area between the catalyst and reactants, thereby increasing the catalytic efficiency, reducing the loss of copper ions and improving the recycling capability of the catalyst.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a copper-aluminum bimetal composite polyvinylidene fluoride membrane and a preparation method thereof.
Background
The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The Fenton reaction is a water treatment technology using a catalyst, and the traditional Fenton reaction utilizes iron ions in the catalyst and hydrogen peroxide to oxidize a plurality of known organic compounds such as carboxylic acid, alcohol and ester into inorganic states, so that the Fenton reaction has the capability of removing refractory organic pollutants. The pH required in the traditional Fenton reaction process is harsh, and a large amount of iron-containing sludge is generated after the reaction is finished. In the Fenton-like oxidation technology, copper is adopted to replace iron because the performance of copper in a Fenton system is superior to that of iron, and on one hand, copper has a wider pH activity range than that of iron; on the other hand, the reaction rate of monovalent copper ions and hydrogen peroxide is higher than that of divalent iron ions, and divalent copper is easier to be reduced by hydrogen peroxide.
At present, a copper-based catalyst is used in a Fenton-like oxidation technology, and when hydrogen peroxide reacts with the copper-based catalyst, extra decomposition of the hydrogen peroxide often occurs to generate oxygen and water, so that the utilization rate of the hydrogen peroxide is low, and a large amount of hydrogen peroxide loss is caused in the actual water treatment process. In addition, the leaching problem of copper ions is solved, and for homogeneous reaction, the copper ions are directly in an aqueous solution and cannot be separated, so that the copper ions cannot be recycled, and secondary pollution is caused; in the case of heterogeneous reaction, although copper ions are on the carrier, the copper ions are released from the carrier due to long-term use, and the loss of the copper ions is also caused.
Therefore, in the current fenton-like oxidation reaction, the utilization rate of hydrogen peroxide is not high, and copper ions are difficult to recover after the copper-based catalyst is used.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a copper-aluminum bimetal composite polyvinylidene fluoride membrane and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a copper-aluminum bimetal composite polyvinylidene fluoride film, which comprises the following steps:
dissolving crystalline aluminum chloride, copper nitrate trihydrate and urea in water, dissolving under a magnetic force condition, drying the dissolved liquid under an air condition to obtain an intermediate, calcining the intermediate under an air condition to obtain a copper-aluminum bimetallic catalyst, and grinding the prepared copper-aluminum bimetallic catalyst into powder;
dissolving polyvinylidene fluoride powder and polyvinylpyrrolidone powder in a solvent to obtain a polyvinylidene fluoride solution with a concentration range (10-40%), adding a powdery copper-aluminum bimetallic catalyst into the polyvinylidene fluoride solution, and dissolving under a magnetic force condition to obtain polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetallic spinning solution; wherein, the concentration range of the polyvinylidene fluoride is (10-40)%, the concentration range of the polyvinylpyrrolidone is (1-6%), the content of copper ions is 0.025mmol/g, and the content of aluminum ions is 0.18 mmol/L);
putting polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetal spinning solution into an electrostatic spinning device, setting the spinning voltage to be 12-13kV, and the injection speed of the spinning solution to be 0.5-3mL/h, starting electrostatic spinning, after the spinning is finished, taking off the tin foil, attaching a copper-aluminum bimetal composite polyvinylidene fluoride film on the tin foil, and storing under a dry condition.
The total drying time of the copper-aluminum bimetallic catalyst intermediate is not less than 12 h.
The calcining temperature of the copper-aluminum bimetallic catalyst is 550 ℃, and the total calcining time is 4 hours.
The solvent is one or more of N, N-dimethylformamide, acetone, dimethyl sulfoxide, N-dimethyl amide and dichloromethane.
The electrostatic spinning device comprises an injector, a receiver and an electrostatic generator, wherein the positive pole of the electrostatic generator is connected to the needle head of the injector, the negative pole of the electrostatic generator is connected to the receiver, and tinfoil for receiving the copper-aluminum bimetal composite polyvinylidene fluoride film is paved on the receiver.
The distance between the receiver and the syringe needle is 10-15 cm.
The syringe was a 5mL syringe.
The electrostatic spinning is carried out at room temperature, wherein the room temperature is 20 ℃ and the humidity is 45%.
A second aspect of the present invention provides a copper-aluminum bimetal composite polyvinylidene fluoride film, which is prepared based on the above method.
Compared with the prior art, the above one or more technical schemes have the following beneficial effects:
1. mixing the prepared copper-aluminum bimetallic catalyst powder and polyvinylidene fluoride powder, dissolving in a solvent, and wrapping the copper-aluminum bimetallic catalyst on polyvinylidene fluoride fibers in an electrostatic spinning mode to form a fiber membrane, thereby obtaining the copper-aluminum bimetallic composite polyvinylidene fluoride membrane.
2. The high specific surface area of the polyvinylidene fluoride fiber membrane is utilized to increase the contact area of the catalyst and the reactant, thereby increasing the catalytic efficiency.
3. By utilizing the corrosion resistance and the mechanical strength of the polyvinylidene fluoride fiber, the copper-aluminum bimetal attached to the fiber membrane is not easy to be decomposed or torn by the membrane body to reduce the service life.
4. The copper-aluminum bimetallic catalyst is wrapped on the polyvinylidene fluoride fiber membrane, so that the polyvinylidene fluoride forms a carrier fiber membrane of the copper-aluminum bimetallic catalyst, the adsorbability of the polyvinylidene fluoride fiber membrane can reduce the loss of copper ions, and the recycling capability of the copper-aluminum bimetallic catalyst is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic diagram of a process for preparing a copper-aluminum bimetal composite polyvinylidene fluoride film according to one or more embodiments of the present invention;
FIG. 2 is a schematic diagram illustrating the effect of a copper-aluminum bimetal composite polyvinylidene fluoride film on catalyzing hydrogen peroxide to degrade bisphenol A under different pH conditions according to one or more embodiments of the present invention;
FIG. 3 is a schematic illustration of a copper-aluminum bimetal provided by one or more embodiments of the present invention;
FIG. 4 is a schematic of the microstructure of a PVDF fiber wrapped copper-aluminum bimetallic catalyst at 50 μm according to one or more embodiments of the invention;
FIG. 5 is a schematic of the microstructure of a PVDF fiber wrapped copper-aluminum bimetallic catalyst at 20 μm according to one or more embodiments of the invention;
fig. 6 is a schematic microstructure diagram of a copper-aluminum bimetallic catalyst coated with PVDF fibers at 10 μm according to one or more embodiments of the invention.
Detailed Description
The invention is further described with reference to the following figures and examples.
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Polyvinylidene fluoride (PVDF) is an organic polymer material, namely fluororesin, and is white particles or powdery solid with excellent performance. The PVDF has the main characteristics that: firstly, the heat-resistant coating has excellent thermal stability and good heat resistance; secondly, the mechanical strength is very high, and the shock resistance is high; thirdly, the paint has good chemical stability and is not easy to corrode; fourthly, the film has good film forming property, is easy to be made into various films, and has wide application in the aspect of film preparation.
Polyvinylpyrrolidone (PVP), a non-ionic polymer, is a common polymer.
As described in the background art, the reaction conditions of the conventional fenton are severe, and the iron sludge is treated, which is high in cost in the treatment process. The problem that the traditional Fenton reaction conditions are harsh is solved to a certain extent by adopting a copper-based catalyst in the existing novel Fenton technology, but the problems that the reaction rate of hydrogen peroxide is not high and a copper material is difficult to recover still exist.
Therefore, the following example provides a preparation method of a copper-aluminum bimetal composite polyvinylidene fluoride membrane, which comprises the steps of mixing and dissolving the prepared copper-aluminum bimetal catalyst powder and PVDF/PVP powder in a solvent, wrapping the copper-aluminum bimetal catalyst on a PVDF fiber membrane in an electrostatic spinning mode, and improving the contact area of the catalyst and a reactant by utilizing the high specific surface area of the PVDF fiber membrane so as to improve the catalytic efficiency. The copper-aluminum bimetallic catalyst is wrapped on the PVDF fiber membrane, so that the loss of copper ions can be reduced, and the recycling capability of the catalyst is improved. The adsorption capacity of the PVDF membrane is fully exerted, and the recycling is simple.
The first embodiment is as follows:
as shown in fig. 1, a preparation method of a copper-aluminum bimetal composite polyvinylidene fluoride film comprises the following steps:
dissolving crystalline aluminum chloride, copper nitrate trihydrate and urea in water, dissolving under a magnetic force condition, drying the dissolved liquid under an air condition to obtain an intermediate, calcining the intermediate under an air condition to obtain a copper-aluminum bimetallic catalyst, and grinding the prepared copper-aluminum bimetallic catalyst into powder;
dissolving polyvinylidene fluoride powder and polyvinylpyrrolidone powder in a solvent, adding a powdery copper-aluminum bimetallic catalyst into a polyvinylidene fluoride solution, and dissolving under a magnetic force condition to obtain polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetallic spinning solution;
putting polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetal spinning solution into an electrostatic spinning device, starting electrostatic spinning, taking off tin foil after the spinning is finished, attaching a copper-aluminum bimetal composite polyvinylidene fluoride film on the tin foil, and storing under a dry condition.
The method comprises the following specific steps:
(1) preparation of copper-aluminum bimetal composite PVDF film
Preparing a copper-aluminum bimetallic catalyst: a hydrothermal method is adopted to prepare the copper-aluminum bimetallic catalyst, 4.82g of crystalline aluminum chloride, 0.60g of copper nitrate trihydrate and 4g of urea are accurately weighed, dissolved in 60mL of deionized water, and placed on a magnetic stirrer to be stirred for 60min at normal temperature. And putting the stirred liquid into a crucible, covering the crucible, putting the crucible into a vacuum drying box, and drying the crucible for 12 hours at the temperature of 180 ℃ in the air to obtain an intermediate. And (3) opening a cover of the material in the air, placing the material for 5min, immediately covering the cover, placing the material in a muffle furnace, and calcining the material for 4h at 550 ℃ in the air to obtain the green copper-aluminum bimetallic catalyst. And then put into an agate mortar, and the material is ground into powder.
Preparing PVDF/PVP and Cu-Al bimetallic spinning solution: accurately weighing 2.0g of PVDF solid and 0.4g of PVP powder, placing the PVDF solid and the PVP powder in a ground glass bottle, moving 7mL of N, N-Dimethylformamide (DMF) and 3mL of acetone in the ground glass bottle, covering the ground glass bottle, placing the ground glass bottle on a magnetic stirrer, and stirring the ground glass bottle at normal temperature for 120min until the PVDF solid and the PVP powder are completely dissolved. And (3) accurately weighing 0.2g of copper-aluminum bimetallic catalyst, adding the copper-aluminum bimetallic catalyst into the dissolved liquid, and stirring for 120min to obtain the PVDF/PVP and Cu-Al bimetallic spinning solution.
In the embodiment, PVP is used as a pore-forming agent for forming a microporous structure in the prepared PVDF fiber membrane, if the content of PVP is low, the prepared membrane is compact, and if the pore diameter is too small, the water permeability is low, so that the final using effect is influenced; and if the content of PVP is high, the aperture ratio of the membrane is large, and the mechanical strength of the prepared membrane is not enough, so that the membrane material is easy to damage in the running process.
Preparing a copper-aluminum bimetal composite PVDF film: the desired spinning solution was drawn up using a 5mL gauge syringe and placed in an electrospinning apparatus. And (3) spreading tinfoil on the receiver, connecting the receiver with a negative electrode of a power supply, connecting the needle of the syringe with a positive electrode, and keeping the distance between the receiver and the needle of the syringe to be about 12 cm. After the needle head is aligned to the center of the receiver, setting the voltage to be 12-13kV and the injection speed to be 3mL/h, opening a switch of the electrostatic spinning device, and starting to manufacture the electrostatic spinning film. After preparation, the film was removed from the receiver along with the tinfoil and allowed to air dry. Taking off the tinfoil after air drying to obtain PVDF/PVPCu-Al2O3And (3) a membrane.
In this example, PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer) and PVP were used together as a film forming material.
(2) Effect of copper-aluminum bimetal composite PVDF film catalyzing hydrogen peroxide to degrade bisphenol A (BPA)
Influence of pH on the degradation Effect: as shown in fig. 2, the influence of the catalytic performance of the copper-aluminum bimetal composite PVDF film and the removal rate of bisphenol a under different pH conditions. As a result of analysis of the experimental data, the removal rate of bisphenol a was 81.37% at pH 3, 81.37% at pH 5, 86.01% at pH 7, 81.37% at pH 9 and 72.08% at pH 11 at 180 min. As can be seen from fig. 1, the removal rate was more than 80% at pH 3 to 9, and the removal rate was significantly reduced at pH 11. The removal rate in a medium-strong alkali environment is poor, and the generated free radicals are reduced because copper ions are inactive in an alkali environment.
The influence of the adding amount of hydrogen peroxide on the degradation effect is as follows: as shown in FIG. 3, the effect of different concentrations of hydrogen peroxide on bisphenol A removal rate. Analysis of experimental data revealed that at 180min, the initial concentration of hydrogen peroxide was 5mmol/L, the removal rate of bisphenol A was 81.37%, the removal rate of 7.5mmol/L was 92.21%, the removal rate of 10mmol/L was 91.44%, the removal rate of 12.5mmol/L was 86.01%, and the removal rate of 15mmol/L was 91.43%. When the initial concentration of the hydrogen peroxide is 15, 12.5 and 7.5mmol/L, the removal rate of the bisphenol A is more than 80 percent. Generally, the higher the concentration of the hydrogen peroxide is, the higher the degradation rate is, but the excessive hydrogen peroxide can react with hydroxyl radicals, so that when the hydrogen peroxide is added to reach a certain amount, the removal rate of the bisphenol A is not obviously improved. Therefore, in the practical application process, a certain concentration of hydrogen peroxide needs to be maintained, so that pollutants in the sewage can be effectively removed, and the economic cost is effectively controlled.
Stability of copper-aluminum bimetal composite PVDF film: the effect on the degradation efficiency of bisphenol A after repeated use. The removal rate of bisphenol A in the 1 st cycle is 89.11%, and the removal rate is higher than 80%; the removal rate of bisphenol A was 75.6% at the 5 th pass, and 70% at the 10 th pass. The concentration of leached copper ions after the 1 st cycle is as follows: 0.59mg/L, 0.14mg/L for the 4 th time, and 0.23mg/L for the 10 th time. Along with the increase of the circulation times, the concentration of the leached copper ions is continuously reduced, and after the circulation time reaches the 4 th time, the concentration of the copper ions tends to be stable and is stabilized to about 0.2 mg/L. Indicating that the leaching of copper ions can be stabilized after a plurality of cycles.
And (3) an ultrafiltration circulation process: performing circulation experiment with ultrafilter, placing the prepared membrane in ultrafilter, water inlet pressure of 0.4MPa, and filtering area of 150cm2And the running time is 180 min. After a month of cycle experiment, the removal rate of bisphenol A is about 80%, which shows that the copper-aluminum bimetal composite PVDF membrane has high catalytic effect and cycle stability in the ultrafiltration cycle process. On one hand, because of high water inlet pressure in the ultrafiltration machine, the catalyst in the membrane is more fully contacted with the bisphenol A; on the other hand, the membrane is fixed in the ultrafilter without falling off and the like.
After a one-month continuous ultrafiltration cycle experiment, the surface structure of the copper-aluminum bimetal composite PVDF membrane is complete and has no phenomena of falling off, cracking and the like by observation. The membrane has high structural strength and can resist the water inlet pressure (0.4MPa) of the ultrafilter, and the copper-aluminum bimetal composite PVDF membrane can be used in actual engineering and has very high engineering application potential.
The preparation method comprises the steps of mixing and dissolving the prepared copper-aluminum bimetallic catalyst powder and PVDF/PVP powder in a solvent, and wrapping the copper-aluminum bimetallic catalyst on PVDF fibers in an electrostatic spinning mode to form a fiber membrane, so that the copper-aluminum bimetallic composite polyvinylidene fluoride membrane is obtained.
The particles in fig. 4-6 are copper aluminum bimetallic catalysts coated with PVDF fibers.
The high specific surface area of the PVDF fiber membrane is utilized to increase the contact area of the catalyst and the reactant, thereby increasing the catalytic efficiency.
By utilizing the corrosion resistance and the mechanical strength of the PVDF fiber, the copper-aluminum bimetal attached to the fiber membrane is not easy to be decomposed or torn by the membrane body to reduce the service life.
The copper-aluminum bimetallic catalyst is wrapped on the PVDF fiber membrane, so that the PVDF forms a carrier fiber membrane of the copper-aluminum bimetallic catalyst, the adsorption property of the fiber membrane can reduce the loss of copper ions, and the recycling capability of the catalyst is improved.
Example two:
the embodiment provides a copper-aluminum bimetal composite polyvinylidene fluoride film which is prepared based on the method in the first embodiment.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a copper-aluminum bimetal composite polyvinylidene fluoride film is characterized by comprising the following steps: the method comprises the following steps:
dissolving crystalline aluminum chloride, copper nitrate trihydrate and urea, drying after dissolving to obtain an intermediate, calcining the intermediate to obtain a copper-aluminum bimetallic catalyst, and grinding the copper-aluminum bimetallic catalyst into powder;
dissolving polyvinylidene fluoride powder and polyvinylpyrrolidone powder in a solvent, adding a powdery copper-aluminum bimetallic catalyst into a polyvinylidene fluoride solution, and dissolving to obtain polyvinylidene fluoride/polyvinylpyrrolidone and copper-aluminum bimetallic spinning solution;
and placing the polyvinylidene fluoride/polyvinylpyrrolidone and the copper-aluminum bimetal spinning solution in an electrostatic spinning device for electrostatic spinning, attaching a copper-aluminum bimetal composite polyvinylidene fluoride film on the tin foil after the spinning is finished, and storing under a dry condition.
2. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 1, which is characterized in that: the total drying time of the copper-aluminum bimetallic catalyst intermediate is not less than 12 h.
3. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 1, which is characterized in that: the solvent is one or more of N, N-dimethylformamide, acetone, dimethyl sulfoxide, N-dimethyl amide and dichloromethane.
4. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 1, which is characterized in that: the electrostatic spinning device comprises an injector, a receiver and an electrostatic generator.
5. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 4, characterized in that: the positive pole of the static generator is connected to the needle of the syringe.
6. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 5, characterized in that: the negative pole of the static generator is connected to the receiver, and tinfoil for receiving the copper-aluminum bimetal composite polyvinylidene fluoride film is paved on the receiver.
7. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 6, characterized in that: the distance between the receiver and the syringe needle is 10-15 cm.
8. The preparation method of the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 1, which is characterized in that: the electrospinning is carried out at room temperature.
9. The method for preparing the copper-aluminum bimetal composite polyvinylidene fluoride film as claimed in claim 8, wherein the method comprises the following steps: the room temperature condition is 20 ℃ of temperature and 45% of humidity.
10. A copper-aluminum bimetal composite polyvinylidene fluoride film is characterized in that: prepared by the process of any one of claims 1 to 9.
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