CN111672335A - Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane - Google Patents
Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane Download PDFInfo
- Publication number
- CN111672335A CN111672335A CN202010496296.6A CN202010496296A CN111672335A CN 111672335 A CN111672335 A CN 111672335A CN 202010496296 A CN202010496296 A CN 202010496296A CN 111672335 A CN111672335 A CN 111672335A
- Authority
- CN
- China
- Prior art keywords
- cuo
- cus
- pvdf
- solution
- composite membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 65
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 17
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000000593 degrading effect Effects 0.000 claims abstract description 9
- 241001460678 Napo <wasp> Species 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 4
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000002638 heterogeneous catalyst Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 239000010865 sewage Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 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 4
- 230000008569 process Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960000740 enrofloxacin Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229960002422 lomefloxacin Drugs 0.000 description 2
- ZEKZLJVOYLTDKK-UHFFFAOYSA-N lomefloxacin Chemical compound FC1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNC(C)C1 ZEKZLJVOYLTDKK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241000692870 Inachis io Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/02—Inorganic material
-
- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/344—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 electromagnetic wave energy
- B01J37/346—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 electromagnetic wave energy of microwave energy
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method and application of a CuO @ CuS/PVDF water treatment composite membrane, wherein the preparation method comprises the following steps: (1) by chemical co-reactionPrecipitation of Na2CO3Mixing the solution with CuSO4Calcining the precipitate generated by the solution reaction to obtain nano CuO powder; (2) adding CuO powder into CuSO4After the solution is evenly stirred, Na is added into the mixed solution2S2O3Stirring the solution to obtain fluorescent green precipitate, and transferring the fluorescent green precipitate into a microwave reactor to prepare CuO @ CuS nano composite powder by a microwave method; (3) adding PVDF particles into DMAC solvent, reacting in 80 ℃ constant temperature water bath to form homogeneous solution, and adding (NaPO) at room temperature3)6PVP and CuO @ CuS nano composite powder are uniformly stirred, kept stand for defoaming, poured onto a plane glass plate, uniformly scraped into a film, and finally soaked in an ethanol solution for demoulding to obtain the CuO @ CuS/PVDF composite film. The CuO @ CuS/PVDF composite membrane prepared by the invention can be used for degrading organic pollutants in water, and has the advantages of strong stability, good oxidation resistance, low cost, simple and convenient operation, environmental protection and no secondary pollution.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a preparation method and application of a CuO @ CuS/PVDF water treatment composite membrane.
Background
Water resources are necessary guarantee for sustainable development, but with the acceleration of urban development and the increase of population, industrial production wastewater, domestic sewage and agricultural breeding sewage are discharged in large quantities, the water environment is rapidly deteriorated, and the utilization of the water resources is influenced. Pollutants in water are mainly divided into organic pollutants, inorganic pollutants and microorganisms, wherein the organic pollutants are difficult to degrade, the pollutants are various in types, and the toxicity of the pollutants has bad influence on the biological environment, so that various environmental problems can be caused, such as blockage of a sewage treatment plant, adverse influence on aquatic organism communities, increase of biochemical oxygen demand, damage to aquatic ecosystems and aquatic organisms, and serious harm to human health.
In recent years, as a novel oxidation process, an advanced oxidation process (SR-AOPs) based on sulfate radicals (SO4 · -) has the advantages of high catalytic efficiency, good stability, low cost and the like compared with other AOPs such as electrochemical oxidation and the like, and thus has gained more and more attention and is often used for effectively degrading organic pollutants in water and soil. With the intensive research on SR-AOPs, there are various methods for activating Persulfate (PS), and transition metal activation is classified into heterogeneous catalysts and homogeneous catalysts. In addition, the water treatment membrane technology is one of the most advanced sewage treatment technologies, can solve the conversion of sewage and reclaimed water, simultaneously solves the problems of water pollution and water resource shortage, and has strategic significance for the utilization and protection of water resources in China. Compared with the traditional water treatment mode, the membrane method water treatment has the advantages of low energy consumption, simple process, wide water quality application range, great improvement of effluent water quality and the like, and is currently used in various fields of sewage treatment (including municipal sewage treatment and industrial sewage treatment), feed water purification (including municipal feed water purification and industrial feed water purification), seawater desalination (brackish water desalination) and pure water preparation and the like. The water treatment membrane can be divided into an inorganic membrane and an organic membrane according to different manufacturing materials. The organic membrane technology has the advantages of strong stability, good oxidation resistance, low cost, simple and convenient operation, environmental protection, no secondary pollution and the like, and is widely applied to the fields of water resource, industrial special separation and the like.
At present, the degradation difficulty of organic pollutants in water is high, the problems of poor stability, easy agglomeration, difficult recovery and the like still exist if only a heterogeneous catalyst is selected for degradation, and based on the outstanding advantages of the heterogeneous catalyst and the water treatment membrane technology, the heterogeneous catalyst can be an effective means for degrading the organic pollutants in the water if the heterogeneous catalyst and the water treatment membrane technology can be combined.
Disclosure of Invention
Aiming at the defects pointed out in the background technology, the invention provides a preparation method and application of a CuO @ CuS/PVDF water treatment composite membrane, aiming at solving the problems in the prior art in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a CuO @ CuS/PVDF water treatment composite membrane comprises the following steps:
(1) preparation of nano CuO powder
Chemical coprecipitation method is adopted to mix Na2CO3Mixing the solution with CuSO4Solution reaction to generate basic copper carbonateStanding for 3 hours at room temperature, centrifugally washing by deionized water and absolute ethyl alcohol, placing the washed precipitate in an oven at 80 ℃ for drying for 12 hours, then placing the dried precipitate in a muffle furnace, and calcining for 2 hours at 400 ℃ to obtain nano CuO powder;
(2) preparation of CuO @ CuS nano composite powder
Preparing CuO @ CuS nano composite powder by adopting a microwave method, namely firstly, preparing CuSO4·5H2O and Na2S2O3Respectively dissolved in deionized water to form CuSO4Solution and Na2S2O3Solution, then adding the nano CuO powder to the CuSO4Adding Na into the solution, stirring until the mixture is uniformly mixed, and adding the Na into the mixed solution2S2O3Stirring the solution for 10 minutes to obtain fluorescent green precipitate, transferring the fluorescent green precipitate into a microwave reactor to react for 20 minutes to obtain a blue-black precipitate product, washing the blue-black precipitate product with absolute ethyl alcohol and deionized water, and drying the washed blue-black precipitate product in a drying oven at 60 ℃ for 12 hours to finally obtain CuO @ CuS nano composite powder;
(3) preparation of CuO @ CuS/PVDF composite membrane
Adding quantitative dry polyvinylidene fluoride (PVDF) particles into a Dimethylacetamide (DMAC) solvent, placing the mixture in a constant-temperature water bath stirrer at the temperature of 80 ℃ for stirring until a homogeneous solution is formed, and then adding quantitative (NaPO) into the mixture at the dry room temperature3)6PVP and the CuO @ CuS nano composite powder are slowly stirred to be uniformly mixed, kept stand for 48 hours for defoaming, poured on a plane glass plate, uniformly scraped into a film with the thickness of 200 mu m, and finally soaked in Et-OH2And (3) stripping in an ethanol solution with the ratio of O to 1:2 to obtain the CuO @ CuS/PVDF composite membrane.
Preferably, the molar ratio of CuO to CuS in the CuO @ CuS nanocomposite powder is 2: 1.
Preferably, in step (3), the DMAC, PVDF, (NaPO) is3)6PVP, and CuO @ CuS nanocomposite powder were 73.5 wt.%, 20 wt.%, 1.5 wt.%, 4 wt.%, and 1 wt.%, respectively.
The invention further provides a CuO @ CuS/PVDF composite water treatment membrane.
The invention also provides an application of the CuO @ CuS/PVDF composite membrane for water treatment in degradation of organic pollutants in water.
Preferably, the CuO @ CuS/PVDF composite water treatment membrane is applied to degradation treatment of medical wastewater.
Preferably, 0.4g/L of persulfate is added when the CuO @ CuS/PVDF composite membrane for water treatment is used for degrading organic pollutants in water, and the initial pH value of degradation is 3-9.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) according to the invention, the CuO @ CuS nano composite material is prepared to create the heterogeneous catalyst, so that the product has good reaction selectivity and wide pH tolerance, and the pH range is about 3-9.
(2) The transition metal element in the heterogeneous catalyst is selected from copper element, and the copper element resource is relatively rich according to the research of element abundance. In addition, CuO and CuS nano particles are used as effective catalysts of a PS activation system, and have the advantages of high efficiency, no toxicity and low cost.
(3) The CuO @ CuS/PVDF organic composite membrane prepared by combining the heterogeneous catalyst and the PVDF organic membrane has the advantages of strong stability, good oxidation resistance, low cost, simplicity and convenience in operation, environmental friendliness, no secondary pollution and the like.
Drawings
FIG. 1 is a flow chart of the preparation of a CuO @ CuS/PVDF water treatment composite membrane provided by the embodiment of the invention.
FIG. 2 is a comparative water flux plot of a CuO @ CuS/PVDF water treatment composite membrane provided by an embodiment of the invention.
Fig. 3 is a diagram illustrating the optimization result of the composition ratio of CuO to CuS provided in the embodiment of the present invention.
FIG. 4 is a graph showing the result of degradation of rhodamine B by activating PS with the CuO @ CuS/PVDF water treatment composite membrane provided by the embodiment of the invention.
FIG. 5 is a graph showing the results of degradation of various antibiotics by PS activated by the CuO @ CuS/PVDF composite membrane for water treatment according to the embodiment of the present invention.
FIG. 6 is a graph showing the results of pH tolerance of an activated PS system of the CuO @ CuS/PVDF composite membrane for water treatment according to the embodiment of the present invention.
FIG. 7 is a result graph of repeatability of the activated PS system of the CuO @ CuS/PVDF composite membrane for water treatment according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the CuO @ CuS/PVDF water treatment composite membrane has the preparation flow with reference to figure 1, and comprises the following specific steps:
(1) preparation of nano CuO powder
25mL of 3mol/L Na is added by a chemical coprecipitation method2CO3The solution was mixed with 40mL of 3mol/L CuSO4The solution reacts to generate basic copper carbonate (peacock blue precipitate) to obtain a precursor of the nano CuO. And then standing at room temperature for 3 hours, centrifugally washing by using deionized water and absolute ethyl alcohol, placing the washed precipitate in an oven at 80 ℃ for drying for 12 hours, then placing the dried precipitate in a muffle furnace, and calcining at 400 ℃ for 2 hours to obtain nano CuO powder.
(2) Preparation of CuO @ CuS nano composite powder
Preparing CuO @ CuS nano composite powder by adopting a microwave method, firstly, 0.1mol of CuSO4·5H2O and 0.1mol Na2S2O3Respectively dissolved in 50mL of deionized water to form CuSO4Solution and Na2S2O3Solution, adding the prepared CuO powder into CuSO4Adding Na into the solution, stirring until the mixture is uniformly mixed, and adding Na into the mixed solution2S2O3Stirring the solution for 10 minutes to obtain a fluorescent green precipitate, transferring the fluorescent green precipitate into a microwave reactor, and reacting for 20 minutes under the following reaction conditions: 2450MHz and 650W, reacting for 9s per microwave, stopping standing for 21s to obtain a bluish black precipitate, washing with absolute ethyl alcohol and deionized water, and drying in a 60 ℃ oven for 12 hours to finally obtain CuO @ CuS nano composite powder.
(3) Preparation of CuO @ CuS/PVDF composite membrane
Adding 20 wt.% of dry polyvinylidene fluoride (PVDF) particles to 73.5 wt.% of Dimethylacetamide (DMAC) solvent, stirring in a 80 ℃ constant temperature water bath stirrer until a homogeneous solution is formed, and then adding 1.5 wt.% of (NaPO) at dry room temperature3)64 wt.% of PVP and 1 wt.% of CuO @ CuS nano composite powder prepared by the method are slowly stirred to be uniformly mixed, kept stand for 48 hours for defoaming, poured on a plane glass plate, uniformly scraped into a film with a thickness of 200 mu m, and finally soaked in Et-OH H2And (3) stripping in an ethanol solution with the ratio of O to 1:2 to obtain the CuO @ CuS/PVDF composite membrane.
The CuO @ CuS/PVDF composite membrane prepared by the invention is respectively subjected to membrane flux tests with a pure PVDF membrane, a CuO/PVDF membrane and a CuS/PVDF membrane, and the results are shown in figure 2, so that the CuO @ CuS/PVDF composite membrane has obviously reduced membrane flux and is obviously higher than the CuO/PVDF membrane and the CuS/PVDF membrane compared with the pure PVDF membrane, and the membrane properties can effectively prolong the retention time of an organic pollutant solution on the composite membrane, thereby achieving the effect of fully catalyzing and degrading the organic pollutants.
Example 2
When the CuO @ CuS/PVDF water treatment composite membrane degrades organic pollutants in water, firstly, the CuO @ CuS/PVDF water treatment composite membrane is added into water to be processed containing the organic pollutants, 0.4g/L of Persulfate (PS) is added, and the initial pH value of degradation is controlled to be 3-9. And then the pollutants are fully contacted under the action of physical external force (namely water pressure, stirring and the like), so that the catalytic degradation of the pollutants is finally realized.
(1) Based on the catalytic degradation efficiency, the composite ratio of CuO and CuS in the CuO @ CuS nano composite powder is optimized, the molar ratio of CuO to CuS is respectively set to be 1:100, 1:50, 1:1, 2:1 and 3:1, the CuO @ CuS nano composite powder is prepared, then an organic matter degradation reaction is carried out, a certain amount of sample is taken out from a pollutant solution within a certain time interval in the degradation process, an ultraviolet spectrophotometer is adopted to detect the absorbance of filtrate under a specific wavelength, the pollutant degradation efficiency is determined through the measurement of the absorbance, the result is shown in figure 3, and finally, the optimal composite ratio of CuO to CuS is optimized and determined to be 2:1, the degradation efficiency is optimal, and the degradation can reach 63.2 percent in about 100 min. The composite ratio of CuO to CuS is 2: in the process of degrading organic pollutants in water by the CuO @ CuS/PVDF composite membrane prepared by 1, the degradation efficiency is changed within 40min as shown in figure 4, and it can be seen that the catalytic degradation efficiency is as high as 86.5% within 40 min.
(2) The composite ratio of CuO to CuS is 2: the degradation conditions of the CuO @ CuS/PVDF water treatment composite membrane prepared by 1 on organic tetracycline, enrofloxacin, ciprofloxacin and lomefloxacin are shown in figure 5, and it can be seen that the activated PS of the CuO @ CuS/PVDF water treatment composite membrane has obvious degradation effects on various novel antibiotics (tetracycline, enrofloxacin, ciprofloxacin and lomefloxacin), so that the CuO @ CuS/PVDF water treatment composite membrane can be applied to deep treatment in the fields of medical wastewater and the like, and the CuO @ CuS/PVDF water treatment composite membrane has a wide application range in the field of water treatment.
(3) The composite ratio of CuO to CuS is 2:1, when the CuO @ CuS/PVDF water treatment composite membrane prepared by the method degrades organic pollutants in water, pollutant solutions with different initial pH values are set, and the pH tolerance of the CuO @ CuS/PVDF water treatment composite membrane is analyzed, and the result is shown in figure 6, which shows that the CuO @ CuS/PVDF water treatment composite membrane has excellent pH tolerance and excellent degradation efficiency within the pH range of 3-9, so that the CuO @ CuS/PVDF water treatment composite membrane prepared by the method is suitable for organic wastewater with the pH value of 3-9.
(4) For further testing, the composite ratio of CuO to CuS is 2:1, and performing an experiment for degrading organic pollutants by repeatedly using the CuO @ CuS/PVDF water treatment composite membrane, wherein the result is shown in figure 7, which shows that the CuO @ CuS/PVDF water treatment composite membrane still has excellent degradation efficiency when being repeatedly used for 8 times, so that the CuO @ CuS/PVDF water treatment composite membrane prepared by the invention has good stability in the process of degrading organic pollutants in water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A preparation method of a CuO @ CuS/PVDF water treatment composite membrane is characterized by comprising the following steps:
(1) preparation of nano CuO powder
Chemical coprecipitation method is adopted to mix Na2CO3Mixing the solution with CuSO4The solution reacts to generate basic copper carbonate, the basic copper carbonate is kept stand for 3 hours at room temperature, then is centrifugally washed by deionized water and absolute ethyl alcohol, and the washed precipitate is placed in an oven at 80 ℃ for drying for 12 hours, then is placed in a muffle furnace and is calcined for 2 hours at 400 ℃ to obtain nano CuO powder;
(2) preparation of CuO @ CuS nano composite powder
Preparing CuO @ CuS nano composite powder by adopting a microwave method, namely firstly, preparing CuSO4·5H2O and Na2S2O3Respectively dissolved in deionized water to form CuSO4Solution and Na2S2O3Solution, then adding the nano CuO powder to the CuSO4Adding Na into the solution, stirring until the mixture is uniformly mixed, and adding the Na into the mixed solution2S2O3Stirring the solution for 10 minutes to obtain fluorescent green precipitate, transferring the fluorescent green precipitate into a microwave reactor to react for 20 minutes to obtain a blue-black precipitate product, washing the blue-black precipitate product with absolute ethyl alcohol and deionized water, and drying the washed blue-black precipitate product in a drying oven at 60 ℃ for 12 hours to finally obtain CuO @ CuS nano composite powder;
(3) preparation of CuO @ CuS/PVDF composite membrane
Adding quantitative dry polyvinylidene fluoride (PVDF) particles into a Dimethylacetamide (DMAC) solvent, placing the mixture in a constant-temperature water bath stirrer at the temperature of 80 ℃ for stirring until a homogeneous solution is formed, and then adding quantitative (NaPO) into the mixture at the dry room temperature3)6PVP and the CuO @ CuS nano composite powder are slowly stirred to be uniformly mixed, kept stand for 48 hours for defoaming, poured on a plane glass plate, uniformly scraped into a film with the thickness of 200 mu m, and finally soaked in Et-OH2And (3) stripping in an ethanol solution with the ratio of O to 1:2 to obtain the CuO @ CuS/PVDF composite membrane.
2. The method of claim 1 for preparing a CuO @ CuS/PVDF composite membrane in a water treatment system, wherein the molar ratio of CuO to CuS in the CuO @ CuS nanocomposite powder is 2: 1.
3. The method for preparing the CuO @ CuS/PVDF composite membrane as claimed in claim 1, wherein in step (3), the DMAC, PVDF and (NaPO) are used3)6PVP, and CuO @ CuS nanocomposite powder were 73.5 wt.%, 20 wt.%, 1.5 wt.%, 4 wt.%, and 1 wt.%, respectively.
4. A CuO @ CuS/PVDF water treatment composite membrane prepared by the preparation method as set forth in any one of claims 1 to 3.
5. The use of the CuO @ CuS/PVDF composite membrane as defined in claim 4 for water treatment to degrade organic contaminants in water.
6. The use of claim 5, wherein said CuO @ CuS/PVDF composite water treatment membrane is used in the degradation treatment of medical wastewater.
7. The application of claim 5 or 6, wherein 0.4g/L of persulfate is added when the CuO @ CuS/PVDF composite membrane for water treatment is used for degrading organic pollutants in water, and the initial pH value of degradation is 3-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010496296.6A CN111672335B (en) | 2020-06-03 | 2020-06-03 | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010496296.6A CN111672335B (en) | 2020-06-03 | 2020-06-03 | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111672335A true CN111672335A (en) | 2020-09-18 |
| CN111672335B CN111672335B (en) | 2021-09-10 |
Family
ID=72453481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010496296.6A Expired - Fee Related CN111672335B (en) | 2020-06-03 | 2020-06-03 | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111672335B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113753939A (en) * | 2021-09-27 | 2021-12-07 | 武汉大学 | Spherical sea urchin-shaped copper oxide particles and preparation method and application thereof |
| CN114068907A (en) * | 2021-11-16 | 2022-02-18 | 江苏科技大学 | CuO @ Cu-BTC composite electrode with rod-shaped structure and preparation method thereof |
| CN115283020A (en) * | 2022-01-12 | 2022-11-04 | 伊犁师范大学 | Preparation method and application of S-nZVI/PVDF (polyvinylidene fluoride) water treatment composite membrane |
| CN115634587A (en) * | 2022-09-19 | 2023-01-24 | 长春工业大学 | Preparation and application of flower-like CuO/CF-PVDF (CuO/CF-polyvinylidene fluoride) photo-thermal film |
| CN116237063A (en) * | 2023-02-17 | 2023-06-09 | 兰州大学 | Yttrium promoted carbon dioxide reduction catalyst and its preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0747155B2 (en) * | 1988-11-17 | 1995-05-24 | 三井石油化学工業株式会社 | Treatment method of phosphorus-containing wastewater |
| CN103638827A (en) * | 2013-12-11 | 2014-03-19 | 天津工业大学 | Iron-heavy metal nano particle/PVDF (polyvinylidene fluoride) hybrid membrane and preparation method thereof |
| CN104383930A (en) * | 2014-11-25 | 2015-03-04 | 辽宁大学 | Zinc ferrite-loaded carbon nano tube catalyst prepared by microwave-hydrothermal method and application of catalyst in degrading organic pollutants in water |
| CN106390777A (en) * | 2016-10-28 | 2017-02-15 | 西北大学 | Copper hydroxide nanowire/polyvinylidene fluoride hybrid ultrafiltration membrane and preparation method thereof |
-
2020
- 2020-06-03 CN CN202010496296.6A patent/CN111672335B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0747155B2 (en) * | 1988-11-17 | 1995-05-24 | 三井石油化学工業株式会社 | Treatment method of phosphorus-containing wastewater |
| CN103638827A (en) * | 2013-12-11 | 2014-03-19 | 天津工业大学 | Iron-heavy metal nano particle/PVDF (polyvinylidene fluoride) hybrid membrane and preparation method thereof |
| CN104383930A (en) * | 2014-11-25 | 2015-03-04 | 辽宁大学 | Zinc ferrite-loaded carbon nano tube catalyst prepared by microwave-hydrothermal method and application of catalyst in degrading organic pollutants in water |
| CN106390777A (en) * | 2016-10-28 | 2017-02-15 | 西北大学 | Copper hydroxide nanowire/polyvinylidene fluoride hybrid ultrafiltration membrane and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LI HE等: "《Microwave-assisted Synthesis of CuS/Graphene Composite for Enhanced Lithium Storage Properties》", 《ELECTROCHIMICA ACTA》 * |
| REN SHOUJIE等: "《Enhanced catalytic performance of Zr modified CuO/ZnO/Al2O3 catalyst for methanol and DME synthesis via CO2 hydrogenation》", 《JOURNAL OF CO2 UTILIZATION》 * |
| YAO YUNJIN等: "《Heteroatoms doped metal iron–polyvinylidene fluoride (PVDF) membrane for enhancing oxidation of organic contaminants》", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113753939A (en) * | 2021-09-27 | 2021-12-07 | 武汉大学 | Spherical sea urchin-shaped copper oxide particles and preparation method and application thereof |
| CN114068907A (en) * | 2021-11-16 | 2022-02-18 | 江苏科技大学 | CuO @ Cu-BTC composite electrode with rod-shaped structure and preparation method thereof |
| CN115283020A (en) * | 2022-01-12 | 2022-11-04 | 伊犁师范大学 | Preparation method and application of S-nZVI/PVDF (polyvinylidene fluoride) water treatment composite membrane |
| CN115634587A (en) * | 2022-09-19 | 2023-01-24 | 长春工业大学 | Preparation and application of flower-like CuO/CF-PVDF (CuO/CF-polyvinylidene fluoride) photo-thermal film |
| CN116237063A (en) * | 2023-02-17 | 2023-06-09 | 兰州大学 | Yttrium promoted carbon dioxide reduction catalyst and its preparation method |
| CN116237063B (en) * | 2023-02-17 | 2023-08-15 | 兰州大学 | Yttrium promoted carbon dioxide reduction catalyst and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111672335B (en) | 2021-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111672335B (en) | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane | |
| CN113198516A (en) | Iron-nitrogen co-doped biochar catalyst, and preparation method and application thereof | |
| CN113877581B (en) | Copper ferrite spinel material and preparation method and application thereof | |
| CN107051468A (en) | Load the preparation method and application of poly-metal deoxide ozone catalytic oxidation catalyst | |
| CN112958092B (en) | Activated persulfate catalyst and preparation method and application thereof | |
| CN113385237A (en) | Composite catalytic membrane for rapidly activating PMS (permanent magnet synchronous Motor), preparation method and application thereof, and method for treating organic wastewater | |
| CN113457710A (en) | PDI/g-C3N4/Bi2WO6Composite photocatalyst and preparation method and application thereof | |
| CN105056986A (en) | Method for preparing flake shaped bismuth oxide nitrate hydroxide photocatalyst and catalyst application | |
| CN103962160B (en) | Fenton carrier of a kind of carbon-based solid acid and its preparation method and application | |
| CN111111683A (en) | Composite photocatalyst and preparation method thereof | |
| CN114433084B (en) | Preparation method and application of hollow carbon/silicon composite microsphere catalyst with core-shell structure | |
| CN113354059B (en) | Method for promoting ferric iron/hydrogen peroxide system to degrade environmental pollutants by using amorphous red phosphorus | |
| CN111229200A (en) | Bismuth oxide modified Ti3+Self-doping TiO2Preparation method of heterojunction photocatalyst | |
| CN114272916B (en) | High-catalytic-activity mullite material, and preparation method and application thereof | |
| CN109382089B (en) | Preparation method of self-cleaning fiber | |
| CN113019359B (en) | MnO (MnO) 2 Preparation method and application of triangular-plate Fenton-like catalyst | |
| CN113354060A (en) | Method for realizing efficient degradation of environmental pollutants by using red phosphorus in ferric iron/persulfate system | |
| CN115245825B (en) | Fenton-like catalyst converted from animal manure and synthesis method and application thereof | |
| CN110975874A (en) | Magnetic Bi25FeO40Preparation method and catalytic application of nano material | |
| CN114522713B (en) | Preparation method and application of cobalt nanoparticle/boron nitride composite material | |
| CN113634237B (en) | UIO-66-OH/DE composite material and treatment method of sewage containing SMX | |
| CN116272424B (en) | CuFeS2Modified catalytic ceramic membrane and preparation method and application thereof | |
| CN116870920B (en) | Preparation method and application of cuprous oxide-vanadium dioxide/vanadium pentoxide photocatalyst | |
| CN110980893B (en) | Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method | |
| CN115569665A (en) | Manganese dioxide octahedral molecular sieve catalyst and synthesis method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210910 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |