CN115569653A - Polymerization nanoparticle heterogeneous water treatment catalyst, preparation method and application - Google Patents
Polymerization nanoparticle heterogeneous water treatment catalyst, preparation method and application Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 title abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002738 chelating agent Substances 0.000 claims abstract description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 claims description 21
- 229960002036 phenytoin Drugs 0.000 claims description 21
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 16
- 229960003405 ciprofloxacin Drugs 0.000 claims description 8
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 7
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 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 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- STXKJSYMVDTOSJ-UHFFFAOYSA-M chlorocopper hexahydrate Chemical compound [Cu]Cl.O.O.O.O.O.O STXKJSYMVDTOSJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000011949 solid catalyst Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910052950 sphalerite Inorganic materials 0.000 description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229960000314 zinc acetate Drugs 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical group [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 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
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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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
- 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
-
- B01J35/23—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a polymerization nanoparticle multiphase water treatment catalyst, a preparation method and application thereof, wherein the method comprises the following steps: (1) Dissolving a copper source, an organic chelating agent and zinc acetate in water and stirring to obtain a mixed system A; (2) Dissolving sulfide in water and stirring to obtain a mixed system B; (3) Under the condition of water bath stirring, dropwise adding the mixed system B into the mixed system A to obtain a mixed system C; (4) And (3) cooling the mixed system C to room temperature, continuously stirring at room temperature to obtain a mixed system D, filtering to obtain a precipitate, washing with deionized water and methanol, and drying to obtain the polymerized nano particle multiphase water treatment catalyst. The method has the advantages of simple preparation process, low energy consumption in the preparation process and easy separation. The catalyst has a special polymerization nanoparticle structure, belongs to a solid catalyst, and has a good degradation and removal effect on organic pollutants difficult to biodegrade when used together with hydrogen peroxide in a wide pH range.
Description
Technical Field
The invention relates to the technical field of preparation and application of water treatment catalyst materials, in particular to a polymerization nanoparticle multiphase water treatment catalyst, a preparation method and application.
Background
With the rapid development of the pharmaceutical industry, the annual consumption of drugs is enormous. Statistically, the worldwide consumption of antibiotic drugs has reached 10 to 20 million tons per year, accounting for about 60% of all drug consumptions. However, most of the drugs are not absorbed by the organism after being taken, but released into the environment with the metabolites, including soil, water, and feces. The evolution of drug-resistant genes and drug-resistant super bacteria is accelerated; on the other hand, these pharmaceutical ingredients inhibit the usual biological processes. These increase the risk of environmental pollution and the cost of disposal, and therefore more efficient and inexpensive methods are needed.
In the existing advanced oxidation water treatment technology, homogeneous Fenton reaction (Fe) 2+ +H 2 O 2 ) Due to Fe in its reaction 2+ Can quickly activate hydrogen peroxide to generate strong-oxidizing OH, and has wide prospect of being applied to treating wastewater of medicines and the like. However, the practical application of the method has the problems of narrow pH corresponding range (2-3), iron mud generated after reaction, difficult separation of active components, high energy consumption and the like, so that the further application of the method is limited.
Therefore, how to break the bottleneck of the application of the limit fenton technology and design a more efficient and cheaper fenton catalyst is a problem to be solved urgently. In recent years, researchers have made studies on this problem, and have made some efforts to develop a heterogeneous fenton catalyst system having a structure of a metal-organic polymer, etc., but new problems have arisen, including complicated synthesis steps of a heterogeneous fenton catalyst, low catalytic activity under neutral conditions, low stability, low hydrogen peroxide utilization rate, etc.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a polymeric nanoparticle heterogeneous water treatment catalyst, a preparation method thereof, and an application of the catalyst to solve the above-mentioned problems.
In order to realize the purpose, the invention adopts the technical scheme that:
a method for preparing a polymeric nanoparticle heterogeneous water treatment catalyst, comprising the steps of:
(1) Dissolving a copper source, an organic chelating agent and zinc acetate in deionized water, and violently stirring to obtain a mixed system A;
(2) Dissolving sulfide in deionized water, and violently stirring to obtain a mixed system B;
(3) Dropwise adding the mixed system B into the mixed system A under the condition of water bath stirring to obtain a mixed system C;
(4) And (3) cooling the mixed system C to room temperature, continuously stirring at room temperature to obtain a mixed system D, filtering the mixed system D, taking the precipitate, washing with deionized water and methanol, and drying to obtain the polymerized nano particle multiphase water treatment catalyst.
Preferably, the copper source is at least one of copper chloride hexahydrate and copper nitrate trihydrate, and the organic chelating agent is at least one of disodium ethylene diamine tetraacetate, polyvinyl alcohol and citric acid.
Preferably, in the step (1), in the mixed system A, the concentration of the copper source is 5-10 mmol/L, the concentration of the organic chelating agent is 10-30 g/L, and the concentration of the zinc acetate is 0.1-0.5 mol/L.
Preferably, in the step (2), the sulfide is at least one of sodium sulfide and potassium sulfide.
Preferably, in the step (2), the sulfide concentration in the mixed system B is 0.1-0.5 mol/L.
Preferably, in the step (3), the water bath temperature is 80 ℃ and the stirring time is 1h.
Preferably, in the step (3), the volume ratio of the mixed system A to the mixed system B is 3:1 to 5:1.
preferably, in the step (4), the continuous stirring time is 10 to 14 hours.
Preferably, in the step (4), the polymerized nano-particle heterogeneous water treatment catalyst is obtained after drying.
The polymerization nanoparticle heterogeneous water treatment catalyst prepared by the method.
The polymerization nano-particle heterogeneous water treatment catalyst prepared by the method has a typical solid catalyst formed by polymerization of nano-particles, and the main component of the catalyst is a zinc sulfide sphalerite structure. The special structure of the catalyst is the combination of copper element and zinc blende crystal. In the catalyst, internal electron transfer exists in the synthesis process, and the electron arrangement on the surface of the catalyst is disturbed. Rearrangement of electrons on the surface of the catalyst initiates change of the polarity of the catalyst, so that hydrogen peroxide or pollutants in water can be efficiently used as an electron donor to maintain balance of system charge.
The invention also provides an application of the polymerization nanoparticle multi-phase water treatment catalyst in degrading medicinal organic pollutants in water.
The polymerization nanoparticle multiphase water treatment catalyst is combined with hydrogen peroxide to generate a large amount of active oxygen species (hydroxyl free radicals, superoxide free radicals, singlet oxygen and the like), is used for treating medical organic pollutants in water, and can be applied to the field of environmental remediation.
The invention also provides a method for treating the organic pollutants in the water, which comprises the following steps: adding the polymerization nanoparticle heterogeneous water treatment catalyst and hydrogen peroxide into a water body containing organic pollutants, and uniformly mixing.
Preferably, the pharmaceutical organic contaminant may include at least one of Ciprofloxacin (CIP), phenytoin (PHT), sulfamethoxazole (SMZ).
The polymerization nanoparticle multi-phase water treatment catalyst, the preparation method and the application have the beneficial effects that:
the preparation method has the advantages of simple process, low energy consumption in the preparation process and easy separation.
The polymerization nanoparticle multiphase water treatment catalyst has good combined activity with hydrogen peroxide, convenient use and wide pH response range, does not need to consider the pH value condition of a system in the reaction process, and has good degradation removal effect on the removal of organic pollutants difficult to biodegrade under acidic, neutral and alkaline conditions.
The polymerization nanoparticle heterogeneous water treatment catalyst has a special polymerization nanoparticle structure and belongs to a solid catalyst.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a polymerized nanoparticle heterogeneous water treatment catalyst prepared according to a preferred embodiment of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of a polymeric nanoparticle heterogeneous water treatment catalyst prepared according to a preferred embodiment of the present invention;
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) graph of a polymeric nanoparticle heterogeneous water treatment catalyst prepared according to a preferred embodiment of the present invention;
FIG. 4 is a graph showing the degradation results of ciprofloxacin, phenytoin and sulfamethoxazole by the polymeric nanoparticle heterogeneous water treatment catalyst prepared by the preferred embodiment;
FIG. 5 is a graph showing the degradation results of ciprofloxacin by the polymeric nanoparticle heterogeneous water treatment catalyst prepared according to a preferred embodiment of the present invention in solutions with different pH values.
FIG. 6 is a schematic illustration of a fixed bed reactor as required in a preferred embodiment of the present invention;
FIG. 7 is a graph of the operational stability of a fixed bed reactor built with the polymeric nanoparticle heterogeneous water treatment catalyst prepared according to a preferred embodiment of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
A method for preparing a polymeric nanoparticle heterogeneous water treatment catalyst, comprising the steps of:
(1) Dissolving a copper source, an organic chelating agent and zinc acetate in deionized water, and violently stirring to obtain a mixed system A;
(2) Dissolving sulfide in deionized water, and violently stirring to obtain a mixed system B;
(3) Dropwise adding the mixed system B into the mixed system A under the condition of water bath stirring to obtain a mixed system C;
(4) And (3) cooling the mixed system C to room temperature, continuously stirring at room temperature to obtain a mixed system D, filtering the mixed system D, taking the precipitate, washing with deionized water and methanol, and drying to obtain the polymerized nano particle multiphase water treatment catalyst.
The polymerization nano-particle heterogeneous water treatment catalyst prepared by the method.
The polymerization nano-particle heterogeneous water treatment catalyst prepared by the method has a typical solid catalyst formed by polymerization of nano-particles, and the main component of the catalyst is a zinc sulfide sphalerite structure. The special structure of the catalyst is the combination of copper element and zinc blende crystal. In the catalyst, internal electron transfer exists in the synthesis process, and the electron arrangement on the surface of the catalyst is disturbed. Rearrangement of electrons on the surface of the catalyst initiates change of the polarity of the catalyst, so that hydrogen peroxide or pollutants in water can be efficiently used as an electron donor to maintain balance of system charge.
The invention also provides an application of the polymerization nanoparticle multi-phase water treatment catalyst in degrading medicinal organic pollutants in water.
Example 1
Referring to fig. 1-7, an embodiment of the present invention provides a method for preparing a polymeric nanoparticle heterogeneous water treatment catalyst, which includes the following steps:
(1) Adding 0.5mmol of copper nitrate trihydrate, 2g of polyvinyl alcohol and 50mmol of anhydrous zinc acetate into 100mL of deionized water, and violently stirring to obtain a mixed system A;
(2) Adding 10mmol of sodium sulfide into 20mL of deionized water, and violently stirring to obtain a mixed system B;
(3) Dropwise adding the mixed system B into the mixed system A under the condition of water bath stirring at the temperature of 80 ℃, and keeping the water bath and stirring for 1h to obtain a mixed system C;
(4) And (3) cooling the mixed system C to room temperature, continuously stirring for 14h at the room temperature to obtain a mixed system D, filtering the mixed system D, taking the precipitate, washing with deionized water and methanol, and drying to obtain the polymerized nano particle multiphase water treatment catalyst.
Scanning electron microscope characterization is performed on the polymerization nanoparticle heterogeneous water treatment catalyst prepared in example 1, and as shown in fig. 1, the scanning electron microscope characterization is an SEM image of the polymerization nanoparticle heterogeneous water treatment catalyst prepared in example 1, and it can be seen from the SEM image that the morphology of the catalyst is a solid catalyst formed by polymerization of nanoparticles.
As shown in fig. 2, the XRD pattern of the polymeric nanoparticle heterogeneous water treatment catalyst of the catalyst prepared in example 1 shows that the main component of the catalyst is zinc sulfide sphalerite structure, and the introduction of copper causes the shift of (0010) crystal plane and (110) crystal plane, i.e. the introduction of copper does not collapse the original structure or form unit cells of sulfide and oxide of copper, but affects the growth of sphalerite crystal itself, reflecting the combination of copper element and sphalerite crystal.
As shown in fig. 3, an XPS diagram of the polymerization nanoparticle heterogeneous water treatment catalyst of the catalyst prepared in example 1 shows that the copper element in the catalyst exists in a low valence state, which indicates that an internal electron transfer process exists during the synthesis of the catalyst, and the electron arrangement on the surface of the catalyst is disturbed, and the rearrangement of the electrons on the surface of the catalyst induces a change in the polarity of the catalyst, so that the catalyst can efficiently use hydrogen peroxide or organic pollutants in water as an electron donor to maintain the balance of system charge.
Example 2
The method for degrading organic pollutants in water comprises the following steps: 0.02g of the polymeric nanoparticle heterogeneous water treatment catalyst prepared in example 1 and 50. Mu.L of hydrogen peroxide were put into 50mL of a 10mg/L contaminant solution, and the Fenton reaction was started by continuously stirring while maintaining a natural pH of about 7.0 at a constant temperature of 35 ℃.
The above contaminants are Ciprofloxacin (CIP), phenytoin (PHT) and Sulfamethoxazole (SMZ).
Sampling at different time points to detect the concentration of pollutants, wherein the experimental result is shown in figure 4, the degradation rate of ciprofloxacin is over 80% at 20 minutes, the degradation rates of phenytoin and sulfamethoxazole can reach 60% -70%, and the degradation rate of phenytoin reaches 100% at 120 minutes.
Example 3
In this example, the polymeric nanoparticle heterogeneous water treatment catalyst prepared in example 1 was examined for its response range to pH and its tendency to change pH of the solution during the reaction process, and the effect of removing phenytoin from the aqueous solution was tested, including the following steps:
(1) Preparing 5 parts of 50mL 10mg/L phenytoin solution, and adjusting the initial pH value of the 5 parts of phenytoin solution from acidity to alkalinity to 3.5, 4.4, 7.8, 9.4 and 10.1 respectively by using dilute nitric acid/sodium hydroxide;
(2) 0.02g of the polymeric nanoparticle heterogeneous water treatment catalyst prepared in example 1 and 50. Mu.L of hydrogen peroxide were put into solutions having different pH values, and the temperature was kept at 35 ℃ and the mixture was continuously stirred.
The concentration of phenytoin is sampled and detected at different times, the experimental result is shown in figure 5, the degradation rate of phenytoin reaches 100% in 120 minutes under the wide pH range of the initial solution, the above result fully reflects the wide pH response range of the polymeric nanoparticle heterogeneous water treatment catalyst, and the polymeric nanoparticle heterogeneous water treatment catalyst has good degradation and removal effects on phenytoin under acidic, neutral and alkaline conditions.
Example 4
In this example, the cycling stability of the polymeric nanoparticle heterogeneous water treatment catalyst prepared in example 1 tested the effect of continuously removing phenytoin, comprising the following steps:
(1) Preparing 10mg/L phenytoin solution, adding hydrogen peroxide with the concentration of about 10mM to obtain a mixed solution of phenytoin and hydrogen peroxide,
(2) Building a reaction device, wherein the reaction device is used for pumping the mixed solution of phenytoin and hydrogen peroxide into the fixed bed reactor through a peristaltic pump and discharging water from the other end;
(3) Setting a contrast experiment, dividing the experiment group into an experiment group and a control group, wherein the experiment group comprises: 0.5g of the polymeric nanoparticle heterogeneous water treatment catalyst prepared in example 1 was added to a fixed bed reactor, and the only difference between the control group and the experimental group in this example is: the control group did not add catalyst to the fixed bed reactor;
(4) The natural pH was maintained at room temperature at about 7.0, the hydraulic retention time was controlled at 60 minutes, and the peristaltic pump was started.
In the step (2), the reaction device is schematically shown in FIG. 6.
The results of detecting the concentration of phenytoin at the water outlet of the fixed bed reactors of the experimental group and the control group which are sampled at different times are shown in fig. 7, and the results show that the polymerized nano-particle multiphase water treatment catalyst continuously reacts in the fixed bed reactor, the phenytoin removal activity is not obviously reduced in 60 minutes, the phenytoin removal rate is still close to 50% after the circulating reaction is over 400 hours, and the results fully show that the polymerized nano-particle multiphase water treatment catalyst has good stability and repeatability and can be applied to the treatment of actual polluted water for a long time.
It should be noted that, within the scope of the present invention described above, other technical solutions obtained by selecting different components, ratios and process conditions can achieve the technical effects of the present invention, and therefore, they are not listed one by one.
The method provided by the embodiment of the invention has the advantages of simple preparation process, low energy consumption in the preparation process and easiness in separation. The catalyst prepared by the invention has a special polymerization nanoparticle structure, belongs to a solid catalyst, and has a good degradation and removal effect on organic pollutants difficult to biodegrade when used together with hydrogen peroxide in a wide pH range.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of a polymerized nano-particle heterogeneous water treatment catalyst is characterized by comprising the following steps:
(1) Dissolving a copper source, an organic chelating agent and zinc acetate in deionized water, and violently stirring to obtain a mixed system A;
(2) Dissolving sulfide in deionized water, and violently stirring to obtain a mixed system B;
(3) Dropwise adding the mixed system B into the mixed system A under the condition of water bath stirring to obtain a mixed system C;
(4) And (3) cooling the mixed system C to room temperature, continuously stirring at room temperature to obtain a mixed system D, filtering the mixed system D, taking the precipitate, washing with deionized water and methanol, and drying to obtain the polymerized nano particle multiphase water treatment catalyst.
2. The preparation method according to claim 1, wherein in the step (1), the copper source is at least one of copper chloride hexahydrate and copper nitrate trihydrate, and the organic chelating agent is at least one of disodium ethylenediaminetetraacetate, polyvinyl alcohol and citric acid.
3. The preparation method according to claim 1, wherein in the step (1), the copper source concentration of the mixed system A is 5 to 10mmol/L, the organic chelating agent concentration is 10 to 30g/L, and the zinc acetate concentration is 0.1 to 0.5mol/L.
4. The method according to claim 1, wherein in the step (2), the sulfide is at least one of sodium sulfide and potassium sulfide.
5. The production method according to claim 1, wherein in the step (2), the sulfide concentration in the mixed system B is 0.1 to 0.5mol/L, and the volume ratio of the mixed system A to the mixed system B is 3:1 to 5:1.
6. the process according to claim 1, wherein in the step (3), the temperature of the water bath is 80 ℃ and the stirring time is 1 hour.
7. The method according to claim 1, wherein the stirring time in the step (4) is 10 to 14 hours.
8. A polymeric nanoparticle heterogeneous water treatment catalyst prepared according to the method of any one of claims 1 to 7.
9. Use of the polymeric nanoparticle heterogeneous water treatment catalyst of claim 8 for the treatment of pharmaceutical organic pollutants in water.
10. A method for treating organic pharmaceutical pollutants in water, which is characterized by comprising the following steps:
adding the polymeric nanoparticle heterogeneous water treatment catalyst of claim 8 and hydrogen peroxide to a body of water containing organic contaminants and mixing well; the medicinal organic pollutants comprise at least one of ciprofloxacin, phenytoin and sulfamethoxazole.
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| US20120103909A1 (en) * | 2010-09-23 | 2012-05-03 | Molycorp Minerals, Llc | Particulate cerium dioxide and an in situ method for making and using the same |
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| US20120103909A1 (en) * | 2010-09-23 | 2012-05-03 | Molycorp Minerals, Llc | Particulate cerium dioxide and an in situ method for making and using the same |
| CN110342568A (en) * | 2019-08-09 | 2019-10-18 | 陕西科技大学 | A kind of silk ball flower shape zinc oxide copper sulfide and preparation method thereof |
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