CN111992218A - Copper-based catalyst for degrading antibiotics and preparation method thereof - Google Patents
Copper-based catalyst for degrading antibiotics and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 45
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 45
- 239000010949 copper Substances 0.000 title claims abstract description 45
- 230000000593 degrading effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 72
- 238000001035 drying Methods 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000005470 impregnation Methods 0.000 claims abstract description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 23
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000003751 zinc Chemical class 0.000 claims abstract description 15
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 12
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000004098 Tetracycline Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a copper-based catalyst for degrading antibiotics and a preparation method thereof, wherein the preparation method of the copper-based catalyst comprises the following steps: (1) preparing an aqueous solution containing polyvinyl alcohol, copper salt and zinc salt to obtain a solution a; preparing an ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain a solution b; mixing the solution a and the solution b to obtain an impregnation solution; (2) mixing the carrier and the impregnation liquid, aging and drying; (3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment; (4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst. The preparation method is simple, easy to operate, relatively low in production cost, high in activity and good in thermal stability, and the catalyst is particularly suitable for being used as a catalyst for degrading antibiotics and can be widely applied to treatment of antibiotic wastewater.
Description
Technical Field
The invention relates to the technical field of copper-based catalyst materials, in particular to a copper-based catalyst for degrading antibiotics and a preparation method thereof.
Background
Antibiotics are produced in the world in big war twice, and are used as an important chemical agent, which plays an important role in preventing and treating human diseases and animal and plant diseases, China is a main production country of the antibiotics, although the yield is continuously increased, the utilization rate of raw materials is low due to various aspects such as technology and the like, a large amount of residual antibiotics exist in discharged wastewater, the environment is seriously polluted, the realization of economic benefits of pharmaceutical enterprises is influenced, and the social benefits of the enterprises are also seriously influenced.
The treatment technology of the water body containing the antibiotics mainly comprises the following steps: (1) physical method, antibiotics in water body are adsorbed, concentrated and separated under the condition of no chemical form change, including physical adsorption, extraction, membrane separation and the like; (2) biological method, which removes antibiotics in water body by using the absorption, accumulation, enrichment, flocculation and other actions of microorganism or plant, and comprises activated sludge method, anoxic/aerobic method, flocculation precipitation and the like; (3) chemical methods, in which antibiotics in water react with chemical substances to be removed, or chemical morphological changes occur under other initiation conditions to be degraded and removed, include advanced oxidation, photocatalytic oxidation, electrochemical oxidation, and the like.
The antibiotic wastewater belongs to refractory organic wastewater, and the strong inhibition effect of the residual antibiotic on microorganisms can cause the wastewater treatment process to be complex, the cost to be high and the effect to be unstable. Therefore, in the treatment of antibiotic wastewater, physical treatment can be used as a pretreatment method of subsequent biochemical treatment to reduce suspended matters in water and biological inhibiting substances in wastewater. At present, the physical treatment methods mainly include coagulation, sedimentation, air-float, adsorption, reverse osmosis and filtration. The coagulation method is that after coagulant is added, the particles losing charges are stirred to contact with each other to form flocculant, so that the flocculant is convenient to precipitate or filter to achieve the purpose of separation. After coagulation treatment, the concentration of pollutants can be effectively reduced, and the biodegradability of wastewater can be improved. The common coagulants in the treatment of antibiotic pharmaceutical wastewater include: polymeric ferric sulfate, ferric trichloride, ferric salt, polymeric ferric aluminum sulfate, polyacrylamide and the like. Sedimentation is the process of separating or removing suspended particles of higher density than water by gravity sedimentation. The air flotation uses highly dispersed micro-bubbles as carriers to adsorb pollutants in the wastewater, so that the apparent density of the bubbles is less than that of water, and the bubbles float upwards to realize the process of solid-liquid separation or liquid-liquid separation. Generally including an aerated air-float, a dissolved air-float, a chemical air-float and an electrolytic air-float. The adsorption method is to purify waste water by adsorbing some pollutants in the waste water with a porous solid to recover or remove the pollutants. Commonly used adsorbents include activated carbon, activated coal, humic acid and adsorbent resins. The method has the advantages of low investment, simple process, convenient operation and convenient treatment. The reverse osmosis method is to separate concentrated solution from dilute solution with semi-permeable membrane, apply pressure over the osmotic pressure of the solution with pressure difference as driving force, change the natural osmosis direction, and permeate the water pressure in the concentrated solution to one side of the dilute solution. The purposes of sewage concentration and purification are achieved.
Because the physical method can only realize the concentration and transfer of the antibiotics, the fundamental removal of the antibiotics can not be realized; the biological method has poor effect of removing antibiotics in the water body; the chemical method can effectively degrade and remove antibiotics in the water body, and simultaneously has the problems of high cost and difficult recovery of chemical reagents. And the method for enriching by adopting a physical adsorption method and degrading the antibiotics by adopting a chemical catalysis method has certain feasibility and application prospect. Therefore, the research and development of the copper-based catalyst capable of degrading the antibiotics can reduce the cost and improve the recycling efficiency, and the method has important significance for the technical innovation and the engineering application of the removal of the antibiotics in the water body.
Disclosure of Invention
In view of the disadvantages of the prior art, it is an object of the present invention to provide a copper-based catalyst for degrading antibiotics; another object of the present invention is to provide a method for preparing the copper-based catalyst for degrading antibiotics.
In order to realize the invention, the technical scheme is as follows:
a preparation method of a copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing polyvinyl alcohol, copper salt and zinc salt to obtain a solution a; preparing an ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain a solution b; mixing the solution a and the solution b to obtain an impregnation solution;
(2) mixing the carrier and the impregnation liquid, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
As a preferred technical solution of the present invention, the method for preparing the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.1-0.2mol/L polyvinyl alcohol, 2-3mol/L copper salt and 1-2mol/L zinc salt to obtain a solution a; preparing 0.2-0.3mol/L of ethanol solution of gamma-glycidyl ether oxypropyl trimethoxy silane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 0.9-1.1 to obtain impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
Preferably, the polyvinyl alcohol in step (1) is at least one selected from the group consisting of polyvinyl alcohol 600, polyvinyl alcohol 800, polyvinyl alcohol 1000, and polyvinyl alcohol 2000.
Preferably, the copper salt in step (1) is at least one selected from copper nitrate, copper chloride and copper sulfate.
Preferably, the zinc salt in step (1) is at least one selected from zinc nitrate, zinc chloride and zinc sulfate.
Preferably, the carrier in the step (2) is activated carbon; the carrier is in the shape of a strip, a sheet, a column or a sphere.
Preferably, the aging condition in the step (2) is room temperature aging for 5-10 h.
Preferably, the drying condition in the step (2) is that the drying temperature is 100-150 ℃, and the drying time is 15-20 h.
Preferably, the hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 140-180 ℃ in an inert atmosphere, and then a mixed gas of steam and inert gas is introduced, wherein the volume percentage content of the steam in the mixed gas is 70-80%, and the balance is the inert gas; the treatment time is 3-6 h; and finally, switching to inert gas, and purging for 1-2h, wherein the inert gas is nitrogen.
Preferably, the roasting condition in the step (4) is that the roasting temperature is 550-850 ℃ and the roasting time is 5-25 h.
Preferably, the roasting condition in the step (4) is that the roasting temperature is 600-700 ℃, and the roasting time is 8-10 h.
The invention also provides a copper-based catalyst for degrading antibiotics, which is prepared by adopting the method.
The invention has the beneficial effects that:
(1) in the preparation process of the copper-based catalyst, on one hand, the adhesiveness of metal salt on a carrier is improved by adding a gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent, and on the other hand, the dispersion wettability of the metal salt is improved by adding polyvinyl alcohol.
(2) The inventor of the invention discovers through a large number of experiments that the optimal dosage ratio of the copper salt and the zinc salt is obtained by adjusting the dosage ratio of the copper salt and the zinc salt in the scheme; under the optimal proportion, the adsorption and enrichment capacity of the copper-based catalyst to the antibiotics is improved, and the catalytic degradation efficiency of the antibiotics on the surface of the copper-based catalyst is obviously improved under the irradiation of visible light.
(3) The preparation method is simple, easy to operate, relatively low in production cost, high in activity and good in thermal stability, and the catalyst is particularly suitable for being used as a catalyst for degrading antibiotics and can be widely applied to treatment of antibiotic wastewater.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.15mol/L polyvinyl alcohol 800, 2.5mol/L copper nitrate and 1.5mol/L zinc nitrate to obtain a solution a; preparing 0.25mol/L ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 1 to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Example 2
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.1mol/L polyvinyl alcohol 800, 2mol/L copper nitrate and 1mol/L zinc nitrate to obtain a solution a; preparing 0.2mol/L ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 0.9 to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Example 3
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.2mol/L polyvinyl alcohol 800, 3mol/L copper nitrate and 2mol/L zinc nitrate to obtain a solution a; preparing 0.3mol/L ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 1.1 to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Comparative example 1
Compared with example 1, the difference is only that "1.5 mol/L zinc salt aqueous solution" is replaced by "3 mol/L zinc salt aqueous solution".
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.15mol/L polyvinyl alcohol 800, 2.5mol/L copper nitrate and 3mol/L zinc nitrate to obtain a solution a; preparing 0.25mol/L ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 1 to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Comparative example 2
Compared with example 1, the difference is only that "1.5 mol/L zinc salt aqueous solution" is replaced by "0.5 mol/L zinc salt aqueous solution".
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.15mol/L polyvinyl alcohol 800, 2.5mol/L copper nitrate and 0.5mol/L zinc nitrate to obtain a solution a; preparing 0.25mol/L ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 1 to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Comparative example 3
The only difference compared to example 1 is that "solution b" is replaced by "ethanol".
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 0.15mol/L polyvinyl alcohol 800, 2.5mol/L copper nitrate and 1.5mol/L zinc nitrate to obtain a solution a; mixing the solution a and ethanol according to the volume ratio of 1: 1 to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Comparative example 4
Compared with example 1, the difference is only that "preparing an aqueous solution containing 0.15mol/L polyvinyl alcohol, 2.5mol/L copper salt and 1.5mol/L zinc salt to obtain solution a" is replaced by "preparing an aqueous solution containing 2.5mol/L copper salt and 1.5mol/L zinc salt to obtain solution a".
The preparation method of the copper-based catalyst for degrading antibiotics comprises the following steps:
(1) preparing an aqueous solution containing 2.5mol/L copper nitrate and 1.5mol/L zinc nitrate to obtain a solution a; preparing 0.25mol/L ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain solution b; and (3) mixing the solution a and the solution b according to a volume ratio of 1: 1, mixing to obtain an impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
The carrier in the step (2) is activated carbon, and the carrier is strip-shaped; the aging condition is aging at room temperature of 25 ℃ for 7 h; the drying conditions were a drying temperature of 120 ℃ and a drying time of 18 h.
The hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 160 ℃ in an inert atmosphere, and then mixed gas of water vapor and inert gas is introduced, wherein the volume percentage of the water vapor in the mixed gas is 75%, and the balance is the inert gas; the treatment time is 5 h; and finally, switching to inert gas, and purging for 1.5h, wherein the inert gas is nitrogen.
The roasting condition in the step (4) is that the roasting temperature is 650 ℃, the roasting time is 5h at the constant temperature of 650 ℃, and the heating rate during roasting is 10 ℃/min.
Test example
100mg of the copper-based catalyst for degrading antibiotics prepared in the examples 1-3 and the comparative examples 1-4 is added into 100mL of tetracycline solution with the concentration of 20mg/L, the mixture is subjected to uniform ultrasonic treatment, the mixture is subjected to reaction for 60min (magnetic stirring) under a dark condition, after adsorption and desorption balance is achieved, the mixture is subjected to photocatalytic degradation reaction under visible light with the wavelength lambda being more than 420nm for 150min, and the photocatalytic degradation of tetracycline in a water body is completed. After the photocatalytic degradation reaction is finished, collecting the residual sample, drying, and carrying out photocatalytic degradation on the tetracycline water body under the same experimental conditions for 4 times in total. Sampling 3mL every 30min, measuring the characteristic peak value of tetracycline in the solution by using an ultraviolet-visible spectrophotometer, converting the characteristic peak value into concentration, calculating degradation rates of different cycles, and taking an average value. Specific results are shown in table 1.
Table 1: test result table
| A degradation rate% | |
| Example 1 | 98.5 |
| Example 2 | 96.1 |
| Example 3 | 96.8 |
| Comparative example 1 | 58.2 |
| Comparative example 2 | 53.7 |
| Comparative example 3 | 50.4 |
| Comparative example 4 | 58.9 |
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (10)
1. A preparation method of a copper-based catalyst for degrading antibiotics is characterized by comprising the following steps:
(1) preparing an aqueous solution containing polyvinyl alcohol, copper salt and zinc salt to obtain a solution a; preparing an ethanol solution of gamma-glycidyl ether oxypropyltrimethoxysilane to obtain a solution b; mixing the solution a and the solution b to obtain an impregnation solution;
(2) mixing the carrier and the impregnation liquid, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
2. The process for preparing a copper-based catalyst for degrading antibiotics according to claim 1, wherein:
(1) preparing an aqueous solution containing 0.1-0.2mol/L polyvinyl alcohol, 2-3mol/L copper salt and 1-2mol/L zinc salt to obtain a solution a; preparing 0.2-0.3mol/L of ethanol solution of gamma-glycidyl ether oxypropyl trimethoxy silane to obtain solution b; mixing the solution a and the solution b according to the volume ratio of 1: 0.9-1.1 to obtain impregnation liquid;
(2) mixing the carrier and the impregnation liquid in equal volume, aging and drying;
(3) placing the material obtained in the step (2) in a tube furnace for hydro-thermal treatment;
(4) and (4) roasting the material obtained in the step (3) to obtain the copper-based catalyst.
3. The process for preparing a copper-based catalyst for the degradation of antibiotics according to claim 1 or 2, characterized in that: the polyvinyl alcohol is at least one selected from the group consisting of polyvinyl alcohol 600, polyvinyl alcohol 800, polyvinyl alcohol 1000, and polyvinyl alcohol 2000.
4. The process for preparing a copper-based catalyst for the degradation of antibiotics according to claim 1 or 2, characterized in that: the copper salt is selected from at least one of copper nitrate, copper chloride and copper sulfate; the zinc salt is selected from at least one of zinc nitrate, zinc chloride and zinc sulfate.
5. The process for preparing a copper-based catalyst for the degradation of antibiotics according to claim 1 or 2, characterized in that: the carrier is activated carbon.
6. The method for preparing a copper-based catalyst for degrading antibiotics according to claim 5, wherein: the carrier is in the shape of a strip, a sheet, a column or a sphere.
7. The process for preparing a copper-based catalyst for the degradation of antibiotics according to claim 1 or 2, characterized in that: and (3) aging in the step (2) at room temperature for 5-10 h.
8. The process for preparing a copper-based catalyst for the degradation of antibiotics according to claim 1 or 2, characterized in that: the hydrothermal treatment in the step (3) is carried out under the condition of raising the temperature to 140-180 ℃ in an inert atmosphere, and then mixed gas of steam and inert gas is introduced, wherein the volume percentage of the steam in the mixed gas is 70-80%, and the balance is the inert gas; the treatment time is 3-6 h; and finally, switching to inert gas, and purging for 1-2h, wherein the inert gas is nitrogen.
9. The process for preparing a copper-based catalyst for the degradation of antibiotics according to claim 1 or 2, characterized in that: the roasting condition in the step (4) is that the roasting temperature is 550-850 ℃, and the roasting time is 5-25 h.
10. A copper-based catalyst for degrading antibiotics, characterized in that: prepared by the method of any one of claims 1 to 9.
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