CN112121823A - ZnO/CuO-CeO for removing VOCs2Preparation method and application of/FeSx composite catalyst - Google Patents
ZnO/CuO-CeO for removing VOCs2Preparation method and application of/FeSx composite catalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910005432 FeSx Inorganic materials 0.000 title claims abstract description 21
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 41
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
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- 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
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
The invention belongs to the field of environmental protection, and particularly relates to ZnO/CuO-CeO for removing VOCs (volatile organic compounds)2A preparation method and application of a/FeSx composite catalyst. The preparation method comprises the following steps: firstly zinc acetate and H3BTC is used as a raw material to prepare Zn-BTC, cerium acetylacetonate and copper acetylacetonate are adsorbed on a framework in the self-assembly process of the MOF framework, and then Zn-BTC/Cu-Ce is calcined in a muffle furnace to obtain ZnO/CuO-CeO with a Zn-BTC framework2And finally with Na2S solution and FeCl2Preparing FeSx by using solution as raw material and loadingIn ZnO/CuO-CeO2Thereby obtaining ZnO/CuO-CeO2the/FeSx composite catalyst. The composite catalyst prepared by the invention can reduce the reaction temperature of catalytic oxidation, and has high removal rate and short removal time in low-concentration VOCs.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to ZnO/CuO-CeO for removing VOCs (volatile organic compounds)2A preparation method and application of a/FeSx composite catalyst.
Background
In recent years, air pollution has strong diffusivity and invisible characteristics, so that long-term harm is generated in a large range, and the air pollution is gradually focused on people. The composition of atmospheric pollutants is quite complex, and besides suspended particles, other gaseous volatile organic pollutants exist in the air. Volatile Organic Compounds (VOCs) are a large class of carbon-based chemicals that readily volatilize into the air at ambient conditions, typically having a boiling point between 50-260 ℃ at normal atmospheric pressure. It not only can induce photochemical smog, ozone and haze and other environmental pollution problems, but also can seriously harm human health. They are generally derived from industrial reaction processes, waste gas emissions. According to the data of 2015, VOCs discharged in industrial processes account for 43% of artificial discharge amount of domestic VOCs, and the discharge amount of VOCs tends to increase year by year. The volatile substances are in various forms, including aromatic hydrocarbons, ketones, alcohols, halogenated hydrocarbons, aldehydes, epoxides, phenols, aromatic amines, and derivatives thereof. VOCs generally have the characteristics of strong volatility, irritation and the like, enter human bodies through breathing and skin, and cause a lot of physiological reactions to cause discomfort; VOCs belong to volatile substances and have the dangerous characteristics of flammability and explosiveness; VOCs are identified as one of the major causes of haze formation in the atmosphere, as well as photochemical smog and ozone layer destruction.
The treatment technology of the VOCs is mainly divided into two categories, namely a recovery method and a destruction method, and the difference between the two methods is whether the molecular structure of the VOCs is destroyed or not. The treatment techniques can be specifically classified into a condensation method, a membrane separation method, an adsorption method, an absorption method, a photolysis method, a combustion method, and a catalytic oxidation method; among these methods, the adsorption method, the photocatalyst method and the catalytic oxidation method have a great potential. The adsorption method is mainly used for collecting and separating VOCs components through a porous adsorbent, so that the aim of purifying waste gas is fulfilled; however, most of the absorbent in the method is an organic solvent, generally has the characteristics of certain toxicity and pollution, and can cause secondary environmental pollution problem in the subsequent absorption. The photocatalysis method mainly utilizes photo-generated carriers (electrons and holes) and H formed by the excited photocatalyst in a catalysis center2The strong oxidizing power of O-formed active species (such as. OH) completely degrades most of toxic VOCs molecules into non-toxic small molecules such as CO2And H2O, etc.; but when the concentration of the organic matter on the surface of the catalyst is too high,the photocatalyst may be deactivated.
The catalytic oxidation method is to perform VOC and O under certain conditions (temperature, pressure and the like)2The flameless oxidative degradation reaction is carried out on the surface of the catalyst, the reaction temperature is generally 200-450 ℃, and compared with other technologies for VOC treatment, the catalytic oxidation method has the characteristics of simple operation, strong controllability, short retention time and high treatment efficiency. The catalytic oxidation technology has wide application range, is very suitable for treating waste gas without recovery value generated in various industrial processes, and has great research value. However, the catalytic oxidation method is expected to lower the neutralization reaction temperature in practical use, and further improvement in the removal rate and reaction time of VOCs at low concentrations is required.
Disclosure of Invention
In order to solve the problems of higher reaction temperature, low removal rate in low-concentration VOCs and long reaction time of the catalytic oxidation method in the background art, the invention provides ZnO/CuO-CeO2A preparation method of a/FeSx composite catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
ZnO/CuO-CeO for removing VOCs2The preparation method of the/FeSx composite catalyst comprises the following steps:
the method comprises the following steps: dissolving a certain amount of zinc acetate in 50mL of deionized water, and adding a proper amount of H3BTC is dissolved in 100mL of ethanol-DMF mixed solution, cerium acetylacetonate and copper acetylacetonate are dissolved in deionized water according to a certain proportion to obtain a mixed solution A; slowly dropping the mixed solution A into an aqueous solution of zinc acetate, and performing ultrasonic treatment for 30-40min to obtain a mixed solution B; dropping the mixed solution B into H under stirring in water bath at 30-40 deg.C3BTC in ethanol, then the mixture was allowed to stir at room temperature for 3-4 h. Then transferring the mixed solution into a reaction kettle to react for 12-18h at the temperature of 120-140 ℃, washing the mixed solution for 5 times by using ethanol after the reaction, and placing the product in a vacuum drying box at the temperature of 110 ℃ for 18-24 h.
Step two: and (3) heating the dried sample to 500 ℃ in a muffle furnace at the speed of 10 ℃/min and calcining the sample at the temperature for 2-4h to obtain the metal oxide porous composite.
Step three: adding a proper amount of Na2S is added into deionized water in a water bath at 50-60 ℃, a certain amount of FeCl is added after stirring for 20-30min2The aqueous solution was slowly added with Na using a peristaltic pump2In an aqueous solution of S. Then placing the mixture into a water bath with the temperature of 70-80 ℃ for standing for 24h, then adding the compound prepared in the step two into the solution, stirring the mixture at room temperature for 5-7h, continuing to place the solution for aging, filtering the solution after aging to obtain a solid, washing the product for 3 times respectively by using ethanol and deionized water, and freeze-drying to obtain the ZnO/CuO-CeO2the/FeSx composite catalyst.
In the step one, the addition amount of the zinc acetate is 0.02-0.03mol, and the zinc acetate and the H are3The mass ratio of BTC is 1:1-1:1.4, and the mass ratio of zinc acetate, cerium acetylacetonate and copper acetylacetonate is 10 (1.1-1.7) to (2.5-4.8).
Na in the third step2The mass ratio of S to zinc acetate is 1:6-1:9, FeCl2And Na2The mass ratio of S is 1:1-1:1.5, and the aging time in the water bath is 24-36 h.
Preferably, in the first step, the volume ratio of the ethanol to the DMF mixed solution is 2:1-4:1, and the concentration of the mixture in the mixed solution A is 0.2 g/mL.
Preferably, the dropping speed of the mixed solution A in the step one is 2ml/min, and the dropping speed of the mixed solution B is 6 ml/min.
Preferably, Na in step three2S concentration of 0.6mol/L, FeCl2The concentration of the solution was 0.6 mol/L.
On the other hand, the application of the composite catalyst in VOCs removal is also provided.
Has the advantages that: the invention provides ZnO/CuO-CeO2the/FeSx composite catalyst effectively solves the problems of high reaction temperature, low removal rate in low-concentration VOCs and long reaction time of catalytic oxidation in the prior art. According to the invention, the zinc oxide obtained by preparing the Zn-BTC precursor and calcining has the framework structure of the Zn-BTC material and larger specific surface area. In Zn2+And H3In the process of forming three-dimensional Zn-BTC by BTC ligand self-assembly, addingThe cerium acetylacetonate and the copper acetylacetonate can be firmly and uniformly adsorbed on the MOF framework, and after the metal oxide porous composite is formed by calcining, CuO-CeO on the ZnO framework2The distribution is uniform, the particles are not agglomerated together, and the contact rate of the oxide and the VOCs molecules is improved. In ZnO/CuO-CeO2The surface of (A) is loaded with FeSx, on the one hand, the unsaturated S atom in FeSx is relative to ZnO/CuO-CeO2The catalytic oxidation performance is improved to a certain extent, and on the other hand, FeSx has the capability of adsorbing, capturing and converting organic matters such as aromatic hydrocarbons.
Drawings
FIG. 1 is a graph showing the removal rate of VOCs at different temperatures for the composite catalysts of examples 1-4 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The method comprises the following steps: 3.67g of zinc acetate was dissolved in 50mL of deionized water, and 5.87g of H3BTC was dissolved in a mixture of 66.7mL of ethanol and 33.3mL of DMF, followed by dissolving 1.53g of cerium acetylacetonate and 2.51g of copper acetylacetonate in 27.8mL of deionized water to obtain a mixed solution A; then dropping the mixed solution A into an aqueous solution of zinc acetate at the speed of 2ml/min, and carrying out ultrasonic treatment for 30min to obtain a mixed solution B; dropping the mixed solution B into H at the speed of 6ml/min under the stirring of water bath at the temperature of 40 DEG C3BTC in ethanol, then the mixture was allowed to stir at room temperature for 3-4 h. Then the mixed solution is transferred into a reaction kettle to react for 12 hours at 120 ℃, ethanol is used for washing for 5 times after the reaction, and the product is placed in a vacuum drying oven at 110 ℃ for 18 hours.
Step two: the dried sample was heated to 500 ℃ in a muffle furnace at a rate of 10 ℃/min and calcined at that temperature for 2 hours to obtain a metal oxide porous composite.
Step three: 0.26g of Na2S is dissolved in 5.5ml of deionized water under the water bath of 60 ℃, 5.5ml of FeCl with the concentration of 0.6mol/L is stirred for 20-30min2The aqueous solution was added slowly with a peristaltic pump. And then placing the solution in a water bath at 80 ℃ for standing for 24h, adding 3.6g of the compound prepared in the step two into the solution, stirring the solution at room temperature for 7h, continuing to place the solution for aging, filtering the solution after aging to obtain a solid, washing the product for 3 times respectively by using ethanol and deionized water, and freeze-drying to obtain the composite catalyst.
Example 2
The method comprises the following steps: 5.5g of zinc acetate was dissolved in 50mL of deionized water, 6.29g of H3BTC was dissolved in a mixture of 80mL of ethanol and 20mL of DMF, followed by dissolving 1.37g of cerium acetylacetonate and 1.96g of copper acetylacetonate in 23.6mL of deionized water to obtain a mixed solution A; then dropping the mixed solution A into an aqueous solution of zinc acetate at the speed of 2ml/min, and carrying out ultrasonic treatment for 40min to obtain a mixed solution B; dropping the mixed solution B into H at the speed of 6ml/min under the stirring of water bath at the temperature of 30 DEG C3BTC in ethanol, then the mixture was allowed to stir at room temperature for 3-4 h. Then the mixed solution is transferred into a reaction kettle to react for 18 hours at the temperature of 140 ℃, ethanol is used for washing for 5 times after the reaction, and the product is placed in a vacuum drying oven at the temperature of 110 ℃ for 20 hours.
Step two: the dried sample was heated to 500 ℃ in a muffle furnace at a rate of 10 ℃/min and calcined at that temperature for 4 hours to obtain a metal oxide porous composite.
Step three: 0.26g of Na2S is dissolved in 5.5ml of deionized water under the water bath of 50 ℃, 3.7ml of FeCl with the concentration of 0.6mol/L is stirred for 20-30min2The aqueous solution was added slowly with a peristaltic pump. And then placing the mixture into a water bath at 70 ℃ for standing for 24h, then adding 4g of the compound prepared in the second step into the solution, stirring the mixture at room temperature for 6h, continuing to place the solution for aging, filtering the solution after aging to obtain a solid, washing the product for 3 times respectively by using ethanol and deionized water, and freeze-drying to obtain the composite catalyst.
Example 3
The method comprises the following steps: 4.8g of zinc acetate are dissolvedDissolved in 50mL of deionized water, 6.72g of H3BTC was dissolved in a mixture of 72mL of ethanol and 28mL of DMF, followed by dissolving 1.44g of cerium acetylacetonate and 2.4g of copper acetylacetonate in 26.4mL of deionized water to obtain a mixed solution A; then dropping the mixed solution A into an aqueous solution of zinc acetate at the speed of 2ml/min, and carrying out ultrasonic treatment for 32min to obtain a mixed solution B; dropping the mixed solution B into H at the speed of 6ml/min under the stirring of a water bath at 34 DEG C3BTC in ethanol, then the mixture was allowed to stir at room temperature for 3-4 h. Then the mixed solution is transferred into a reaction kettle to react for 17 hours at 132 ℃, after the reaction, the mixed solution is washed for 5 times by ethanol, and the product is placed in a vacuum drying oven at 110 ℃ for 22 hours.
Step two: the dried sample was heated to 500 ℃ in a muffle furnace at a rate of 10 ℃/min and calcined at that temperature for 4 hours to obtain a metal oxide porous composite.
Step three: 0.29g of Na2S is dissolved in 6.2ml of deionized water in 56 ℃ water bath, 5.7ml of water FeCl with the concentration of 0.6mol/L is added after stirring for 20-30min2The solution was added slowly using a peristaltic pump. And then placing the solution in a water bath at 72 ℃ for standing for 24h, then adding 3.9g of the compound prepared in the step two into the solution, stirring the solution at room temperature for 5h, continuing to place the solution for aging, filtering the solution after aging to obtain a solid, washing the product for 3 times respectively by using ethanol and deionized water, and freeze-drying to obtain the composite catalyst.
Example 4
The method comprises the following steps: 5.2g of zinc acetate was dissolved in 50mL of deionized water, 6.76g of H3BTC was dissolved in a mixture of 70mL of ethanol and 330mL of DMF, followed by dissolving 1.82g of cerium acetylacetonate and 3.12g of copper acetylacetonate in 27.8mL of deionized water to obtain a mixed solution A; then dropping the mixed solution A into an aqueous solution of zinc acetate at the speed of 2ml/min, and carrying out ultrasonic treatment for 37min to obtain a mixed solution B; dropping the mixed solution B into H at the speed of 6ml/min under stirring in a water bath at 38 DEG C3BTC in ethanol, then the mixture was allowed to stir at room temperature for 3-4 h. Then the mixed solution is transferred into a reaction kettle to react for 15 hours at 127 ℃, ethanol is used for washing for 5 times after the reaction, and the product is placed in a vacuum drying oven at 110 ℃ for 24 hours.
Step two: the dried sample was heated to 500 ℃ in a muffle furnace at a rate of 10 ℃/min and calcined at that temperature for 3 hours to obtain a metal oxide porous composite.
Step three: 0.31g of Na2S is dissolved in 6.6ml of deionized water in a water bath at 58 ℃, 6.6ml of FeCl with the concentration of 0.6mol/L is stirred for 20-30min2The aqueous solution was added slowly with a peristaltic pump. And then placing the mixture into a water bath at 76 ℃ for standing for 24h, then adding 4.7g of the compound prepared in the step two into the solution, stirring the mixture at room temperature for 5h, continuing to place the solution for aging, filtering the solution after aging to obtain a solid, washing the product for 3 times respectively by using ethanol and deionized water, and freeze-drying to obtain the composite catalyst.
Comparative example 1
A Co-Mn composite oxide catalyst was prepared as comparative example 1 by the preparation method disclosed in patent CN 107362800B.
The specific analysis is as follows:
in order to verify the effective effect of the composite catalyst prepared by the preparation method of the present invention in the removal process of VOCs, the catalysts of examples 1 to 4 and comparative example 1 were used to simulate the experiments of VOCs treatment. The specific experimental results are shown in the figure I. The experimental simulation gas is a mixture of benzene, ether, butane and air; wherein the volume ratio of benzene, ether and butane is 2:3:1, and the volume ratio of the total volume of benzene, ether and butane to the volume in air is 1: 9.
FIG. 1 is a graph showing the removal rate of VOCs at different temperatures for the composite catalysts of examples 1-4 of the present invention and comparative example 1. It can be seen from the graph that examples 1-4 had a certain removal rate at 100 c and the removal rate for VOCs gas rose rapidly with increasing temperature and 80% conversion was achieved at 200 c; while comparative example 1 had a removal rate of 0 at 100 c, its removal rate was only about 10% even when it was raised to 150 c, and it could reach 80% removal at a temperature of about 250 c. Meanwhile, the highest removal rate of examples 1-4 is more than 98%, while that of comparative example 1 is only 93%. Fig. 1 illustrates both the extremely high removal of VOCs by the composite catalyst of the present invention and the low temperature required for the composite catalyst to treat VOCs.
TABLE 1
Table 1 is a statistical table of the time taken from the start of heating until the removal rate of VOCs was 20%, 40%, 60%, and 80% for example 1 and comparative example 1, respectively. From the analysis in the table, it can be seen that the time required for example 1 and comparative example 1 to reach 20% differs by 17min due to the high temperature required for comparative example 1, while the time for both at 40% and 60% is further increased because example 1 has a faster removal rate than comparative example 1; the difference in required temperature and removal rate resulted in 80% removal being achieved in much shorter time for example 1 than for comparative example 1.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (7)
1. ZnO/CuO-CeO for removing VOCs2The preparation method of the/FeSx composite catalyst is characterized by comprising the following steps:
the method comprises the following steps: dissolve Zinc acetate in 50mL deionized water, H3BTC is dissolved in 100mL of ethanol-DMF mixed solution, and cerium acetylacetonate and copper acetylacetonate deionized water obtain mixed solution A; then dropping the mixed solution A into an aqueous solution of zinc acetate, and carrying out ultrasonic treatment for 30-40min to obtain a mixed solution B; dropping the mixed solution B into H under stirring in water bath at 30-40 deg.C3BTC in ethanol, then allowing the mixture to stir at room temperature for 3-4 h; then transferring the mixed solution into a reaction kettle to react for 12-18h at the temperature of 120-140 ℃, washing the mixed solution for 5 times by using ethanol after the reaction, and placing the product in a vacuum drying box at the temperature of 110 ℃ for 18-24 h;
step two: heating the dried sample to 500 ℃ in a muffle furnace at a speed of 10 ℃/min and calcining for 2-4h at the temperature to obtain a metal oxide porous composite;
step three: adding a proper amount of Na2S is added into deionized water in a water bath at 50-60 ℃, a certain amount of FeCl is added after stirring for 20-30min2The aqueous solution was slowly added with Na using a peristaltic pump2S in an aqueous solution. Then placing the mixture into a water bath with the temperature of 70-80 ℃ for standing for 24h, then adding the compound prepared in the step two into the solution, stirring the mixture at room temperature for 5-7h, continuing to place the solution for aging, filtering the solution after aging to obtain a solid, washing the product for 3 times respectively by using ethanol and deionized water, and freeze-drying to obtain the ZnO/CuO-CeO2the/FeSx composite catalyst.
2. The method of claim 1 wherein the ZnO/CuO-CeO is used to remove VOCs2The preparation method of the/FeSx composite catalyst is characterized in that the addition amount of the zinc acetate in the step one is 0.02-0.03mol, and the zinc acetate and the H are3The mass ratio of BTC is 1:1-1:1.4, and the mass ratio of zinc acetate, cerium acetylacetonate and copper acetylacetonate is 10 (1.1-1.7) to (2.5-4.8); na in the third step2The mass ratio of S to zinc acetate is 1:6-1:9, FeCl2And Na2The mass ratio of S is 1:1-1:1.5, and the aging time in the water bath is 24-36 h.
3. The method of claim 1 wherein the ZnO/CuO-CeO is used to remove VOCs2The preparation method of the/FeSx composite catalyst is characterized in that the addition amount of zinc acetate in the step one is 0.02-0.03mol, the volume ratio of the zinc acetate to the zinc acetate in the ethanol-DMF mixed solution is 2:1-4:1, and the concentration of the mixture in the mixed solution A is 0.2 g/mL.
4. The method of claim 1 wherein the ZnO/CuO-CeO is used to remove VOCs2The preparation method of the/FeSx composite catalyst is characterized in that in the step one, the dropping speed of the mixed solution A is 2ml/min, and the dropping speed of the mixed solution B is 6 ml/min.
5. Zn for removing VOCs according to claim 1O/CuO-CeO2The preparation method of the/FeSx composite catalyst is characterized in that Na is added in the third step2The concentration of the S aqueous solution is 0.6mol/L, FeCl2The concentration of the aqueous solution was 0.6 mol/L.
6. The method according to any one of claims 1 to 5, wherein ZnO/CuO-CeO is used for removing VOCs2The composite catalyst prepared by the/FeSx composite catalyst is characterized in that the load capacity of CuO on ZnO in the catalyst is 24.7-47.4 wt%, and CeO2The loading on ZnO is 22.3wt percent to 37.2wt percent.
7. The method according to any one of claims 1 to 6, wherein the ZnO/CuO-CeO is used for removing VOCs2The composite catalyst prepared by the/FeSx composite catalyst is applied to the removal of VOCs by catalytic oxidation.
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