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
- Publication number
- CN112121823A CN112121823A CN202011122838.XA CN202011122838A CN112121823A CN 112121823 A CN112121823 A CN 112121823A CN 202011122838 A CN202011122838 A CN 202011122838A CN 112121823 A CN112121823 A CN 112121823A
- Authority
- CN
- China
- Prior art keywords
- cuo
- ceo
- zno
- composite catalyst
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004246 zinc acetate Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000002431 foraging effect Effects 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000006378 damage Effects 0.000 description 4
- 239000001273 butane Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- -1 CO2And H2O Chemical class 0.000 description 1
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
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
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011122838.XA CN112121823A (en) | 2020-10-20 | 2020-10-20 | ZnO/CuO-CeO for removing VOCs2Preparation method and application of/FeSx composite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011122838.XA CN112121823A (en) | 2020-10-20 | 2020-10-20 | ZnO/CuO-CeO for removing VOCs2Preparation method and application of/FeSx composite catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112121823A true CN112121823A (en) | 2020-12-25 |
Family
ID=73853821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011122838.XA Withdrawn CN112121823A (en) | 2020-10-20 | 2020-10-20 | ZnO/CuO-CeO for removing VOCs2Preparation method and application of/FeSx composite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112121823A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892534A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | MO for VOC purificationx/CuxPreparation of O/Cu photocatalyst |
-
2020
- 2020-10-20 CN CN202011122838.XA patent/CN112121823A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892534A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | MO for VOC purificationx/CuxPreparation of O/Cu photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108722497B (en) | TiO 22-MOFs photocatalyst, preparation method and application thereof | |
| CN109248679B (en) | VOCs normal-temperature degradation efficient catalyst and preparation and application thereof | |
| CN108772056B (en) | Preparation of supported cordierite catalyst and photo-thermal synergetic oxidation of VOCs | |
| CN106975481A (en) | The preparation method of alkaline earth metal doping MnO2 catalyst with efficient photo-thermal concerted catalysis purifying VOCs | |
| CN112337461A (en) | Composite material of strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene | |
| CN109054034B (en) | Bimetallic copper/cobalt metal-organic framework material and preparation method and application thereof | |
| CN113262808A (en) | Water-soluble graphite-phase carbon nitride nanosheet catalyst for efficiently removing formaldehyde at room temperature and preparation method thereof | |
| CN102443454B (en) | Oxygen carrier of chemical-looping combustion and preparation method and application thereof | |
| CN113769767B (en) | Conductive catalytic film, preparation method thereof and method for purifying flue gas by coupling ozone through conductive catalytic film | |
| CN112121823A (en) | ZnO/CuO-CeO for removing VOCs2Preparation method and application of/FeSx composite catalyst | |
| CN112691542B (en) | Metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds), and preparation method and application thereof | |
| CN108786896A (en) | A kind of preparation method of noble metal catalyst | |
| CN112058217A (en) | Silicon-based adsorption material capable of being rapidly regenerated and method for microwave in-situ degradation of organic pollutants | |
| CN115090279B (en) | Titanium dioxide supported catalyst for purifying malodorous VOCs in grain and oil processing industry and preparation method thereof | |
| CN111215067A (en) | Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst | |
| CN114452974B (en) | MnO 2 Base formaldehyde removal material, ultrasonic-microwave auxiliary preparation method thereof and application thereof in formaldehyde catalytic oxidation | |
| CN112588298A (en) | Composite catalyst for air purification and preparation method and application thereof | |
| CN112892554A (en) | Two-dimensional layered material with diatomic active phase and preparation method and application thereof | |
| CN113600219A (en) | Catalyst for catalytic oxidation of VOCs and preparation method thereof | |
| CN112387109A (en) | Perfluoropolymer-based titanium dioxide air purification coating and preparation method thereof | |
| Tokoro et al. | The photo-catalytic mechanism for formaldehyde by carbonized TiO2-woody composites | |
| CN115555018B (en) | Catalyst for low-temperature ozone catalytic oxidation of VOCs and preparation method thereof | |
| CN116272860B (en) | VOCs treated regenerated activated carbon and preparation method thereof | |
| RU2771045C1 (en) | Sorption-catalytic material for neutralization of emissions of vocal organic compounds | |
| CN112588299A (en) | Method for treating polluted air based on composite catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201225 |
|
| WW01 | Invention patent application withdrawn after publication |