CN111068666A - Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof - Google Patents
Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof Download PDFInfo
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- CN111068666A CN111068666A CN201911125327.0A CN201911125327A CN111068666A CN 111068666 A CN111068666 A CN 111068666A CN 201911125327 A CN201911125327 A CN 201911125327A CN 111068666 A CN111068666 A CN 111068666A
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- sepiolite
- noble metal
- silver
- temperature oxidation
- oxidation catalyst
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000004113 Sepiolite Substances 0.000 title claims abstract description 54
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 54
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 4
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims abstract description 4
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000004332 silver Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 20
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 16
- 229940071536 silver acetate Drugs 0.000 claims description 16
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910001260 Pt alloy Inorganic materials 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 239000002131 composite material Substances 0.000 abstract description 21
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 239000002082 metal nanoparticle Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000004887 air purification Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 20
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000000877 morphologic effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003905 indoor air pollution Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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Abstract
The invention discloses a sepiolite-supported noble metal formaldehyde room-temperature oxidation catalyst and a preparation method thereof, and belongs to the technical field of indoor air purification. The catalyst consists of sepiolite and noble metal nanoparticles, the noble metal nanoparticles are one of silver, platinum and palladium or one of silver-platinum, silver-palladium and silver-platinum-palladium alloys, the particle size of the nanoparticles is 5-20nm, and the loading capacity is 1-15 wt%. The preparation method provided by the invention is based on the principles of ion adsorption, exchange and the like, and the sepiolite-supported noble metal formaldehyde room-temperature oxidation catalyst is prepared by the processes of impregnation, freeze drying, heat treatment reduction and the like, metal nanoparticles are uniformly supported and dispersed on the sepiolite, the stability is good, the composite catalyst has excellent catalytic activity and stability, and the composite catalyst has important application prospects in the technical field of catalysis such as formaldehyde room-temperature oxidation and the like.
Description
Technical Field
The invention relates to a preparation method of a sepiolite-supported noble metal formaldehyde room-temperature oxidation catalyst material, belonging to the field of indoor air purification.
Background
Human life activities can not breathe, and more than 75% of the time of modern people is indoor activities, especially the time of old, young, weak and sick people indoor activities is more. The indoor air pollution is more direct and intimate with the health. At present, China is in the rapid development stage of urbanization, and the problem of indoor air pollution caused by decoration and construction is not considered with the increase of urban area. Among them, formaldehyde is one of serious indoor air pollutants, and has wide sources and high toxicity. Therefore, how to scientifically and effectively remove formaldehyde in air has become an object of increasing attention of researchers.
At present, there are many methods for removing formaldehyde pollution in air, and the commonly used methods for removing formaldehyde pollution include physical adsorption methods (such as activated carbon, molecular sieve, etc.), biological methods, ozone oxidation methods, plant degradation methods, catalytic oxidation methods, and the like. The physical adsorption method mainly uses the adsorption of porous materials such as activated carbon to remove formaldehyde, but is easily affected by the absorption pore size and faces the problem of secondary pollution caused by desorption; the ozone oxidation method has low reaction efficiency and also has the problem of secondary pollution; plant degradation can degrade formaldehyde to some extent, but its absorption capacity for formaldehyde is limited, making mass production difficult(ii) a Although the biological method has good effect of removing formaldehyde, once microorganisms are leaked, the danger is larger; the catalytic oxidation method is that the catalyst catalyzes oxygen in the air and organic pollutants to generate chemical reactions such as oxidation decomposition and the like, thereby decomposing the organic pollutants such as formaldehyde and the like. The technology can effectively deal with the characteristic of formaldehyde release, does not need additional conditions and can not cause secondary pollution, and can stably and efficiently convert formaldehyde into CO which is no longer harmful2And H2O, is a research hotspot in various treatment modes.
The key point of removing formaldehyde by the catalytic oxidation method is the selection of a catalyst, and the catalyst by the catalytic oxidation method can be divided into a noble metal catalyst and a non-noble metal catalyst. Non-noble metal catalysts are difficult to perform at room temperature. The noble metal catalyst can be loaded on different types of carriers to carry out formaldehyde catalytic oxidation at low temperature even at room temperature. Sepiolite is a natural fibrous hydrous magnesium silicate clay mineral, in the structural unit of which silicon-oxygen tetrahedron and magnesium-oxygen octahedron are mutually alternated, and has the transition type characteristics of a layered and chain structure. The ideal structural formula can be expressed as Si12O30Mg8·(OH)4(H2O)4·8H2And O. The sepiolite has the advantages of adsorbability, cation exchange property, large storage capacity, low price and the like due to the special structure, so the sepiolite has a very wide application prospect.
In conclusion, the sepiolite supported noble metal formaldehyde room temperature oxidation catalyst is prepared by taking sepiolite as a carrier and carrying out the processes of water solution impregnation, freeze drying, heat treatment reduction and the like of noble metal salt. The noble metal nano particles are one of silver, platinum and palladium or one of silver-platinum, silver-palladium and silver-platinum-palladium alloy, and the noble metal exists in a 0-valent form. The particle size of the nano particles is 5-20nm, and the load is adjustable within 1-15 wt%. The composite catalyst prepared by the invention has the advantages that the metal nano particles are uniformly loaded and dispersed on the sepiolite, the stability is good, the composite catalyst has excellent catalytic activity and stability, and the composite catalyst has important application prospects in the technical fields of catalysis such as formaldehyde room-temperature oxidation and the like.
Disclosure of Invention
The invention discloses a preparation method of a sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst, and aims to provide a simple and efficient catalytic material aiming at the prior art, so as to solve the problems of low formaldehyde pollution decomposition efficiency and complex catalytic process in the prior indoor air.
In order to realize the purpose, the invention provides a composite catalytic material which takes sepiolite porous ceramic balls as a carrier and is prepared by the processes of precious metal aqueous solution impregnation, freeze drying, heat treatment reduction and the like, wherein precious metal nano particles are loaded on the surface of sepiolite. The obtained composite material has excellent catalytic performance, is environment-friendly and has wide application prospect.
The invention relates to a preparation method of a sepiolite supported noble metal formaldehyde room temperature oxidation catalyst, which mainly comprises the steps of preparing a noble metal aqueous solution, vacuum impregnation, freeze drying to obtain a noble metal precursor, heat treatment and the like, and is characterized in that:
(1) completely dissolving precious metal salt in distilled water to obtain metal salt solution with certain concentration, wherein the metal salt is any one of silver acetate, chloroplatinic acid, palladium dichloride or a mixture of silver acetate/palladium dichloride, silver acetate/chloroplatinic acid and a mixture of silver acetate/palladium dichloride/metal chloroplatinate;
(2) putting the sepiolite porous ceramic ball into a metal salt solution, adopting a vacuum impregnation process, fully impregnating for 5-30 hours at a certain temperature, wherein the vacuum impregnation temperature is 20-90 ℃, taking out, and carrying out freeze drying treatment to obtain the sepiolite porous ceramic ball loaded with metal cations;
(3) and (3) placing the impregnated sepiolite porous ceramic balls in a tubular furnace, carrying out thermal reduction in a reducing atmosphere, and cooling to obtain the sepiolite noble metal-loaded catalyst material.
The sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst has the following advantages: the sepiolite supported noble metal composite catalyst has stable morphology, can stably exist in indoor and other environments, and cannot form secondary pollution; the composite catalyst shows excellent formaldehyde catalytic oxidation activity, high catalytic selectivity and good catalytic stability, and products of formaldehyde catalytic oxidation are carbon dioxide and water, so that the composite catalyst has no environmental pollution.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
(1) 50ml of distilled water is taken, 0.01mol of palladium chloride is added to be dissolved, and the solution is magnetically stirred for 1 hour to obtain precursor solution.
(2) And (2) soaking 5g of sepiolite with the particle size of 3mm in the precursor solution obtained in the step (1) to ensure that the precursor solution overflows the carrier, putting the sepiolite in a vacuum drying oven for vacuum impregnation for 6 hours at the impregnation temperature of 60 ℃, taking out the sepiolite for freeze drying at the freezing temperature of-40 ℃, the vacuum degree of 10Pa for 12 hours, and drying for 48 hours to obtain the precursor of the palladium chloride/sepiolite composite catalytic material.
(3) And (3) placing the precursor sample obtained in the step (2) in a tubular furnace with the initial temperature of room temperature, introducing hydrogen and argon atmosphere, and carrying out heat treatment at the temperature of 800 ℃ for 2 hours to obtain the nano palladium/sepiolite composite catalytic material with stable morphological structure.
Example 2
(1) 50ml of distilled water is taken, 0.02mol of chloroplatinic acid is added for dissolution, and the precursor solution is obtained after magnetic stirring for 1 hour.
(2) And (2) soaking 5g of sepiolite with the particle size of 3mm in the precursor solution obtained in the step (1) to ensure that the precursor solution overflows the carrier, putting the sepiolite in a vacuum drying oven for vacuum impregnation for 6 hours at the impregnation temperature of 60 ℃, taking out the sepiolite for freeze drying at the freezing temperature of-40 ℃, the vacuum degree of 10Pa for 12 hours, and drying for 48 hours to obtain the precursor of the chloroplatinic acid/sepiolite composite catalytic material.
(3) And (3) placing the precursor sample obtained in the step (2) in a tubular furnace with the initial temperature of room temperature, introducing hydrogen and argon atmosphere, and carrying out heat treatment at the temperature of 800 ℃ for 2 hours to obtain the nano platinum/sepiolite composite catalytic material with stable morphological structure.
Example 3
(1) 50ml of distilled water is taken, 0.02mol of silver acetate is added for dissolution, and the precursor solution is obtained after magnetic stirring for 1 hour.
(2) 3g of sepiolite with the grain diameter of 3mm is soaked in the precursor solution obtained in the step (1), the precursor solution is enabled to permeate the carrier, the carrier is placed in a vacuum drying oven for vacuum impregnation for 6 hours, the impregnation temperature is 60 ℃, the sepiolite is taken out for freeze drying, the freezing temperature is-40 ℃, the vacuum degree is 10Pa, the freezing time is 12 hours, and the precursor of the silver acetate/sepiolite composite catalytic material is obtained after drying for 48 hours.
(3) And (3) placing the precursor sample obtained in the step (2) in a tubular furnace with the initial temperature of room temperature, introducing hydrogen and argon atmosphere, and carrying out heat treatment at the temperature of 600 ℃ for 2 hours to obtain the nano silver/sepiolite composite catalytic material with stable morphological structure.
Example 4
(1) 50ml of distilled water is taken, 0.02mol of silver acetate and chloroplatinic acid are respectively added for dissolution, and the precursor solution is obtained after magnetic stirring for 1 hour.
(2) 3g of sepiolite with the particle size of 3mm is soaked in the precursor solution obtained in the step (1), the precursor solution is enabled to permeate through the carrier, the carrier is placed in a vacuum drying oven for vacuum impregnation for 6 hours, the impregnation temperature is 60 ℃, the sepiolite is taken out for freeze drying, the freezing temperature is-40 ℃, the vacuum degree is 10Pa, the freezing time is 12 hours, and the precursor of the silver acetate and chloroplatinic acid sepiolite composite catalytic material is obtained after drying for 48 hours.
(3) And (3) placing the precursor sample obtained in the step (2) in a tubular furnace with the initial temperature of room temperature, introducing hydrogen and argon atmosphere, and carrying out heat treatment at the temperature of 600 ℃ for 2 hours to obtain the nano silver platinum/sepiolite composite catalytic material with stable morphological structure.
Example 5
(1) 50ml of distilled water is taken, 0.02mol of silver acetate and palladium chloride are respectively added to dissolve, and the mixture is magnetically stirred for 1 hour to obtain a precursor solution.
(2) 3g of sepiolite with the particle size of 3mm is soaked in the precursor solution obtained in the step (1), the precursor solution is enabled to permeate through the carrier, the carrier is placed in a vacuum drying oven for vacuum impregnation for 6 hours, the impregnation temperature is 60 ℃, the sepiolite is taken out for freeze drying, the freezing temperature is-40 ℃, the vacuum degree is 10Pa, the freezing time is 12 hours, and the precursor of the silver acetate and palladium chloride sepiolite composite catalytic material is obtained after drying for 48 hours.
(3) And (3) placing the precursor sample obtained in the step (2) in a tubular furnace with the initial temperature of room temperature, introducing hydrogen and argon atmosphere, and carrying out heat treatment at the temperature of 600 ℃ for 1 hour to obtain the nano silver-palladium/sepiolite composite catalytic material with stable morphological structure.
Example 6
(1) 50ml of distilled water is taken, 0.01mol of silver acetate, palladium chloride and chloroplatinic acid are respectively added to dissolve, and the precursor solution is obtained after magnetic stirring for 1 hour.
(2) 3g of sepiolite with the particle size of 3mm is soaked in the precursor solution obtained in the step (1), the precursor solution is enabled to permeate through the carrier, the carrier is placed in a vacuum drying oven for vacuum impregnation for 6 hours, the impregnation temperature is 60 ℃, the sepiolite is taken out for freeze drying, the freezing temperature is-40 ℃, the vacuum degree is 10Pa, the freezing time is 12 hours, and the precursor of the silver acetate, chloroplatinic acid and palladium chloride/sepiolite composite catalytic material is obtained after drying for 48 hours.
(3) And (3) placing the precursor sample obtained in the step (2) in a tubular furnace with the initial temperature of room temperature, introducing hydrogen and argon atmosphere, and carrying out heat treatment at the temperature of 600 ℃ for 2 hours to obtain the nano silver, platinum and palladium/sepiolite composite catalytic material with stable morphological structure.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (5)
1. A sepiolite supported noble metal formaldehyde room temperature oxidation catalyst material is characterized in that: the catalyst material comprises sepiolite porous ceramic balls and precious metal nano-particles, wherein the diameter of the sepiolite porous ceramic balls in the catalyst material is 2-5mm, the pore diameter of the sepiolite porous ceramic balls is 30nm-2 mu m, the precious metal nano-particles are silver, platinum, palladium or one of silver-platinum alloy, silver-palladium alloy and silver-platinum-palladium alloy, and the loading capacity of the precious metal nano-particles is 1-15 wt%.
2. The preparation method of the sepiolite-supported noble metal formaldehyde room temperature oxidation catalyst according to claim 1, which is characterized in that: the method comprises the following steps:
(1) completely dissolving precious metal salt in distilled water to obtain metal salt solution with certain concentration, wherein the metal salt is any one of silver acetate, chloroplatinic acid, palladium dichloride or a mixture of silver acetate/palladium dichloride, silver acetate/chloroplatinic acid and a mixture of silver acetate/palladium dichloride/metal chloroplatinate;
(2) putting the sepiolite porous ceramic ball into a metal salt solution, adopting a vacuum impregnation process, fully impregnating for 5-30 hours at a certain temperature, wherein the vacuum impregnation temperature is 20-90 ℃, taking out, and carrying out freeze drying treatment to obtain the sepiolite porous ceramic ball loaded with metal cations;
(3) and (3) placing the impregnated sepiolite porous ceramic balls in a tubular furnace, carrying out thermal reduction in a reducing atmosphere, and cooling to obtain the sepiolite noble metal-loaded catalyst material.
3. The preparation method of the sepiolite-supported noble metal formaldehyde room temperature oxidation catalyst according to claim 2, characterized in that: the concentration of the metal salt solution in the step (1) is 0.01-2 mol/L.
4. The preparation method of the sepiolite-supported noble metal formaldehyde room temperature oxidation catalyst according to claim 2, characterized in that: the temperature of the cold trap in the freeze drying in the step (2) is between 40 ℃ below zero and 60 ℃ below zero, the freezing time is 0.5 to 1 day, the vacuum degree is 1 to 100Pa, and the drying time is 2 to 3 days.
5. The preparation method of the sepiolite-supported noble metal formaldehyde room temperature oxidation catalyst according to claim 2, characterized in that: the reducing atmosphere in the step (3) is provided by hydrogen/argon gas mixture or coke, the reducing temperature is 200-800 ℃, and the reaction time is 1-4 hours.
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