CN112156780A - Monoatomic formaldehyde oxidation catalyst prepared by combustion method and preparation method and application thereof - Google Patents
Monoatomic formaldehyde oxidation catalyst prepared by combustion method and preparation method and application thereof Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000009841 combustion method Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 238000002791 soaking Methods 0.000 claims description 26
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 238000002485 combustion reaction Methods 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 230000002269 spontaneous effect Effects 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 4
- 230000010718 Oxidation Activity Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract 1
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
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- 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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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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Abstract
The invention belongs to a catalyst for formaldehyde catalytic oxidation reaction and a preparation method and application thereof, and particularly relates to a manganese oxide loaded noble metal monatomic formaldehyde oxidation catalyst and a preparation method and application thereof. The invention takes manganese oxide with formaldehyde catalytic oxidation activity as an active carrier, can supplement precious metal active centers, and improves the catalyst reaction activity through synergistic effect. Through modulation of a preparation mode, catalyst composition content and relevant key conditions, the distribution of the noble metal active centers of the catalyst is adjusted, the coordination number of noble metal atoms is reduced, and the noble metal active centers with monoatomic distribution are obtained. The characteristics of various valence states of manganese species, rich pore structure and more defect sites are utilized to realize uniform and stable position falling of the noble metal single atom, so that better catalytic activity and stability are obtained.
Description
Technical Field
The invention belongs to a catalyst for formaldehyde catalytic oxidation reaction and a preparation method and application thereof, and particularly relates to a noble metal monoatomic formaldehyde oxidation catalyst prepared by a combustion method and a preparation method and application thereof.
Background
Formaldehyde has definite carcinogenic and teratogenic effects and is an important indoor pollutant. At present, the formaldehyde pollution is mainly treated by ventilation, biological purification, physical adsorption, plasma, photocatalytic oxidation, catalytic oxidation and the like. The application scenes of the ventilation method and the biological purification method are limited, and the purification effect is unstable; the physical adsorption method has the problems of saturated regeneration of the adsorption material and difficult long-term continuous work; the plasma method and the photocatalytic oxidation method have good treatment effect, but the treated product may have secondary pollution. Compared with the method, the catalytic oxidation method has the advantages of high formaldehyde conversion efficiency, large gas treatment capacity, complete treatment, no adsorption saturation, low process energy consumption, no secondary pollution, easy control of operation conditions in practical application and simple process flow, and becomes a hotspot of indoor air pollution treatment technology research.
The key of the formaldehyde catalytic oxidation reaction lies in the selection of the active center of the catalyst and the design of the catalyst structure. As a widely applied catalytic material, the noble metal has unfilled d-electron orbitals, the surface is easy to adsorb reactants, the adsorption strength is moderate, an active intermediate product is favorably formed, the activity and the stability of the catalyst are good, and the catalyst is the most common catalytic material in the catalytic oxidation reaction of formaldehyde. However, the precious metals are scarce and expensive, and the amount of the precious metals seriously affects the raw material cost of the catalyst. How to improve the utilization rate of noble metal atoms under the condition of lower loading capacity so as to improve the catalytic efficiency becomes a key problem which needs to be solved urgently for the application of noble metal catalysts.
Previous researches show that the electronic environment, the crystal structure, the interface property and the dispersion condition of an active center can be adjusted to a certain degree through the synthesis of noble metal alloy, the doping of non-noble metal auxiliary agents and the modulation of carrier types and carrier microstructures, and the catalytic efficiency of platinum is improved. However, the characterization results confirm that, in these studies, the obtained noble metal species still exist in the form of nanoclusters in the catalyst, a large number of atoms in the cluster phase do not directly participate in the catalytic reaction, and the utilization rate of noble metal atoms also has the potential of further improvement.
In 2011, the single atom catalysis concept was first proposed by the team of academists, the institute of chemistry and physics, the institute of academy of sciences, China. The method is to load metal atoms with catalytic activity on a catalyst carrier in a monodispersed manner. From the coordination information, no conventional metal-metal bond occurs in the catalyst. The single-molecule catalyst has 100% atom utilization rate and has obvious price advantage when loading noble metal materials. The invention adopts manganese oxide with a porous structure, a variable valence state and certain formaldehyde oxidation activity as a carrier, introduces the preparation mode of a single-atom catalyst into the preparation of the noble metal/manganese oxide catalyst, and designs and synthesizes the single-atom noble metal-based manganese oxide catalyst so as to achieve the aim of high-efficiency catalytic conversion of formaldehyde.
The invention content is as follows:
the invention aims to provide a catalyst for formaldehyde catalytic oxidation reaction and a preparation method and application thereof, and particularly relates to a manganese oxide-loaded noble metal monatomic formaldehyde oxidation catalyst and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows: a monoatomic formaldehyde oxidation catalyst prepared by a combustion method comprises the following components in percentage by weight: 0.01-1.5 wt% of noble metal, and the balance of manganese oxide carrier, wherein the valence of manganese in the manganese oxide carrier is between +2 and + 4.
The noble metal is at least 2 of platinum, ruthenium, palladium and gold;
the specific surface area of the manganese oxide carrier is 50-200 m2Per g, pore volume of 0.1-0.5 cm3/g；
A preparation method of a monatomic formaldehyde oxidation catalyst prepared by a combustion method comprises the steps of dipping a manganese oxide carrier in a solution of 0.5-1.3 g/ml of soluble salt of noble metal and organic fuel for 6-24 hours, placing a mixture in a muffle furnace after dipping, heating at 300-400 ℃, roasting at 350-450 ℃ for 1-3 hours after spontaneous combustion, cooling, and granulating to obtain a finished product catalyst.
The soluble salt of the noble metal is nitrate of the noble metal;
the organic fuel is at least one of glycol, urea and glycine;
the adding amount of the organic fuel is 10-75 wt% of the mass of the catalyst.
The application of the monatomic formaldehyde oxidation catalyst prepared by the combustion method is used for catalytic conversion of formaldehyde in air under a static or forced ventilation state, the reaction temperature is-15-100 ℃, and the air formaldehyde concentration applicable to the environment is 0.01-1.0 mg/m3。
The invention has the beneficial effects that: (1) manganese oxide with formaldehyde catalytic oxidation activity is used as an active carrier, so that a precious metal active center can be supplemented, and the catalyst reaction activity is improved through a synergistic effect. (2) Through modulation of a preparation mode, catalyst composition content and relevant key conditions, the distribution of the noble metal active centers of the catalyst is adjusted, the coordination number of noble metal atoms is reduced, and the noble metal active centers with monoatomic distribution are obtained. (3) The characteristics of various valence states of manganese species, rich pore structure and more defect sites are utilized to realize uniform and stable position falling of the noble metal single atom, so that better catalytic activity and stability are obtained. (4) The catalyst is prepared by adopting a combustion method, the migration of noble metal particles is promoted in the high-temperature combustion process, the preparation process is rapid, the noble metal atoms of the finished catalyst are uniformly dispersed, and the catalytic activity is good.
Detailed Description
The preparation process disclosed in this patent is further described below by way of specific examples, but the present invention is not limited by the following examples.
Example 1
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 100m2Per g, pore volume 0.1cm3Manganese is +4 in valence/g. Preparing chloroplatinic acid solution with platinum concentration of 1.0g/ml and preparing nitric acid with gold concentration of 0.5g/mlAnd (3) adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of urea into 1ml of platinum nitrate solution and 1ml of gold nitrate solution to obtain 30ml of gold solution in total. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the concentration of formaldehyde in the air can be controlled from 0.8mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 2
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 150m2Per g, pore volume 0.4cm3Manganese is +2 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of glycine, and totaling 30 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 3
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 200m2Per g, pore volume 0.5cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 2.0g/ml, preparing a ruthenium nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the ruthenium nitrate solution, adding 24ml of deionized water, 4ml of ethylene glycol and 4ml of urea, and totaling 34 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the manganese oxide-manganese-And (4) preparing a catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the concentration of formaldehyde in the air can be controlled from 0.9mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 4
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 100m2Per g, pore volume 0.1cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 2.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 1ml of ethylene glycol and 1ml of urea, and totaling 28 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 12h under the stirring condition, placing the mixture in a muffle furnace after soaking, heating to 350 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 5000h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 5
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 12000m2Per g, pore volume 0.3cm3Manganese is +2 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of urea, and totaling 30 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction airspeed is 6000h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 6
Taking manganese oxide10g of carrier, and the specific surface area of the manganese oxide carrier is 100m2Per g, pore volume 0.1cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of glycine, and totaling 30 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 5000h-1The reaction temperature is 30 ℃, and the concentration of formaldehyde in the air can be controlled from 0.5mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 7
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 200m2Per g, pore volume 0.2cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 3ml of ethylene glycol and 2ml of urea, and totaling 31 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0.05mg/m3The conversion was 95%.
Example 8
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 100m2Per g, pore volume 0.1cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of urea, and totaling 30 ml. Into the solutionAdding 10g of manganese oxide carrier, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. Placing 5g of the obtained catalyst in a glass cover with the volume of 10L, reacting at 30 ℃ for 24h to control the formaldehyde concentration in the air from 1.0mg/m3Reduced to 0mg/m3The conversion was 100%.
Example 9
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 100m2Per g, pore volume 0.1cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of urea, and totaling 30 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. Placing 5g of the obtained catalyst in a glass cover with the volume of 10L, reacting at 40 ℃ for 24h to control the formaldehyde concentration in the air from 1.0mg/m3Reduced to 0mg/m3The conversion was 100%.
Example 10
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 100m2Per g, pore volume 0.1cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 2ml of ethylene glycol and 2ml of urea, and totaling 30 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. Placing 5g of the obtained catalyst in a glass cover with the volume of 10L, reacting at 50 ℃ for 24h to adjust the formaldehyde concentration in the air from 1.0mg/m3Reduced to 0mg/m3Conversion rate of100%。
Comparative example 1
Taking 10g of alumina carrier, preparing chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 3ml of ethylene glycol and 2ml of urea, and totaling 31 ml. Adding 10g of alumina carrier into the solution, dipping for 6h under the stirring condition, placing the mixture in a muffle furnace after dipping, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0.95mg/m3The conversion was 5%.
Comparative example 2
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 800m2Per g, pore volume 0.9cm3Mg, Mn + 7. Preparing a chloroplatinic acid solution with platinum concentration of 1.0g/ml, preparing a gold nitrate solution with gold concentration of 0.5g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 3ml of ethylene glycol and 2ml of urea, and totaling 31 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0.60mg/m3The conversion was 40%.
Comparative example 3
Taking 10g of manganese oxide carrier, wherein the specific surface area of the manganese oxide carrier is 800m2Per g, pore volume 0.9cm3Manganese is +4 in valence/g. Preparing a chloroplatinic acid solution with platinum concentration of 6.0g/ml, preparing a gold nitrate solution with gold concentration of 5.0g/ml, taking 1ml of the platinum nitrate solution and 1ml of the gold nitrate solution, adding 24ml of deionized water, 3ml of ethylene glycol and 2ml of urea, and totaling 31 ml. Into the solutionAdding 10g of manganese oxide carrier, soaking for 6h under the condition of stirring, placing the mixture in a muffle furnace after soaking, heating to 300 ℃, roasting for 2h at 350 ℃ after spontaneous combustion, cooling and granulating to obtain the finished catalyst. 5g of the obtained catalyst is filled into a fixed bed reactor, and the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the formaldehyde concentration in the air can be controlled from 1.0mg/m within 24 hours3Reduced to 0.70mg/m3The conversion was 30%.
Claims (9)
1. A monoatomic formaldehyde oxidation catalyst prepared by a combustion method is characterized in that: the catalyst comprises the following components in percentage by weight: 0.01-1.5 wt% of noble metal, and the balance of manganese oxide carrier, wherein the valence of manganese in the manganese oxide carrier is between +2 and + 4.
2. The combustion-prepared monatomic formaldehyde oxidation catalyst of claim 1, wherein: the noble metal is at least 2 of platinum, ruthenium, palladium and gold.
3. The combustion-prepared monatomic formaldehyde oxidation catalyst of claim 1, wherein: the specific surface area of the manganese oxide carrier is 50-200 m2Per g, pore volume of 0.1-0.5 cm3/g。
4. A method for preparing a monatomic formaldehyde oxidation catalyst prepared by a combustion method according to claim 1, which is characterized in that: soaking a manganese oxide carrier in a solution of 0.5-1.3 g/ml of soluble salt of a noble metal and an organic fuel for 6-24 hours, placing the mixture in a muffle furnace after the soaking is finished, heating at 300-400 ℃, roasting at 350-450 ℃ for 1-3 hours after spontaneous combustion, and then cooling and granulating to obtain the finished catalyst.
5. The method for preparing a monatomic formaldehyde oxidation catalyst according to claim 4, which is produced by a combustion method, wherein: the soluble salt of the noble metal is nitrate of the noble metal.
6. The method for preparing a monatomic formaldehyde oxidation catalyst according to claim 4, which is produced by a combustion method, wherein: the organic fuel is at least one of glycol, urea and glycine.
7. The method for preparing a monatomic formaldehyde oxidation catalyst according to claim 4, which is produced by a combustion method, wherein: the adding amount of the organic fuel is 10-75 wt% of the mass of the catalyst.
8. The method for preparing a monatomic formaldehyde oxidation catalyst according to claim 4, which is produced by a combustion method, wherein: the noble metal is at least 2 of platinum, ruthenium, palladium and gold.
9. The use of a combustion-prepared monatomic formaldehyde oxidation catalyst of claim 1, wherein: the catalyst is used for catalytic conversion of formaldehyde in air under a static or forced ventilation state, the reaction temperature is-15-100 ℃, and the formaldehyde concentration of the air applicable to the environment is 0.01-1.0 mg/m3。
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