CN112156781A - Monoatomic VOC oxidation catalyst prepared by combustion method and preparation method and application thereof - Google Patents
Monoatomic VOC oxidation catalyst prepared by combustion method and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000009841 combustion method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 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
- 238000000034 method Methods 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 238000002485 combustion reaction Methods 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 16
- 239000010931 gold Substances 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 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
- 230000002269 spontaneous effect Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 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
- 239000010970 precious metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000010718 Oxidation Activity Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 description 34
- 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 24
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 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
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- B01J23/54—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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- 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
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- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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 relates to the field of catalysts for VOC catalytic oxidation reaction, in particular to a monoatomic VOC oxidation catalyst prepared by a combustion method, which 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 invention also relates to a preparation method and application of the monatomic VOC oxidation catalyst. The invention has the beneficial effects that: manganese oxide with VOC catalytic oxidation activity is used as an active carrier, so that a precious metal active center can be supplemented, and the reaction activity of the catalyst is improved through a synergistic effect.
Description
Technical Field
The present invention relates to the field of catalysts for catalytic oxidation reactions of VOCs.
Background
Volatile Organic Compounds (VOC) are important air pollutants. At present, the VOC pollution treatment methods mainly comprise a condensation recovery method, an absorption method, an adsorption method, a biological purification method and a catalytic oxidation method. Wherein the condensation recovery method and the biological purification method are respectively suitable for the treatment of high-concentration VOC and low-concentration VOC; the absorption method and the adsorption method are suitable for treating the VOC with medium and high concentration, have large treatment capacity and good effect, but have the problem of saturated absorption and adsorption. Compared with the method, the catalytic oxidation method is suitable for the treatment of the VOC with medium and low concentration, has wide application scenes, high VOC conversion efficiency, large gas treatment capacity, complete treatment without adsorption saturation, lower process energy consumption, no secondary pollution, easy control of operation conditions in practical application and simple process flow, and has become a hotspot of air pollution treatment technical research.
The key to the catalytic oxidation reaction of VOCs is the selection of the active sites of the catalyst and the design of the catalyst structure. As a widely applied catalytic material, the noble metal has an unfilled d-electron orbit, 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 noble metal is the most common catalytic material in the VOC catalytic oxidation reaction. 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 VOC oxidation activity as a carrier, introduces the preparation mode of a single-atom catalyst into the preparation of a 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 VOC.
The invention content is as follows:
the invention aims to provide a monoatomic VOC oxidation catalyst prepared by a combustion method and a preparation method and application thereof.
In order to achieve the above object, the present invention prepares a supported noble metal catalyst by an immersion combustion method.
The invention adopts the following scheme: a monoatomic VOC 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 monoatomic VOC 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 precious metal and organic fuel for 6-24 hours under the condition of stirring, placing the 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 comprises 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.
Application of monoatomic VOC oxidation catalyst prepared by combustion method for catalytic conversion of VOC in air at the reaction temperature of 200-450 ℃ and the concentration of VOC in air suitable for environment of 1000-6000 mg/m3。
The invention has the beneficial effects that: (1) manganese oxide with VOC catalytic oxidation activity is used as an active carrier, so that a precious metal active center can be supplemented, and the reaction activity of the catalyst 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 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 was charged in a fixed bedIn the reactor, the reaction space velocity is 3600h-1The reaction temperature is 30 ℃, and the VOC concentration in the air can be adjusted to 6000mg/m within 24h3Reduced 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 VOC concentration in the air can be controlled from 5000mg/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 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 VOC concentration in the air can be controlled from 4000mg/m within 24h3Reduced 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 100m2/gPore volume of 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 VOC concentration in the air can be adjusted to 6000mg/m within 24h3Reduced to 0mg/m3The conversion rate is 100 percent
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 VOC concentration in the air can be controlled from 4500mg/m within 24 hours3Reduced to 0mg/m3The conversion was 100%.
Example 6
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 glycine, and totaling 30 ml. Adding 10g of manganese oxide carrier into the solution, soaking for 6 hours under the stirring condition, and finishing the soakingAnd then placing the mixture in a muffle furnace, heating to 300 ℃, roasting at 350 ℃ for 2 hours after spontaneous combustion, and then 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 VOC concentration in the air can be controlled from 5500mg/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 VOC concentration in the air can be adjusted to 6000mg/m within 24h3Reduced to 0mg/m3The conversion was 100%.
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. 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 30 ℃ for 24h to make the VOC concentration in the air from 6000mg/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 make the VOC concentration in the air from 3000mg/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 VOC concentration in the air to 5000mg/m3Reduced to 0mg/m3The conversion was 100%.
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, soaking for 6h under stirring, and mixing after soakingAnd placing the mixture in a muffle furnace, heating to 300 ℃, roasting for 2 hours 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 VOC concentration in the air can be controlled from 5000mg/m within 24 hours3Reduce to 4000mg/m3The conversion was 20%.
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 VOC concentration in the air can be controlled from 5000mg/m within 24 hours3Reduce to 4000mg/m3The conversion was 20%.
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. 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 VOC concentration in the air can be controlled from 4000mg/m within 24h3Reduced to 3000mg/m3The conversion was 25%.
Claims (9)
1. A monoatomic VOC 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. A combustion-prepared monatomic VOC oxidation catalyst according to claim 1, wherein: the noble metal is at least 2 of platinum, ruthenium, palladium and gold.
3. A combustion-prepared monatomic VOC oxidation catalyst according to 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 VOC oxidation catalyst prepared by the combustion method of claim 1, wherein: soaking 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 under a stirring condition, placing the mixture in a muffle furnace after soaking, 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 of claim 4, wherein the method comprises the steps of: the soluble salt of the noble metal is nitrate of the noble metal.
6. The method of claim 4, wherein the method comprises the steps of: the organic fuel comprises at least one of glycol, urea and glycine.
7. The method of claim 4, wherein the method comprises the steps of: the adding amount of the organic fuel is 10-75 wt% of the mass of the catalyst.
8. The method of claim 4, wherein the method comprises the steps of: the noble metal is at least 2 of platinum, ruthenium, palladium and gold.
9. Use of a combustion-prepared monatomic VOC oxidation catalyst of claim 1, wherein: the catalyst is used for catalytic conversion of VOC in air, the reaction temperature is 200-450 ℃, and the concentration of VOC in air suitable for environment is 1000-6000 mg/m3。
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