CN109225216B - Anti-aging catalyst for purifying volatile organic compounds and preparation method thereof - Google Patents
Anti-aging catalyst for purifying volatile organic compounds and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 24
- 230000003712 anti-aging effect Effects 0.000 title description 4
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 104
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 68
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000919 ceramic Substances 0.000 claims abstract description 67
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 28
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 21
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000003883 substance clean up Methods 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 29
- 239000011268 mixed slurry Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 102220042174 rs141655687 Human genes 0.000 claims 1
- 238000004513 sizing Methods 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000007581 slurry coating method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 petrochemical Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- 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
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses an aging-resistant volatile organic compound purification catalyst, wherein an oxidative catalyst coating is coated on the surface of a carrier; the coating contains Al2O3、CeO2、MnO2Noble metal Pt and noble metal Pd; corresponding to one liter of cordierite honeycomb ceramic carrier, Al2O3、CeO2And MnO with MnO2The dosage of the composition is respectively 80-200 g, 5-30 g and 10-30 g; the usage amount of the noble metal Pt and the noble metal Pd is respectively 6-50 g and 10-20 g per cubic foot of cordierite honeycomb ceramic carrier; the preparation method comprises the following steps: impregnation of noble metal oxide solution into Al2O3Al loaded with noble metals Pt and Pd on powder2O3Drying, roasting, grinding and preparing CeO2And MnO2The precursor solution and the precursor solution are dripped into the ground slurry, and the steps of coating, drying and roasting are carried out. The catalyst of the invention has good stability, can effectively catalyze and oxidize the discharged pollutants into pollution-free gas CO2And H2O, thereby meeting the emission regulation requirements.
Description
Technical Field
The invention discloses an anti-aging catalyst for purifying volatile organic compounds, and also discloses an anti-aging catalyst for purifying volatile organic compounds and a preparation method thereof.
Background
VOCs refer to various volatile organic compounds with boiling points of 50-260 ℃ under normal pressure, and are usually discharged by coating, petrochemical, fine chemical enterprises and the like. The environment is seriously harmed and the human health is invaded, so that the national attention is paid, and corresponding laws and regulations are issued to establish the discharge standard of the VOCs.
Volatile organic compounds can be treated in various ways, including direct combustion, catalytic oxidation, adsorption, biological purification, and photocatalytic oxidation. The direct combustion method has high treatment temperature reaching 900 ℃, increases the difficulty and danger of system control, and causes more serious oxynitride generation and secondary pollution due to high temperature. Adsorption methods require a post-treatment system and therefore are not used alone.
The catalytic oxidation method is characterized in that volatile organic compounds are converted into pollution-free carbon dioxide and water in the presence of a catalyst, the operating temperature is generally 300-500 ℃, the system control is relatively simple, the high-temperature risk is low, secondary pollution of oxynitride cannot be generated, and the method has obvious advantages, so that the method is highly concerned. However, the catalytic oxidation treatment technology also has the problems that the catalyst grows up in precious metal particles under the condition of 300-500 ℃ for a long time, the activity is rapidly reduced, and the inactivation is caused, so that the catalyst needs to be frequently replaced, and the cost is too high. The development of catalysts with high stability is therefore central to the problem.
The catalyst stability is related to the catalyst carrier, the initial state and the structure of the noble metal, wherein the noble metal catalyst with the core-shell structure has ultrahigh stability, and is verified in a three-way catalyst and a catalytic hydrogenation catalyst, so that the catalytic oxidation catalyst is prepared into a type with the core-shell structure, the stability of the catalyst is obviously improved, and the operation cost of the catalytic oxidation technology is reduced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an aging-resistant volatile organic compound purification catalyst with high catalytic activity and high durability for toluene.
The invention also aims to provide a preparation method of the aging-resistant volatile organic compound purification catalyst.
According to the technical scheme provided by the invention, in the preparation method of the aging-resistant volatile organic compound purification catalyst, an oxidative catalyst coating is coated on the surface of a cordierite honeycomb ceramic carrier; the oxidative catalyst coating contains Al2O3、CeO2、MnO2Noble metal Pt and noble metal Pd; corresponding to one liter of cordierite honeycomb ceramic carrier, Al2O3In an amount of 80 to 200g of CeO2In an amount of 5 to 30g, MnO2The using amount of (A) is 10-30 g; and the usage amount of the noble metal Pt is 6-50 g and the usage amount of the noble metal Pd is 10-20 g for each cubic foot of cordierite honeycomb ceramic carrier.
The preparation method of the aging-resistant volatile organic compound purification catalyst comprises the following steps:
a. firstly, measuring the volume of a cordierite honeycomb ceramic carrier, and preparing Pt (NO) according to 6-50 g of noble metal Pt and 10-20 g of noble metal Pd corresponding to each cubic foot of cordierite honeycomb ceramic carrier3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixed to form a noble metal mixed oxide as Pt (NO)3)2And Pd (NO)3)25-30 times of the total weight of the above components, stirring and mixing uniformly to form a noble metal mixed oxide solution, and preparing 80-200 g of Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
b. al loaded with noble metal oxide2O3Drying the slurry, controlling the drying temperature at 100-120 ℃, roasting after drying, and controlling the roasting temperatureControlling the roasting time at 500-600 ℃ for 1-3 hours to obtain Al loaded with noble metal Pt and noble metal Pd2O3Powder;
c. loading Al with noble metal Pt and noble metal Pd2O3Pulverizing the powder to D90 ═ 40 μm, preparing into slurry, and then grinding the slurry to D90 of 10-30 μm, wherein the solid content is controlled at 35-40%;
d. 5-30 g of CeO is correspondingly arranged according to each liter of cordierite honeycomb ceramic carrier2And 10 to 30g of MnO2Preparation of CeO2And MnO2A precursor of (5), CeO2And MnO2The precursor is uniformly mixed in the aqueous solution to obtain a precursor aqueous solution;
e. c, dropwise adding the precursor water solution into the slurry obtained in the step c, and uniformly stirring and mixing to obtain mixed slurry;
f. coating the mixed slurry on the surface of a cordierite honeycomb ceramic carrier, and drying the cordierite honeycomb ceramic carrier coated with the mixed slurry, wherein the drying temperature is controlled to be 145-155 ℃;
g. and roasting the dried cordierite honeycomb ceramic carrier at the temperature of 500-600 ℃ for 2-4 hours, and cooling to room temperature after roasting to obtain the aging-resistant catalyst for purifying volatile organic compounds.
The CeO2Is Ce (NO)3)3·6(H2O)。
The MnO2The precursor of (A) is Mn (NO)3)2。
The catalyst of the invention has good stability, and can effectively catalyze and oxidize the discharged pollutants to convert the discharged pollutants into pollution-free gas CO2And H2O, thereby meeting the emission regulation requirements.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Comparative example 1
The preparation method of the organic pollutant catalytic oxidation catalyst comprises the following steps:
(1) the surface of the alumina is loaded with Pt and Pd: the volume of cordierite honeycomb ceramic carrier was measured and Pt (NO) was prepared in accordance with 10g of noble metal Pt and 5g of noble metal Pd per cubic foot of cordierite honeycomb ceramic carrier3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixing to form a noble metal mixed solution according to Pt (NO)3)2And Pd (NO)3)25 times of the total weight of the raw materials, adding PEG200 solution, stirring, mixing, and preparing 190g Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
(2) corresponding 5g of CeO per liter of cordierite honeycomb ceramic carrier2And 10g of MnO2Preparation of Ce (NO)3)3·6(H2O) and Mn (NO)3)2Adding Ce (NO)3)3And Mn (NO)3)2Uniformly mixing the precursor solution and the Al precursor solution in an aqueous solution to obtain a precursor aqueous solution, and dropwise adding the precursor aqueous solution to the Al of the noble metal oxide obtained in the step (1)2O3Stirring and mixing the slurry evenly to obtain mixed slurry;
(3) slurry coating: coating the mixed slurry obtained in the step (2) on the surface of a cordierite honeycomb ceramic carrier;
(4) drying the catalyst: fast drying the cordierite honeycomb ceramic carrier coated with the mixed slurry at the temperature of 150 ℃, wherein the drying time is 3 hours, and evaporating water in the mixed slurry;
(5) roasting the catalyst: and putting the dried carrier into a muffle furnace, roasting for 3 hours at 500 ℃, and naturally cooling to room temperature after heat preservation to obtain the catalyst.
Example 1
The preparation method of the aging-resistant volatile organic compound purification catalyst comprises the following steps:
a. cordierite per cubic foot honeycomb ceramicThe carrier prepared Pt (NO) with 10g of noble metal Pt and 5g of noble metal Pd3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixing the noble metal solutions according to Pt (NO)3)2And Pd (NO)3)2Adding PEG200 solution 10 times of the total weight of the above components, stirring, mixing to obtain noble metal mixed solution, and preparing 190g Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
b. al loaded with noble metal oxide2O3Drying the slurry, controlling the drying temperature at 100 ℃, roasting the dried slurry in a muffle furnace at 500 ℃ for 1 hour to obtain Al loaded with noble metal Pt and noble metal Pd2O3Powder;
c. loading Al with noble metal Pt and noble metal Pd2O3Pulverizing the powder to D90 ═ 40 μm, preparing into slurry, and then grinding the slurry to D90 of 10-30 μm, wherein the solid content is controlled at 35-40%;
d. corresponding 5g of CeO per liter of cordierite honeycomb ceramic carrier2And 10g of MnO2Preparation of Ce (NO)3)3·6(H2O) and Mn (NO)3)2Adding Ce (NO)3)3·6(H2O) and Mn (NO)3)2Uniformly mixing the mixture in an aqueous solution to obtain a precursor aqueous solution;
e. c, dropwise adding the precursor water solution into the slurry obtained in the step c, and uniformly stirring and mixing to obtain mixed slurry;
f. coating the mixed slurry on the surface of a cordierite honeycomb ceramic carrier, and drying the cordierite honeycomb ceramic carrier coated with the mixed slurry, wherein the drying temperature is controlled at 150 ℃;
g. and (3) roasting the dried cordierite honeycomb ceramic carrier for 3 hours in a muffle furnace at the temperature of 500 ℃, and cooling to room temperature after roasting to obtain the aging-resistant catalyst for purifying volatile organic compounds.
In the aging-resistant volatile organic compound-purified catalyst obtained by the preparation method of example 1, an oxidative catalyst coating layer was coated on the surface of a cordierite honeycomb ceramic carrier; the oxidative catalyst coating contains Al2O3、CeO2、MnO2Noble metal Pt and noble metal Pd; corresponding to one liter of cordierite honeycomb ceramic carrier, Al2O3Is 190g of CeO2In an amount of 5g, MnO2The usage amount of (2) is 10 g; and the usage amount of the noble metal Pt is 10g and the usage amount of the noble metal Pd is 5g for each cubic foot of the cordierite honeycomb ceramic carrier.
Comparative example 2
The preparation method of the organic pollutant catalytic oxidation catalyst comprises the following steps:
(1) the surface of the alumina is loaded with Pt and Pd: the volume of cordierite honeycomb ceramic carrier was measured and Pt (NO) was prepared in accordance with 10g of noble metal Pt and 5g of noble metal Pd per cubic foot of cordierite honeycomb ceramic carrier3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixing the noble metal solutions according to Pt (NO)3)2And Pd (NO)3)2Adding PEG200 solution 10 times of the total weight of the above components, stirring, mixing to obtain noble metal mixed solution, and preparing 190g Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
(2) 30g of CeO per liter of cordierite honeycomb ceramic carrier2And 30g of MnO2Preparation of Ce (NO)3)3And Mn (NO)3)2Adding Ce (NO)3)3And Mn (NO)3)2Uniformly mixing the mixture in an aqueous solution to obtain a precursor aqueous solution, and dropwise adding the precursor aqueous solution to the aqueous solution obtained in the step (1)Al of noble metal oxide2O3Stirring and mixing the slurry evenly to obtain mixed slurry;
(3) slurry coating: coating the mixed slurry obtained in the step (2) on the surface of a cordierite honeycomb ceramic carrier;
(4) drying the catalyst: fast drying the cordierite honeycomb ceramic carrier coated with the mixed slurry at the temperature of 150 ℃, wherein the drying time is 3 hours, and evaporating water in the mixed slurry;
(5) roasting the catalyst: and putting the dried carrier into a muffle furnace, roasting for 3 hours at 500 ℃, and naturally cooling to room temperature after heat preservation to obtain the catalyst.
Example 2
The preparation method of the aging-resistant volatile organic compound purification catalyst comprises the following steps:
a. pt (NO) was prepared as 10g of noble metal Pt and 5g of noble metal Pd per cubic foot of cordierite honeycomb ceramic substrate3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixing the noble metal solutions according to Pt (NO)3)2And Pd (NO)3)2Adding PEG200 solution 10 times of the total weight of the above components, stirring, mixing to obtain noble metal mixed solution, and preparing 190g Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
b. al loaded with noble metal oxide2O3Drying the slurry to obtain a crude catalyst, controlling the drying temperature at 100 ℃, roasting the dried crude catalyst in a muffle furnace at 500 ℃ for 3 hours to obtain Al loaded with noble metal Pt and noble metal Pd2O3Powder;
c. loading Al with noble metal Pt and noble metal Pd2O3The powder was pulverized to D90 ═ 40 μm and prepared into a slurry,grinding the slurry until D90 is within 10-30 μm, and the solid content is controlled at 35-40%;
d. 30g of CeO per liter of cordierite honeycomb ceramic carrier2And 30g of MnO2Preparation of Ce (CH)3COOH)2And Mn (CH)3COOH)2Adding Ce (CH)3COOH)2And Mn (CH)3COOH)2Uniformly mixing the mixture in an aqueous solution to obtain a precursor aqueous solution;
e. c, dropwise adding the precursor water solution into the slurry obtained in the step c, and uniformly stirring and mixing to obtain mixed slurry;
f. coating the mixed slurry on the surface of a cordierite honeycomb ceramic carrier, and drying the cordierite honeycomb ceramic carrier coated with the mixed slurry, wherein the drying temperature is controlled at 150 ℃;
g. and (3) roasting the dried cordierite honeycomb ceramic carrier for 3 hours in a muffle furnace at the temperature of 500 ℃, and cooling to room temperature after roasting to obtain the aging-resistant catalyst for purifying volatile organic compounds.
In the aging-resistant volatile organic compound-purified catalyst obtained by the preparation method of example 2, an oxidative catalyst coating was coated on the surface of a cordierite honeycomb ceramic carrier; the oxidative catalyst coating contains Al2O3、CeO2、MnO2Noble metal Pt and noble metal Pd; corresponding to one liter of cordierite honeycomb ceramic carrier, Al2O3Is 190g of CeO2In an amount of 30g, MnO2The using amount of (2) is 30 g; and the usage amount of the noble metal Pt is 10g and the usage amount of the noble metal Pd is 5g for each cubic foot of the cordierite honeycomb ceramic carrier.
Comparative example 3
The preparation method of the organic pollutant catalytic oxidation catalyst comprises the following steps:
(a) the surface of the alumina is loaded with Pt and Pd: the volume of cordierite honeycomb ceramic carrier was measured and Pt (NO) was prepared in accordance with 10g of noble metal Pt and 5g of noble metal Pd per cubic foot of cordierite honeycomb ceramic carrier3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixing the noble metal solutions according to Pt (NO)3)2And Pd (NO)3)220 times of the total weight of the above components, stirring and mixing to obtain a noble metal mixed solution, and preparing 190g of Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
(b) 20g of CeO per liter of cordierite honeycomb ceramic carrier2And 20g of MnO2Preparation of Ce (NO)3)3·6(H2O) and Mn (NO)3)2Adding Ce (NO)3)3·6(H2O) and Mn (NO)3)2Uniformly mixing the precursor solution and the Al precursor solution in an aqueous solution to obtain a precursor aqueous solution, and dropwise adding the precursor aqueous solution to the Al of the noble metal oxide obtained in the step (1)2O3Stirring and mixing the slurry evenly to obtain mixed slurry;
(c) slurry coating: coating the mixed slurry obtained in the step (b) on the surface of a cordierite honeycomb ceramic carrier;
(d) drying the catalyst: fast drying the cordierite honeycomb ceramic carrier coated with the mixed slurry at the temperature of 150 ℃, wherein the drying time is 3 hours, and evaporating water in the mixed slurry;
(e) roasting the catalyst: and putting the dried carrier into a muffle furnace, roasting for 3 hours at 500 ℃, and naturally cooling to room temperature after heat preservation to obtain the catalyst.
Example 3
The preparation method of the aging-resistant volatile organic compound purification catalyst comprises the following steps:
a. the volume of cordierite honeycomb ceramic carrier was measured and Pt (NO) was prepared in accordance with 10g of noble metal Pt and 5g of noble metal Pd per cubic foot of cordierite honeycomb ceramic carrier3)2And Pd (NO)3)2Mixing Pt (NO)3)2And Pd (NO)3)2Mixed to form a noble metal mixed oxide as Pt (NO)3)2And Pd (NO)3)2Adding PEG200 solution 10 times of the total weight of the above components, stirring, mixing to obtain noble metal mixed oxide solution, and preparing 190g Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3Obtaining Al loaded with noble metal oxide on the powder2O3Slurry;
b. al loaded with noble metal oxide2O3Drying the slurry to obtain a crude catalyst, controlling the drying temperature at 100 ℃, roasting the dried crude catalyst in a muffle furnace at 500 ℃ for 2 hours to obtain Al loaded with noble metal Pt and noble metal Pd2O3Powder;
c. loading Al with noble metal Pt and noble metal Pd2O3Grinding the powder to D90 ═ 40 μm to prepare slurry, and grinding the slurry to D90 of 30 μm, wherein the solid content is controlled to be 35-40%;
d. 20g of CeO per liter of cordierite honeycomb ceramic carrier2And 20g of MnO2Preparation of Ce (NO)3)3·6(H2O) and Mn (NO)3)2Adding Ce (NO)3)3·6(H2O) and Mn (NO)3)2Uniformly mixing the mixture in an aqueous solution to obtain a precursor aqueous solution;
e. c, dropwise adding the precursor water solution into the slurry obtained in the step c, and uniformly stirring and mixing to obtain mixed slurry;
f. coating the mixed slurry on the surface of a cordierite honeycomb ceramic carrier, and drying the cordierite honeycomb ceramic carrier coated with the mixed slurry, wherein the drying temperature is controlled at 150 ℃;
g. and (3) roasting the dried cordierite honeycomb ceramic carrier for 3 hours in a muffle furnace at the temperature of 500 ℃, and cooling to room temperature after roasting to obtain the aging-resistant catalyst for purifying volatile organic compounds.
In the aging-resistant volatile organic compound-purified catalyst obtained by the preparation method of example 3, an oxidative catalyst coating was coated on the surface of a cordierite honeycomb ceramic carrier; the oxidative catalyst coating contains Al2O3、CeO2、MnO2PtO and PdO; corresponding to one liter of cordierite honeycomb ceramic carrier, Al2O3Is 190g of CeO2In an amount of 20g, MnO2The using amount of (2) is 20 g; and the usage amount of the noble metal Pt is 10g and the usage amount of the noble metal Pd is 5g for each cubic foot of the cordierite honeycomb ceramic carrier.
The catalysts obtained in comparative example 1, comparative example 2 and comparative example 3 and the catalysts obtained in example 1, example 2 and example 3 were subjected to a catalyst aging performance test.
The aging condition of the catalyst is as follows:
atmosphere conditions: air atmosphere, containing 10% water vapor, temperature 800 deg.C, 20 h.
1. Catalyst activity evaluation conditions:
activity test method: a chromatographic column: ST-30-2, detector temperature: 105 ℃; temperature of the column box: 120 ℃; pressing the column in front: 0.1 mpa; and (3) sample introduction mode: and injecting the sample through a six-way valve.
Atmosphere conditions: toluene: 600ppm, O212%, balance gas: n is a radical of2. The test results are shown in table 1.
TABLE 1 evaluation results of catalyst Activity
As can be seen from table 1, the temperature aging states of the catalysts prepared in example 1, example 2 and example 3 with 99% conversion of toluene were 198 ℃, 185 ℃ and 193 ℃, respectively, and T99 has a significant advantage in low temperature light-off compared to the conventional catalyst.
According to the process, Pt and Pd are loaded on the surface of alumina, and a layer of Mn-Ce composite oxide is loaded on the surface of the alumina, so that a Mn-Ce/Pt-Pd core-shell structure is formed, the core-shell structure has high stability, the thermal stability of the catalytic oxidation catalyst under a high-temperature condition is improved, and the replacement frequency of the catalyst is reduced. In addition, due to the introduction of Mn and Ce, the application of noble metals is reduced, so that the production cost of the catalyst is reduced.
The invention is characterized in that Mn-Ce composite oxide is introduced to improve the catalytic activity of the catalyst, and a core-shell structure is introduced to improve the thermal stability and the sintering resistance of the catalyst and enhance the durability of the catalyst.
Claims (3)
1. A preparation method of an aging-resistant volatile organic compound purification catalyst is characterized by comprising the following steps: the surface of the cordierite honeycomb ceramic carrier is coated with an oxidative catalyst coating; the oxidative catalyst coating contains Al2O3、CeO2、MnO2Noble metal Pt and noble metal Pd; corresponding to one liter of cordierite honeycomb ceramic carrier, Al2O3In an amount of 80 to 200g of CeO2In an amount of 5 to 30g, MnO2The using amount of (A) is 10-30 g; the usage amount of the noble metal Pt is 6-50 g and the usage amount of the noble metal Pd is 10-20 g corresponding to each cubic foot of cordierite honeycomb ceramic carrier;
the preparation method of the aging-resistant volatile organic compound purification catalyst comprises the following steps:
a. firstly, measuring the volume of a cordierite honeycomb ceramic carrier, and preparing Pt (NO) according to 6-50 g of noble metal Pt and 10-20 g of noble metal Pd corresponding to each cubic foot of cordierite honeycomb ceramic carrier3）2And Pd (NO)3）2Mixing Pt (NO)3）2And Pd (NO)3）2Mixed to form a noble metal mixed oxide as Pt (NO)3）2And Pd (NO)3）25-30 times of the total weight of the above components, stirring and mixing uniformly to form a noble metal mixed oxide solution, and preparing 80-200 g of Al per liter of cordierite honeycomb ceramic carrier2O3Powder, adopting an incipient wetness impregnation method to uniformly impregnate the noble metal mixed oxide solution into Al2O3On the powder, the powder is coated with a sizing agent,obtaining Al loaded with noble metal Pt and noble metal Pd2O3Slurry;
b. loading Al with noble metal Pt and noble metal Pd2O3Drying the slurry, controlling the drying temperature at 100-120 ℃, roasting after drying, controlling the roasting temperature at 500-600 ℃ and the roasting time at 1-3 hours to obtain Al loaded with noble metal Pt and noble metal Pd2O3Powder;
c. loading Al with noble metal Pt and noble metal Pd2O3Grinding the powder to D90=40 μm to prepare slurry, and grinding the slurry to D90 of 10-30 μm, wherein the solid content is controlled to be 35-40%;
d. 5-30 g of CeO is correspondingly arranged according to each liter of cordierite honeycomb ceramic carrier2And 10 to 30g of MnO2Preparation of CeO2And MnO2A precursor of (5), CeO2And MnO2The precursor is uniformly mixed in the aqueous solution to obtain a precursor aqueous solution;
e. c, dropwise adding the precursor water solution into the slurry obtained in the step c, and uniformly stirring and mixing to obtain mixed slurry;
f. coating the mixed slurry on the surface of a cordierite honeycomb ceramic carrier, and drying the cordierite honeycomb ceramic carrier coated with the mixed slurry, wherein the drying temperature is controlled to be 145-155 ℃;
g. and roasting the dried cordierite honeycomb ceramic carrier at the temperature of 500-600 ℃ for 2-4 hours, and cooling to room temperature after roasting to obtain the aging-resistant catalyst for purifying volatile organic compounds.
2. The method of claim 1, wherein the catalyst comprises: the CeO2Is Ce (NO)3）3·6（H2O）。
3. The method of claim 1, wherein the catalyst comprises: the MnO2The precursor of (A) is Mn (NO)3）2。
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