CN108325536B - Manganese-copper-based composite oxide doped rare earth element catalyst for catalyzing VOCs (volatile organic compounds), and preparation method and application thereof - Google Patents
Manganese-copper-based composite oxide doped rare earth element catalyst for catalyzing VOCs (volatile organic compounds), and preparation method and application thereof Download PDFInfo
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- CN108325536B CN108325536B CN201810137600.0A CN201810137600A CN108325536B CN 108325536 B CN108325536 B CN 108325536B CN 201810137600 A CN201810137600 A CN 201810137600A CN 108325536 B CN108325536 B CN 108325536B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 35
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 87
- 239000011248 coating agent Substances 0.000 claims abstract description 85
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 53
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 53
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 51
- 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 51
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 72
- 238000001035 drying Methods 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 32
- 239000004202 carbamide Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 11
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 claims description 11
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LBHDWLPRRAROQZ-UHFFFAOYSA-N [Ce].[La].[Hf] Chemical compound [Ce].[La].[Hf] LBHDWLPRRAROQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 6
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001935 peptisation Methods 0.000 claims description 5
- 239000002912 waste gas Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000004584 weight gain Effects 0.000 claims description 3
- 235000019786 weight gain Nutrition 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011159 matrix material Substances 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 14
- -1 hafnium-lanthanum-cerium oxide Chemical compound 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 17
- 238000010981 drying operation Methods 0.000 description 14
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 7
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- 238000011156 evaluation Methods 0.000 description 5
- 239000010815 organic waste Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
A manganese-copper-based composite oxide doped rare earth element catalyst for catalyzing VOCs, a preparation method and application thereof. The catalyst disclosed by the invention takes a cordierite honeycomb ceramic material with high pore volume as a carrier, and a first metal oxide coating, a second metal oxide coating and a third metal oxide coating are sequentially coated from inside to outside; the first metal oxide coating is active aluminum oxide, the second metal oxide coating is hafnium-lanthanum-cerium oxide, and the third metal oxide coating is manganese-copper-based oxide. The catalyst provided by the invention adopts non-noble metal to replace noble metal; the catalyst coating provided by the invention is uniformly dispersed, the active component and the matrix have strong binding force, the catalyst coating is not easy to fall off or crack, the catalyst coating can still keep higher activity under high-speed airflow and thermal shock, the activity of the catalyst coating is stable after repeated use, the catalytic activity of the catalyst coating on VOCs gas is strong, the preparation process is simple, the cost is low, and the catalyst coating is suitable for large-scale production.
Description
Technical Field
The invention relates to a manganese-copper-based composite oxide doped rare earth element catalyst for catalyzing VOCs (volatile organic compounds), and a preparation method and application thereof, belonging to the technical field of environmental protection catalytic materials and atmospheric pollution treatment.
Background
The Volatile Organic Compounds (VOCs) refer to organic compounds with saturated vapor pressure of more than 133.32 Pa at normal temperature and boiling point of 50-260 ℃ below normal pressure, or any organic solid or liquid capable of volatilizing at normal temperature and normal pressure. Mainly produced in petroleum refining industry, industries such as electronics, printing, coating, medicine, spray painting, printing, artificial leather, pesticide, rubber, degreasing of electronic components and the like, and automobile exhaust. VOCs can pose a significant threat to the ecological environment and human health. Under the action of sunlight and heat, the ozone is participated in the reaction of nitrogen oxide to form ozone, which causes the air quality to be poor and is a main component of photochemical smog and urban dust haze in summer; is also an important precursor substance for forming fine particles (PM 2.5) and ozone, the proportion of VOCs in the atmosphere in the PM2.5 accounts for about 20-40%, and partial PM2.5 is converted from VOCs; VOCs are mostly gases with a greenhouse effect, which can cause a series of ecological disasters such as greenhouse effect. Most chemical components have toxicity, and when the concentration of VOCs exceeds a certain concentration, the VOCs can stimulate eyes and respiratory tracts of people, so that skin is allergic, sore throat and hypodynamia; VOCs injure the liver, kidneys, brain and nervous system of a human, resulting in acute and chronic poisoning, even carcinogenesis and mutation. With the improvement of the living standard of people and the increasing requirements on living environment, the effective treatment of the gas attracts the wide attention of people.
The treatment of organic waste gases has been studied for a long time, and some effective control techniques have been developed, such as adsorption, condensation, absorption, biological treatment, membrane separation, photocatalysis, direct combustion, catalytic combustion, and plasma techniques, which are widely used and widely studied. The catalytic combustion method can realize the complete oxidation of VOCs at lower temperature (200-500 ℃) when treating VOCs with large component, low concentration and complex components, and has the advantages of simple equipment, low energy consumption, high purification efficiency, no secondary pollution and the like. Therefore, the catalyst has become one of the most promising approaches, and the core of the technology is the catalyst, and the catalyst with a blocky carrier as a framework matrix is called a monolithic catalyst. The monolithic catalyst has a large number of macroscopic hollow pore channels, and has great advantages in heat transfer, mass transfer and pressure drop compared with a powder catalyst. A commonly used carrier is cordierite honeycomb ceramic, whichThe specific surface area per se is less than 1g/m2It is necessary to disperse the supported active species on the surface of the matrix material. The commonly used active components are noble metals such as platinum, palladium, rhodium, silver, ruthenium and the like, wherein the platinum and the rhodium are most commonly used. From the aspect of catalyst activity, according to the electronic structure of noble metal, the d electronic orbit is not filled, the surface of the particle is easy to absorb reactants, the strength is moderate, an intermediate active compound is favorably formed, and the catalyst has higher catalytic activity; from the aspects of catalyst selectivity and stability, the noble metal catalyst has the characteristics of high temperature resistance, oxidation resistance, corrosion resistance and the like, and has ideal treatment effect and wide application. However, VOCs such as chlorine or sulfur-containing organic compounds can be strongly adsorbed on the surface of the noble metal catalyst or combined with active components after being catalyzed and oxidized, so that the active components are lost, the catalyst is poisoned and inactivated, and other organic compounds are generated to cause secondary pollution. And noble metal catalysts are costly, limiting their use.
In view of the above technical bottlenecks, research and development of oxidative degradation catalysts with low cost, high activity and strong anti-toxicity performance are very important subjects in the field of research of environmental catalytic materials at present, and are receiving wide attention.
Disclosure of Invention
The invention aims to provide a manganese-copper-based composite oxide doped rare earth element catalyst for catalyzing VOCs (volatile organic compounds), and a preparation method and application thereof, aiming at the defects in the prior art. The catalyst disclosed by the invention takes a cordierite honeycomb ceramic material with high pore volume as a carrier, and a first metal oxide coating, a second metal oxide coating and a third metal oxide coating are sequentially coated from inside to outside; the first metal oxide coating is active aluminum oxide, the second metal oxide coating is hafnium-lanthanum-cerium oxide, and the third metal oxide coating is manganese-copper-based oxide.
The technical scheme of the invention is as follows:
the catalyst for catalytic combustion of VOCs is prepared with cordierite honeycomb ceramic matrix as skeleton, active alumina as coating in 5-15 wt%, manganese oxide and/or copper oxide in 1-5 wt% and RE oxide in 0.5-2 wt% as active components.
In the first metal oxide coating, the weight gain ratio of active aluminum oxide is 5% -15%, preferably 10% -15%;
in the second metal oxide coating, the weight increasing ratio of lanthanum oxide, hafnium oxide and cerium oxide is 0.5-2%, preferably 1-2%;
in the third metal oxide coating, the weight increasing ratio of the manganese oxide to the copper oxide is 1% -5%, preferably 2.5% -5%.
The mixed oxide is manganese, copper and rare earth mixed oxide, wherein the rare earth metal can have multiple valence states, 30-60wt% MnO2、15-29wt% CuO、18-33wt% HfO2、18-33wt%La203And 18-33wt% CeO2. The optimal mixture ratio is 43 to 49 weight percent MnO2，23-28wt%CuO，28-33wt% HfO2、28-33wt%La203And 28-33wt% CeO2。
The hafnium oxide is present in the mixture in an amount of less than 50% by weight relative to the amount of lanthanum oxide and cerium oxide present in the mixture. Due to the specific distribution of the above elements with respect to each other, the mixed oxides forming the active components of the catalyst have characteristic semiconductors of the p-type (in these semiconductors, the electrical conductivity increases exponentially with temperature). In these oxides, gaseous oxygen adsorbed on the surface of the substance participates in the oxidation reaction together with lattice oxygen, and the coating stability and the activity of the catalyst can be improved.
In order to be better combined with the coating layer and form a stable and high-efficiency monolithic catalyst, the cordierite honeycomb ceramic carrier is preferably pretreated by the following steps: the cordierite honeycomb ceramic matrix is put into dilute nitric acid (with the preferred concentration of 5% -10%) to be soaked for 4-12 hours, and then is taken out to be dried for 1-6 hours at the temperature of 80-150 ℃.
The loading of the second coating and/or the third coating is one of the cores which can be catalyzed by the catalyst with high efficiency. According to the invention, the total mass of the two metal oxide coatings accounts for 1.5-8% of the mass of the carrier, and the total mass of the two metal oxide coatings accounts for 5-7% of the mass of the carrier.
The invention also provides a preparation method of the catalytic combustion catalyst, which comprises the following steps:
(1) putting cordierite honeycomb ceramic carrier into dilute acid with concentration of 5% -10% to soak for 4-12 hours, taking out and drying for 1-6 hours at 80-150 ℃;
(2) immersing the honeycomb ceramic substrate treated in the step (1) into aluminum sol, taking out, drying, and roasting at 400-900 ℃ for 1-6 hours under the protection of nitrogen to form a first metal oxide coating;
(3) dipping the cordierite honeycomb ceramic obtained in the step (2) into a hafnium-lanthanum-cerium salt solution, taking out, drying, and roasting at 400-600 ℃ for 1-6 hours under the protection of nitrogen to form a second metal oxide coating;
(4) and (4) dipping the cordierite honeycomb ceramic obtained in the step (3) into a manganese-copper salt solution, taking out, drying, and roasting at 400-550 ℃ for 1-6 hours under the protection of nitrogen to form a third metal oxide coating. The preparation method of the aluminum sol comprises the following steps: mixing pseudo-boehmite powder and deionized water in proportion, adding urea, fully stirring at room temperature, dropwise adding concentrated nitric acid to adjust the pH =2-5 of the slurry, and carrying out peptization reaction for 60-240min to obtain stable alumina sol, wherein the pseudo-boehmite powder: deionized water: the mass ratio of urea is as follows: (3-5):(25-30): (1.5-2.5).
In order to ensure that the coating loading reaches the target value, the present invention preferably repeats the operations of soaking and dry firing during the formation of the second metal oxide coating and/or the formation of the third metal oxide coating until the coating loading reaches the target value and then fires.
In the preparation process, the drying is preferably carried out for 1 to 6 hours at the temperature of between 80 and 150 ℃; the calcination is preferably carried out at 400 ℃ to 900 ℃ for 1 to 6 hours. In order to obtain more compact combination and better stability of the catalyst, the roasting temperature of the second metal oxide coating layer formed in the invention is preferably 400-600 ℃, and the roasting temperature of the third metal oxide coating layer formed in the invention is preferably 400-550 ℃. In order to ensure the activity of the third metal oxide coating, nitrogen is preferably used for protection during firing.
The preparation method of the hafnium-lanthanum-cerium salt solution in the step (3) comprises the following steps: dissolving hafnium sulfate, lanthanum sulfate and cerous nitrate hexahydrate in water, adding urea, and stirring at constant temperature (20-50 ℃) to obtain a hafnium-lanthanum-cerium salt solution. Wherein the weight ratio of hafnium sulfate: lanthanum sulfate: cerium nitrate hexahydrate: urea: the water mass ratio is (0.01-0.5): (0.01-0.5): (0.01-0.5): 1: 1.
the preparation method of the manganese-copper salt solution in the step (4) comprises the following steps: adding manganese nitrate and copper nitrate into water, adding urea, and stirring at constant temperature to obtain manganese-copper salt solution. Wherein, manganese nitrate: copper nitrate: urea: the water mass ratio is (0.01-0.5): (0.01-0.5): 1: 1.
the invention further protects the application of the catalytic combustion catalyst in the treatment of industrial volatile organic compound waste gas.
The application specifically comprises the following steps: passing industrial volatile organic waste gas over the catalyst under combustion conditions to convert or degrade the waste gas. As a preferable scheme, the air speed can be 18000--1The total hydrocarbon concentration is 1500-3The temperature of the reactor inlet is 100-300 ℃, preferably 225-300 ℃, more preferably 250-300 ℃, and the high-efficiency degradation of the waste gas can be realized.
The industrial volatile organic waste gas is preferably benzene, toluene, xylene, acetone, cyclohexanone, n-butanol, styrene, ethyl acetate and the like, and the catalyst provided by the invention can embody the best combustion catalysis effect when catalyzing the waste gas.
The invention has the beneficial effects that:
1. the catalyst provided by the invention adopts non-noble metal to replace noble metal, and on one hand, the mixed oxide forming the active component of the catalyst has p-type characteristic semiconductors (in the semiconductors, the conductivity exponentially increases with the temperature) as shown in figure 1. The gaseous oxygen adsorbed on the surface of the substance and the lattice oxygen participate in the oxidation reaction, so that the stability of the coating and the activity of the catalyst can be improved, and the problem of high price of the noble metal is solved. The special perovskite structure overcomes the defects of poor poison resistance and the like of the traditional catalyst, and on the other hand, the non-noble metal raw materials are easy to obtain and the process is simple and convenient; the addition of Ce can not only improve the oxidation-reduction performance of the catalytic catalyst, but also promote the uniform distribution of other active components. Therefore, the catalyst coating provided by the invention is uniformly dispersed, the active component is tightly combined with the carrier, the thermal stability is high, the catalytic activity is strong, the service life is long, and the large-scale industrial production is easy to realize.
2. According to the invention, the noble metal is replaced by the non-noble metal composite oxide of lanthanum, hafnium, cerium, manganese and copper, so that the problems of easy sintering, easy poisoning, high price and the like of the traditional noble metal catalyst are solved, and on the other hand, the metal raw materials are easy to obtain, the process is simple and convenient, the catalytic performance is high, and the large-scale industrial production is easy to realize.
3. The oxide coating is skillfully divided into three layers, the first metal oxide coating is in direct contact with the carrier, the specific surface area of the material is mainly increased, the second metal oxide coating containing hafnium oxide, lanthanum oxide and cerium oxide is wrapped outside the first metal oxide coating, and rare earth ions such as lanthanum and the like contained in the second metal oxide coating are metal oxides with special energy band structures, so that the catalyst has outstanding optical, electric and magnetic properties, and the catalytic activity is further enhanced; and a third metal oxide coating containing manganese oxide and copper oxide is coated outside the catalyst, so that the monolithic catalyst with active components such as hafnium, lanthanum, cerium, manganese, copper and the like uniformly dispersed on the surface of the active alumina is formed. The process ensures that the active components hafnium, lanthanum, cerium, manganese and copper have stronger interaction with the active alumina components, avoids forming spinel compounds as shown in figure 2, has higher catalytic activity and higher thermal stability, and plays a strong role in promoting the catalytic combustion of VOCs organic gases.
Drawings
FIG. 1 is a schematic diagram of a catalyst.
FIG. 2 is an electron micrograph of the catalyst.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The embodiment provides a manganese-copper-based composite oxide doped rare earth element catalyst, which is prepared by the following method:
(1) putting the cordierite honeycomb ceramic matrix into dilute acid with the concentration of 5% for soaking for 4h for pretreatment, taking out and drying at 90 ℃ for 6h for later use.
(2) Immersing the cordierite honeycomb ceramic substrate treated in the step (1) into aluminum sol, taking out and blowing off residual liquid, drying at 90 ℃ for 6 hours, and roasting at 250 ℃ for 2 hours to obtain honeycomb ceramic coated with an alumina coating, wherein the preparation method of the aluminum sol comprises the following steps: mixing pseudo-boehmite powder and deionized water in proportion, adding urea, fully stirring at room temperature, dropwise adding concentrated nitric acid to adjust the pH =2 of the slurry, and carrying out peptization reaction for 60min to obtain stable alumina sol, wherein the pseudo-boehmite powder: deionized water: the mass ratio of urea is as follows: 3:25: 1.5.
(3) 40g of hafnium sulfate and 46g of lanthanum sulfate and 90g of cerium nitrate hexahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at 25 ℃ to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 6h after coating, drying at 100 ℃ for 4h, weighing, repeating the coating and drying operations until the total weight of the load reaches 1.5%, and roasting at 450 ℃ for 1h under the protection of nitrogen to obtain the carrier HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 200g of manganese nitrate and 250g of blue vitriod are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 35 ℃ to prepare slurry B. Dipping the cordierite honeycomb ceramic obtained in the step (3) into the slurry B, standing for 3h at room temperature, drying at 100 ℃, weighing, repeating the dipping and drying operations until the total weight of the load reaches 3%, and putting the carrier in N2Roasting for 6 hours at 600 ℃ in the atmosphere,MnO is finally obtained2-CuO-HfO2-CeO2-La2O3The metal oxide honeycomb ceramic catalyst is shown in figure 1, and the electron microscope image is shown in figure 2.
Example 2
The embodiment provides a manganese-copper-based composite oxide doped rare earth element catalyst, which is prepared by the following method:
(1) putting the cordierite honeycomb ceramic substrate into dilute acid with the concentration of 10% for soaking for 12h for pretreatment, taking out and drying at 150 ℃ for 1h for later use.
(2) Immersing the cordierite honeycomb ceramic substrate treated in the step (1) into aluminum sol, taking out and blowing off residual liquid, drying at 90 ℃ for 6 hours, and roasting at 250 ℃ for 2 hours to obtain honeycomb ceramic coated with an alumina coating, wherein the preparation method of the aluminum sol comprises the following steps: mixing pseudo-boehmite powder and deionized water in proportion, adding urea, fully stirring at room temperature, dropwise adding concentrated nitric acid to adjust the pH =5 of the slurry, and carrying out peptization reaction for 240min to obtain stable alumina sol, wherein the pseudo-boehmite powder: deionized water: the mass ratio of urea is as follows: 5: 30: 2.5.
(3) 45g of hafnium sulfate and 46g of lanthanum sulfate 100g of cerous nitrate hexahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred at 25 ℃ for 1 hour to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 6h after coating, drying at 100 ℃ for 4h, weighing, repeating the coating and drying operations until the total weight of the load reaches 1.5%, and roasting at 400 ℃ for 6h to obtain the load HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 200g of manganese nitrate and 250g of blue vitriod are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 35 ℃ to prepare slurry B. Dipping the cordierite honeycomb ceramic obtained in the step (3) into the slurry B, standing for 3h at room temperature, drying at 100 ℃, weighing, repeating the dipping and drying operations until the total weight of the load reaches 3%, and putting the carrier in N2Roasting at 550 ℃ for 2h in the atmosphere to finally obtain MnO2-CuO-HfO2-CeO2-La2O3A metal oxide honeycomb ceramic catalyst.
Example 3
The embodiment provides a manganese-copper-based composite oxide doped rare earth element catalyst, which is prepared by the following method:
(1) putting the cordierite honeycomb ceramic matrix into dilute acid with the concentration of 8 percent for soaking for 8 hours for pretreatment, taking out and drying at 90 ℃ for 3 hours for later use.
(2) Immersing the cordierite honeycomb ceramic substrate treated in the step (1) into aluminum sol, taking out and blowing off residual liquid, drying at 90 ℃ for 6 hours, and roasting at 250 ℃ for 2 hours to obtain honeycomb ceramic coated with an alumina coating, wherein the preparation method of the aluminum sol comprises the following steps: mixing pseudo-boehmite powder and deionized water in proportion, adding urea, fully stirring at room temperature, dropwise adding concentrated nitric acid to adjust the pH =3 of the slurry, and carrying out peptization reaction for 150min to obtain stable alumina sol, wherein the pseudo-boehmite powder: deionized water: the mass ratio of urea is as follows: 4:28: 2.
(3) 20.5g of hafnium sulfate and 28.3g of lanthanum sulfate, 43.4g of cerium nitrate hexahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred at 25 ℃ for 1 hour to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 6h after coating, drying at 100 ℃ for 4h, weighing, repeating the coating and drying operations until the total load weight is 1.5%, and roasting at 450 ℃ for 2h to obtain the carrier HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 278g of manganese nitrate and 250g of blue vitriod are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 35 ℃ to prepare slurry B. Dipping the cordierite honeycomb ceramic obtained in the step (3) into the slurry B, standing for 3h at room temperature, drying at 100 ℃, weighing, repeating the dipping and drying operations until the total weight of the load reaches 3%, and putting the carrier in N2Roasting at 550 ℃ for 2h in the atmosphere to finally obtain MnO2-CuO-HfO2-CeO2-La2O3A metal oxide honeycomb ceramic catalyst.
Example 4
The embodiment provides a manganese-copper-based composite oxide doped rare earth element catalyst, which is prepared by the following method:
(1) the cordierite honeycomb ceramic matrix is put into dilute acid for soaking pretreatment, and is taken out to be dried for 6 hours at 90 ℃ for standby.
(2) And (2) immersing the cordierite honeycomb ceramic matrix treated in the step (1) into alumina sol, taking out and blowing off residual liquid, drying at 90 ℃ for 6h, and roasting at 250 ℃ for 2h to obtain the honeycomb ceramic coated with the alumina coating.
(3) 25g of hafnium sulfate and 1000g of lanthanum sulfate, 43.4g of cerium nitrate hexahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred at 25 ℃ for 1 hour to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 6h after coating, then drying at 100 ℃ for 4h, weighing, repeating the coating and drying operations until the load total weight reaches 1.5%, and roasting at 450 ℃ for 2h to obtain the load HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 1000g of manganese nitrate and 20g of copper sulfate pentahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 35 ℃ to prepare slurry B. Dipping the cordierite honeycomb ceramic obtained in the step (3) into the slurry B, standing for 3h at room temperature, drying at 100 ℃, weighing, repeating the dipping and drying operations until the total weight of the load reaches 3%, roasting the carrier at 550 ℃ for 2h in the atmosphere of N2, and finally obtaining MnO2-CuO-HfO2-CeO2-La2O3A metal oxide honeycomb ceramic catalyst.
Example 5
The embodiment provides a manganese-copper-based composite oxide doped rare earth element catalyst, which is prepared by the following method:
(1) the cordierite honeycomb ceramic matrix is put into dilute acid for soaking pretreatment, and is taken out to be dried for 6 hours at 90 ℃ for standby.
(2) And (2) immersing the cordierite honeycomb ceramic matrix treated in the step (1) into alumina sol, taking out and blowing off residual liquid, drying at 90 ℃ for 6h, and roasting at 250 ℃ for 2h to obtain the honeycomb ceramic coated with the alumina coating.
(3) 20.5g of hafnium sulfate and 28.3g of lanthanum sulfate, 43.4g of cerium nitrate hexahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred at 25 ℃ for 1 hour to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 6h after coating, then drying at 100 ℃ for 4h, weighing, repeating the coating and drying operations until the load total weight reaches 1.5%, and roasting at 450 ℃ for 2h to obtain the load HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 300g of manganese nitrate and 350g of copper sulfate pentahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 35 ℃ to prepare slurry B. Dipping the cordierite honeycomb ceramic obtained in the step (3) into the slurry B, standing for 3h at room temperature, drying at 100 ℃, weighing, repeating the dipping and drying operations until the total weight of the load reaches 3%, and putting the carrier in N2Roasting at 550 ℃ for 2h in the atmosphere to finally obtain MnO2-CuO-HfO2-CeO2-La2O3A metal oxide honeycomb ceramic catalyst.
Example 6
The embodiment provides a manganese-copper-based composite oxide doped rare earth element catalyst, which is prepared by the following method:
(1) the cordierite honeycomb ceramic matrix is put into dilute acid for soaking pretreatment, and is taken out to be dried for 3 hours at the temperature of 110 ℃ for standby.
(2) And (2) immersing the cordierite honeycomb ceramic matrix treated in the step (1) into alumina sol, taking out and blowing off residual liquid, drying at 120 ℃ for 2h, and roasting at 250 ℃ for 2h to obtain the honeycomb ceramic coated with the alumina coating.
(3) 150g of hafnium sulfate and 350g of lanthanum sulfate and 1000g of cerous nitrate hexahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 40 ℃ to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 4h after coating, drying at 120 ℃ for 3h, and weighingRepeating the coating and drying operations until reaching 2 percent of the total weight of the load, and roasting at 450 ℃ for 1h to obtain the load HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 300g of manganese nitrate and 350g of copper sulfate pentahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 40 ℃ to prepare slurry B. Soaking the cordierite honeycomb ceramic obtained in the step (3) in the slurry B, standing for 2h at room temperature, drying at 120 ℃, weighing, repeating the soaking and drying operations until the total weight of the load reaches 4%, roasting the carrier at 550 ℃ for 2h in an N2 atmosphere, and finally obtaining MnO2-CuO-HfO2-CeO2-La2O3A metal oxide honeycomb ceramic catalyst.
Example 7
(1) The cordierite honeycomb ceramic matrix is put into dilute acid for soaking pretreatment, and is taken out to be dried for 3 hours at the temperature of 110 ℃ for standby.
(2) And (2) immersing the cordierite honeycomb ceramic matrix treated in the step (1) into alumina sol, taking out and blowing off residual liquid, drying at 120 ℃ for 2h, and roasting at 250 ℃ for 2h to obtain the honeycomb ceramic coated with the alumina coating.
(3) 20g of hafnium sulfate and 1000g of lanthanum sulfate and 25g of cerous nitrate hexahydrate are dissolved in 2000g of water, 60g of urea is added, and the mixture is stirred for 1 hour at 40 ℃ to prepare slurry A. Coating the slurry A on cordierite honeycomb ceramic, standing the cordierite honeycomb ceramic at room temperature for 4h after coating, then drying at 120 ℃ for 3h, weighing, repeating the coating and drying operations until the total load weight is 2%, and roasting at 400 ℃ for 1h to obtain the carrier HfO2、CeO2And La2O3A honeycomb ceramic of rare earth metal oxide.
(4) 200g of manganese nitrate and 300g of copper sulfate pentahydrate are dissolved in 2000g of water, 2000g of urea is added, and the mixture is stirred for 1 hour at the temperature of 40 ℃ to prepare slurry B. Soaking the cordierite honeycomb ceramic obtained in the step (3) in the slurry B, standing at room temperature for 2h, drying at 120 ℃, weighing, repeating the soaking and drying operations until the total weight of the load reaches 4%, and placing the carrier in an N2 atmosphereRoasting at 550 ℃ for 1h to finally obtain MnO2-CuO-HfO2-CeO2-La2O3A metal oxide honeycomb ceramic catalyst.
Application example
In order to evaluate the treatment effect of the catalyst on the organic waste gas, the invention carries out activity evaluation and stability evaluation on the catalytic combustion catalyst provided by each embodiment. The evaluation conditions were: the space velocity is 20000 h-1Toluene concentration 1500 mg/m3The reactor inlet temperature was 100 ℃ and 300 ℃ and the evaluation results after 480 hours of continuous operation are shown in Table 1.
It can be seen that the catalytic efficiency of the catalyst provided by each embodiment to toluene at 225-300 ℃ can reach more than 90%, wherein the temperature of 250-300 ℃ can reach more than 98%, and the activity of the catalyst is stable, which indicates that the catalyst provided by the invention has higher stability and is suitable for treating industrial organic waste gas.
Table 1 shows the results of the experiment in which the catalyst provided in each example catalyzes toluene (conversion of toluene after 480 hours of continuous operation at a temperature of 250 ℃).
Table 1: evaluation results of catalyst Activity
As can be seen from Table 1, the catalytic combustion catalyst provided by the invention has high organic matter removal rate, and the high removal rate is still maintained after 480 hours of continuous operation, which indicates that the catalyst has good anti-poisoning performance and stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A catalyst for catalyzing manganese-copper-based composite oxides of VOCs doped with rare earth elements is characterized in that: the catalyst takes cordierite honeycomb ceramic as a carrier and sequentially coats a first metal oxide coating, a second metal oxide coating and a third metal oxide coating from inside to outside; the main components of the first metal oxide coating are active aluminum oxide, the main components of the second metal oxide coating are lanthanum oxide, hafnium oxide and cerium oxide, and the main components of the third metal oxide coating are manganese oxide and copper oxide;
in the first metal oxide coating, the weight gain ratio of active aluminum oxide is 5% -15%; in the second metal oxide coating, the weight increasing ratios of lanthanum oxide, hafnium oxide and cerium oxide are respectively 0.5% -2%; in the third metal oxide coating, the weight increasing ratio of the manganese oxide to the copper oxide is 1% -5% respectively.
2. The catalyst of claim 1 for catalyzing the doping of rare earth elements to manganese-copper based composite oxides of VOCs, wherein: the carrier cordierite honeycomb ceramic is any one of hexagonal, round or square, when the cordierite-based honeycomb ceramic is square, the length is 5-15cm, the width is 5-15cm, the height is 5-15cm, and the density of the upper holes of the cordierite-based honeycomb ceramic is 100-500 meshes.
3. The catalyst of claim 1 for catalyzing the doping of rare earth elements to manganese-copper based composite oxides of VOCs, wherein: in the first metal oxide coating, the weight gain ratio of active aluminum oxide is 10-15%; in the second metal oxide coating, the weight increasing ratios of lanthanum oxide, hafnium oxide and cerium oxide are respectively 1% -2%; in the third metal oxide coating, the weight increasing ratio of the manganese oxide to the copper oxide is 2.5% -5%.
4. The catalyst of claim 1 for catalyzing the doping of rare earth elements to manganese-copper based composite oxides of VOCs, wherein: the oxide contains lower oxide component in MnO2 30-60wt%、CuO15-29wt%、HfO218-33 wt%、La20318-33 wt%、CeO2 18-33 wt%。
5. The method of any one of claims 1 to 4 for preparing a rare earth doped manganese-copper based composite oxide catalyst for catalyzing VOCs comprising the steps of:
(1) putting cordierite honeycomb ceramic carrier into dilute nitric acid with concentration of 5% -10% to soak for 4-12 hours, taking out and drying for 1-6 hours at 80-150 ℃;
(2) immersing the honeycomb ceramic substrate treated in the step (1) into aluminum sol, taking out, drying, and roasting at 400-900 ℃ for 1-6 hours under the protection of nitrogen to form a first metal oxide coating;
(3) dipping the cordierite honeycomb ceramic obtained in the step (2) into a hafnium-lanthanum-cerium salt solution, taking out, drying, and roasting at 400-600 ℃ for 1-6 hours under the protection of nitrogen to form a second metal oxide coating;
(4) and (4) dipping the cordierite honeycomb ceramic obtained in the step (3) into a manganese-copper salt solution, taking out, drying, and roasting at 400-550 ℃ for 1-6 hours under the protection of nitrogen to form a third metal oxide coating.
6. The method of claim 5 for preparing a rare earth doped manganese-copper based composite oxide catalyst for catalyzing VOCs, wherein the method comprises: the preparation method of the alumina sol in the step (2) comprises the following steps: mixing pseudo-boehmite powder and deionized water in proportion, adding urea, fully stirring at room temperature, dropwise adding concentrated nitric acid to adjust the pH =2-5 of the slurry, and carrying out peptization reaction for 60-240min to obtain stable alumina sol, wherein the pseudo-boehmite powder: deionized water: the mass ratio of urea is as follows: (3-5):(25-30): (1.5-2.5).
7. The method of claim 5, wherein the step (3) of preparing the solution of hafnium-lanthanum-cerium salt comprises: dissolving hafnium sulfate, lanthanum sulfate and cerous nitrate hexahydrate in water, adding urea, and stirring at constant temperature to obtain a hafnium-lanthanum-cerium salt solution; wherein, hafnium sulfate: lanthanum sulfate: cerium nitrate hexahydrate: urea: the water mass ratio is (0.01-0.5): (0.01-0.5): (0.01-0.5): 1: 1.
8. the method for preparing the catalyst doped with rare earth elements and used for catalyzing manganese-copper-based composite oxides of VOCs according to claim 5, wherein the method for preparing the manganese-copper salt solution in the step (4) comprises the following steps: adding manganese nitrate and copper nitrate into water, adding urea, and stirring at constant temperature to obtain a manganese-copper salt solution; wherein, manganese nitrate: copper nitrate: urea: the water mass ratio is (0.01-0.5): (0.01-0.5): 1: 1.
9. use of the catalyst of any one of claims 1 to 4 for catalyzing the degradation of VOCs in an exhaust gas catalytic oxidation treatment, wherein the catalyst is based on a manganese-copper based composite oxide doped with a rare earth element.
10. The use of the catalyst of claim 9 for catalyzing the catalytic oxidation treatment degradation of VOCs exhaust gas, wherein the catalyst comprises a manganese-copper based composite oxide doped with a rare earth element, and wherein: and the VOCs waste gas is benzene, toluene, xylene, acetone, cyclohexanone, n-butanol, styrene and/or ethyl acetate.
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