CN114904512A - Mullite-type loaded honeycomb ceramic catalyst surface active coating and preparation method thereof - Google Patents
Mullite-type loaded honeycomb ceramic catalyst surface active coating and preparation method thereof Download PDFInfo
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- CN114904512A CN114904512A CN202210492165.XA CN202210492165A CN114904512A CN 114904512 A CN114904512 A CN 114904512A CN 202210492165 A CN202210492165 A CN 202210492165A CN 114904512 A CN114904512 A CN 114904512A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 167
- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 238000000576 coating method Methods 0.000 title claims abstract description 116
- 239000011248 coating agent Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 38
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 59
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 19
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000000428 dust Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000011195 cermet Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
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- 239000003546 flue gas Substances 0.000 claims description 3
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- 150000008282 halocarbons Chemical class 0.000 claims description 3
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- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
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- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
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- 238000011161 development Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 235000011187 glycerol Nutrition 0.000 description 16
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- 238000007654 immersion Methods 0.000 description 12
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- 239000001294 propane Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910009580 YMnO Inorganic materials 0.000 description 5
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- 239000000969 carrier Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 229920001732 Lignosulfonate Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000006578 abscission Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- B01J35/56—
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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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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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
- B01D53/864—Removing carbon monoxide or hydrocarbons
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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
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0211—Peroxy compounds
- C01B13/0214—Hydrogen peroxide
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention provides a surface active coating of a honeycomb ceramic catalyst and a preparation method thereof, belonging to the technical field of catalysts 2 O 5‑x A is any one of lanthanide series metal elements Sm, Bi and Y orA plurality of transition metal elements, wherein M is any one or more of the first transition metal elements, x is 0-1, and the components of the surface coating of the loaded honeycomb ceramic catalyst are as follows: mullite, gamma-alumina and additives. The catalyst coating provided by the invention has the advantages of small coating loss, uniform dispersion of the coating and stable physicochemical property and state, and the falling rate of the obtained coating is less than 2.5%; the preparation method of the honeycomb ceramic catalyst is simple, green, environment-friendly and pollution-free, so that the large-scale production of the honeycomb ceramic catalyst can be carried out in mass production; the honeycomb ceramic catalyst can be widely applied to the fields of energy, environment, medical treatment and families, and has excellent future application and development prospects.
Description
Technical Field
The invention relates to a material in the technical field of catalysts and a preparation method thereof, and particularly relates to a mullite type (general formula AM) 2 O 5-x Compound) supported honeycomb ceramic catalyst surface active coating and a preparation method thereof.
Background
The honeycomb ceramic has excellent characteristics of high temperature resistance, high mechanical strength, low thermal expansion coefficient, good thermal stability and the like, and is widely used as an integral catalyst carrier material. However, the specific surface area of the honeycomb ceramic carrier is usually smaller, and the wall surface of a narrow pore channel is smooth, so that the loading amount and the stability of the active component are directly influenced. In order to uniformly disperse the active components on the surface of the carrier and have a longer service life, a layer of coating material which has a large specific surface area and is not easy to fall off needs to be coated on the carrier, so that the monolithic catalyst meets the requirements of the application catalysis field. The loading and firmness of the coating on the honeycomb ceramic carrier are important factors influencing the catalytic activity and stability of the catalyst. If the loading amount of the coating is low or the shedding rate is high, the content of the loaded catalytic active component is relatively low and the catalysis is unstable, so that the service performance of the catalyst is seriously influenced. Therefore, the coating with high specific surface area, strong bonding force with the catalyst carrier, large loading capacity and good thermal stability is obtained and is the key for preparing the monolithic catalyst.
Compared with the traditional powder catalyst, the monolithic catalyst is easier to separate from a reaction system, and is used as one of core units of a diesel vehicle aftertreatment device, and the development of a slurry formula and a coating method which have good dispersibility, high bonding strength and good activity is necessary. Patent publication No. CN112547133A discloses a platinum-supported honeycomb ceramic carrier catalyst, which is not suitable for mass production and increases energy consumption because a high-temperature reaction kettle is used in the preparation process of the coating slurry, and the preparation process is complicated. The patent with publication number CN1954916A discloses a preparation method of an active coating of an integral catalyst, which comprises coating the prepared coating slurry on a pretreated integral carrier by a vacuum spraying method, removing the excess slurry by vacuum extraction, drying, and roasting to obtain the active coating. The method has high requirements on equipment, needs a vacuum system, is complex to operate and increases the cost of coating preparation. The patent with publication number CN1160599 discloses a preparation method of a honeycomb ceramic catalyst loaded with noble metal, rare earth metal and transition metal active components, the method takes cordierite honeycomb ceramic coated with an alumina coating as a carrier, the preparation of the alumina coating is to prepare pseudo-boehmite into slurry, add hydrochloric acid for acidification, then add the pseudo-boehmite and alumina sol, add iron-chromium lignosulfonate aqueous solution, and coat the obtained slurry on the honeycomb ceramic carrier. However, the slurry is colloidal, difficult to coat and easy to block the pore channels of the honeycomb ceramic. Therefore, the research and development of the monolithic catalyst with high coating load, low shedding rate and good dispersibility by a simple and low-cost method is of great importance in the field of practical application.
Disclosure of Invention
The invention mainly aims at providing a general formula AM 2 O 5-x The compound-loaded honeycomb ceramic catalyst surface active coating and the preparation method thereof can overcome the defects of the prior art, the prepared catalyst coating has the advantages of small coating loss, uniform dispersion of the coating and stable physicochemical property, the binding force between the coating and the carrier is effectively improved, the coating is not easy to crack and fall off, and the mass production of the large-scale honeycomb ceramic catalyst can be carried out. The honeycomb ceramic catalyst can be widely applied to the field of energy environment, and has excellent future application and development prospects.
In order to achieve the above object, according to one aspect of the present invention, there is provided a honeycomb ceramic catalyst supported by a honeycomb ceramic material having a high pore volume, and a coating material including a mullite-type composite oxide AM 2 O 5-x A is one or more of lanthanide series metal elements, Sm, Bi and Y, M is one or more of first transition series transition metal elements, and x is between 0 and 1.
Further, the surface of the honeycomb ceramic catalyst is coatedThe coating material comprises the following components in percentage by mass: 1-70% of mullite composite oxide AM 2 O 5-x 1.5 to 3 percent of gamma-alumina and 20 to 30 percent of additive.
Further, the additive includes at least two of ethylene glycol, glycerin, methanol, polyvinyl alcohol, zirconium acetate, zirconium sol, aluminum sol, or silica sol, and preferably glycerin, zirconium acetate, and silica sol.
Further, the preparation method of the honeycomb ceramic catalyst comprises the following steps:
first, the general formula AM 2 O 5-x Mixing a compound, gamma-alumina, an additive and water according to a certain proportion, and stirring for a period of time at room temperature to obtain coating slurry;
said general formula AM 2 O 5-x The compound has a particle size of 100 μm or less, and the slurry is stirred for at least 30 min.
Secondly, soaking the honeycomb ceramic in the coating slurry, then removing the redundant slurry in the honeycomb ceramic pore channels by blowing a dust blowing gun, and finally drying and calcining, wherein the coating step is carried out once, and the coating step is optionally repeated for 1-5 times to obtain the coating containing the general formula AM 2 O 5-x Compound surface active coating honeycomb ceramic catalyst.
When the carrier of the honeycomb ceramic catalyst is placed in the slurry containing the mullite composite oxide at a certain angle for dip coating, the angle is 70-90 degrees, and preferably 90 degrees; taking out the impregnated slurry from the slurry, and reversely blowing the redundant slurry in the pore channel; the drying and calcining treatment is as follows: and drying the mixture in a low-temperature environment, and then placing the dried mixture in a muffle furnace for calcining for at least 1 h.
Furthermore, the coating slurry of the honeycomb ceramic catalyst also comprises one or more of perovskite, molecular sieve, metal compound, metal oxide and carbon powder.
Further, the coating slurry of the honeycomb ceramic catalyst may be coated on a carrier other than honeycomb ceramics, preferably a carbon material, a ceramic material, a foam material or a solid acidic material,further preferably ZrO 2 、TiO 2 、 SiO 2 、WO 3 、Nb 2 O 5 、SnO 2 、Al 2 O 3 、Co 3 O 4 、CeO 2 、Fe 2 O 3 Activated carbon, graphene, clay, zeolite, organometallic framework, ceramic foam, cermet, foam, sponge.
Furthermore, the honeycomb ceramic catalyst can be widely applied to the fields of energy, environment, medical treatment and family, such as motor vehicle tail gas treatment, fixed source flue gas catalytic oxidation, volatile organic pollutant purification, indoor and outdoor air purification, odor purification, catalytic decomposition of ozone and hydrogen peroxide and water purification.
The tail gas treatment comprises diesel engine tail gas, automobile tail gas, methanol fuel cell tail gas, industrial tail gas and the like; the volatile organic pollutants refer to alkanes, aromatic hydrocarbons, alkenes, halogenated hydrocarbons, esters, aldehydes, ketones and other organic compounds; the odor means H 2 S、NH 3 Acetic acid, methyl mercaptan, etc.; the object gas for indoor and outdoor air purification comprises NO, CO and CH 4 、NH 3 And other polluting gases; the catalytic decomposition of ozone and hydrogen peroxide is not only limited to room temperature, but also applicable to high temperature environment (40-110 ℃), and the ozone and the hydrogen peroxide can exist in any form; the purification of water includes any substances polluting the environment such as hydrogen peroxide, organic compounds and chlorine in the water.
The technical scheme of the invention is applied, and the general formula is AM 2 O 5-x The compound-loaded honeycomb ceramic catalyst surface active coating has the advantages of small coating loss, uniform coating dispersion and stable physicochemical property, and the shedding rate of the obtained coating is less than 2.5%; meanwhile, the preparation method of the honeycomb ceramic catalyst is simple, green and environment-friendly, and pollution-free, so that the large-scale production of the honeycomb ceramic catalyst can be carried out in a mass production manner. The honeycomb ceramic catalyst can be widely applied to the field of energy environment, and has excellent future application and development prospects.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic of the process of the present invention;
FIG. 2 shows the reaction of the honeycomb ceramic catalyst of example 14 with propane (C), a volatile organic contaminant 3 H 8 ) A graph of the effect of the transformation;
fig. 3 is a graph showing the effect of the honeycomb ceramic catalyst on the conversion of Nitric Oxide (NO) in the exhaust gas of a mobile pollution source in example 15.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
With reference to fig. 1 to 3, the present invention mainly aims at a preparation method of an integral catalyst, and by optimizing a formula and a coating method of a carrier surface active coating slurry, the production cost is reduced, and the integral catalyst can simultaneously have the advantages of low shedding rate, high loading capacity and uniform coating dispersion, and has an extremely important role in pollution treatment, environmental protection and guarantee of human life health and safety in different industries in the field of applied catalysis.
As analyzed in the background of the present application, in the field of monolithic catalyst preparation, honeycomb ceramics are currently used as one of the widely used catalyst carriers, and the specific surface area thereof is usually small and the wall surfaces of the channels are smooth, which has a direct influence on the loading and stability of the surface active coating. The coating with high specific surface area, strong binding force with a catalyst carrier, large loading capacity and good thermal stability is obtained by a simple method, and is the technical core of monolithic catalyst preparation. In the prior art for preparing the honeycomb ceramic catalyst, the preparation and coating processes of coating slurry are complicated, the requirement on equipment is high, and some coating slurries need a high-temperature reaction kettle and a vacuum device, so that the energy consumption is increased, the production cost is increased, and the large-scale production of the coating slurries is not facilitated; in addition, the prepared slurry is sticky and colloidal, and is easy to block the pore channels of the honeycomb ceramics, so that the coating and the uniform dispersion of the coating are not facilitated, the falling rate of the coating is increased, the content of active components is relatively reduced, and the aim of industrial practical application is difficult to achieve.
The application provides a mullite type (general formula AM) for solving the problems of low coating load, high shedding rate and uneven dispersion in the field of preparation of the existing monolithic catalyst 2 O 5-x Compound) loaded honeycomb ceramic catalyst surface active coating and preparation method thereof, the catalyst takes honeycomb ceramic material with high pore volume as carrier, the coating material comprises mullite composite oxide AM 2 O 5-x A is one or more of lanthanide series metal elements, Sm, Bi and Y, M is one or more of first transition series transition metal elements, and x is between 0 and 1.
The mullite-type loaded honeycomb ceramic catalyst coating material has the advantages of small coating loss, uniform coating dispersion and stable physicochemical property, the coating and the carrier have strong bonding force and are not easy to crack, and the obtained falling rate is less than 2.5%; meanwhile, the preparation method of the honeycomb ceramic catalyst is simple, green, environment-friendly and pollution-free, so that mass production can be carried out.
In the above honeycomb ceramic catalyst, AM 2 O 5-x The mullite-type oxide can be prepared by various methods including, but not limited to, hydrothermal synthesis, coprecipitation synthesis, templating method, sol-gel synthesis, citric acid method, organic solution combustion method, spinning method, mechanical synthesis, etc., wherein the citric acid synthesis is preferred to obtain the general formula AM due to the lower synthesis temperature and better sample dispersion 2 O 5-x A type oxide; the honeycomb ceramic carrier has high mechanical strength, is easy to load various single-component or multi-component metal oxides, is not easy to lose in the actual catalytic application process, and has high catalyst activity and long service life.
The surface coating of the honeycomb ceramic catalyst comprises the following components in percentage by mass: 1-70% of mullite composite oxide AM 2 O 5-x 1.5 to 3 percent of gamma-alumina and 20 to 30 percent of additive.
In an embodiment of the present invention, the additive includes at least two of ethylene glycol, glycerin, methanol, polyvinyl alcohol, zirconium acetate, zirconium sol, aluminum sol, or silica sol, and preferably glycerin, zirconium acetate, and silica sol.
As known by the technicians in the field, the preparation and coating of surface coating slurry are the core of the technology for preparing the honeycomb ceramic catalyst, and in order to reduce the cost and energy consumption in the production process and simultaneously obtain better coating loading capacity, dispersion uniformity and reduction of shedding rate, the slurry is prepared by adding the general formula AM 2 O 5-x Mixing the compound, gamma-alumina, an additive and water according to a certain proportion, and stirring at room temperature for a period of time to obtain coating slurry, wherein the stirring time of the slurry is not less than 30 min; then, placing a carrier of the honeycomb ceramic catalyst into the coating slurry for dipping at a certain angle, wherein the angle is 70-90 degrees, and preferably 90 degrees; taking out the impregnated slurry from the slurry, and reversely blowing the redundant slurry in the pore channel; finally, drying the mixture in a low-temperature environment, and then placing the dried mixture in a muffle furnace to calcine for at least 1h to obtain the material containing the general formula AM 2 O 5-x Compound surface active coating honeycomb ceramic catalyst. Mullite AM in honeycomb ceramic catalyst surface coating slurry 2 O 5-x The particle size of the compound affects the contact effect of the coating with the carrier and the stability of the catalyst existing in the equipment, the difference of the contact effect directly results in the difference of the catalytic efficiency and the shedding rate, and in order to balance the contact effect and the stability, AM is preferred 2 O 5-x The compound has a particle size of 100 μm or less.
In an embodiment of the present application, the coating slurry of the honeycomb ceramic catalyst is not limited to the use of mullite AM 2 O 5-x Preparing a honeycomb ceramic catalyst loaded with corresponding components by using one or more of perovskite, molecular sieve, metal compound, metal oxide and carbon powder; in addition to honeycomb ceramics, the coating slurry may be applied to a support other than honeycomb ceramics in order to reduce the cost of catalysis and to minimize catalyst loss during processing due to gas purging. For example, AM will contain mullite 2 O 5-x The coating slurry of the compound is coated on the foamed ceramic so as to utilize the ceramic to carry the foamed ceramic, thereby being beneficial to the passing of the gas to be treated and the contact with the catalyst on one hand, reducing the loss of the catalyst on the other hand, prolonging the service life of the catalyst and reducing the use cost of the catalyst; meanwhile, the specific surface area of the loaded monolithic catalyst can be increased, so that the catalytic efficiency is further improved. Preferably, the support is a carbon material, a ceramic material, a foam material or a solid acidic material, more preferably ZrO 2 、TiO 2 、SiO 2 、WO 3 、 Nb 2 O 5 、SnO 2 、Al 2 O 3 、Co 3 O 4 、CeO 2 、Fe 2 O 3 Activated carbon, graphene, clay, zeolite, organometallic framework, ceramic foam, cermet, foam or sponge. The zeolite molecular sieve can be natural zeolite or synthetic zeolite. Of course, in addition to the above-mentioned carriers, carriers currently used for catalysts may be applied to the present application, and are not listed here.
General formula AM 2 O 5-x The compound-loaded honeycomb ceramic catalyst can be widely applied to the fields of energy, environment, medical treatment and families, and comprises motor vehicle tail gas treatment, fixed source flue gas catalytic oxidation, volatile organic pollutant purification, indoor and outdoor air purification, odor purification, catalytic decomposition of ozone and hydrogen peroxide and water purification.
The tail gas treatment comprises diesel engine tail gas, automobile tail gas, methanol fuel cell tail gas, industrial tail gas and the like; in one embodiment of the present application, the volatile organic pollutants to be purified are alkanes, aromatic hydrocarbons, alkenes, halogenated hydrocarbons, esters, aldehydes, ketones and other organic compounds; the odor means H 2 S、NH 3 Acetic acid, methyl mercaptan, etc.; in one embodiment of the present application, the indoor and outdoor air to be purified comprises NO, CO, CH 4 、NH 3 And any polluting gases; the catalytic decomposition of ozone and hydrogen peroxide is not only limited to room temperature, but also applicable to high temperature environment (40-110 ℃), and the ozone and hydrogen peroxide can be usedIn any form; the purification of water includes any substances polluting the environment such as hydrogen peroxide, organic compounds and chlorine in the water.
The invention reduces the stress generated between the surface coating and the carrier in the drying and calcining processes, so that the carrier is not easy to crack and fall off. Hydroxyl groups on the additive structure unit and the surfaces of the colloidal particles can act through hydrogen bonds, the viscosity of the slurry is increased, and the bonding strength between the coating and the carrier is improved. Compared with the prior art, the preparation method of the honeycomb ceramic catalyst is simple, green, environment-friendly and pollution-free, the obtained surface coating has high load, uniform dispersion and low shedding rate, no energy consumption device is additionally adopted, the production cost is low, and the quantitative and industrial large-scale production is facilitated. The honeycomb ceramic catalyst can be widely applied to the field of energy environment, and has excellent future application and development prospects.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples. The examples and comparative examples of the present invention each calculate and detect the amount of load and the shedding rate by the following means: and (3) placing the prepared honeycomb ceramic catalyst in an ultrasonic cleaner for ultrasonic treatment for 30min, then washing once, drying at 100 ℃, weighing, and calculating the falling rate of the coating according to the falling mass of the coating.
The load capacity and the shedding rate are respectively calculated by the following formulas:
capacity ═ M 1 -M 0 )/M 0 *100％
η＝[(M 1 -M 0 )-(M 2 -M 0 )]/(M 1 -M 0 )*100％
Wherein: eta is the abscission rate, M 1 Mass of honeycomb ceramic catalyst before sonication, M 2 The mass of the honeycomb ceramic catalyst after ultrasonic drying, M 0 Is blank honeycomb ceramic quality.
Example 1
Weighing mullite YMn 2 O 5 16.66g, alumina 0.34g, glycerin 30.00g, water 15.38g, zirconium acetate 12.00g, and silica sol 42.61g were placed in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading of the obtained active coating is 10.90%, and the shedding rate is 2.12%.
Example 2
Weighing mullite SmMn 2 O 5 16.66g, alumina 0.34g, glycerin 30.00g, water 15.38g, zirconium acetate 12.00g, and silica sol 42.61g were placed in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The obtained active coating has a loading of 10.89% and a peeling rate of 2.11%, and the mullite type YMn is described in connection with example 1 2 O 5 And SmMn 2 O 5 Has no influence on the coating effect of the honeycomb ceramics.
Example 3
Weighing mullite YMn 2 O 5 16.66g and 45.38g of water were placed in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading of the obtained active coating is 3.98%, and the shedding rate is 11.89%. This result indicates that the slurry, in the absence of additives and alumina, results in a honeycomb ceramic catalyst with very low coating loading and high exfoliation rate.
Example 4
Weighing mullite YMn 2 O 5 16.66g, glycerol 30.00g and water 15.38g in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading of the obtained active coating is 4.03%, and the shedding rate is 11.72%. Compared with the example 3, the coating loading and the shedding rate are basically unchanged after the additive glycerol is added into the slurry.
Example 5
Weighing mullite YMn 2 O 5 16.66g, glycerol 30.00g, water 15.38g and zirconium acetate 54.61g were put in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading of the obtained active coating is 4.51%, and the shedding rate is 11.06%. Compared with example 4, when the additives of glycerol and zirconium acetate are added simultaneously, the coating loading is slightly improved, and the shedding rate is slightly reduced.
Example 6
Weighing mullite YMn 2 O 5 16.66g, glycerol 30.00g, water 15.38g, zirconium acetate 12.00g, and silica sol 42.61g were put in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading of the obtained active coating is 10.64%, and the shedding rate is 6.12%. Compared with the example 5, after the additives of glycerol, zirconium acetate and silica sol are added simultaneously, the coating load capacity is obviously improved, and the shedding rate is reduced, which shows that the silica sol is the key for increasing the coating load capacity and reducing the shedding rate. With reference to example 1, after further adding alumina into the slurry, the coating peeling rate is reduced to within 3%, which indicates that alumina is an important component for ensuring the low peeling rate coating.
Example 7
Weighing mullite YMn 2 O 5 16.66g, 45.38g of water, 0.34g of alumina and 54.61g of silica sol were placed in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading capacity of the obtained active coating is 9.03%, and the shedding rate is 3.56%. When only the additive silica sol was added to the slurry, the coating load was reduced and the falling rate was increased as compared with example 1.
Example 8
Weighing mullite YMn 2 O 5 16.66g, 45.38g of water, 0.34g of alumina, 12.00g of zirconium acetate and 42.61g of silica sol were put in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading of the obtained active coating is 9.87%, and the shedding rate is 2.98%. Compared with the example 1, when the additive glycerol is not added in the slurry and only zirconium acetate and silica sol are added, the coating load is slightly reduced, and the shedding rate can still be kept within 3 percent. In combination with the results of the above examples, glycerol, zirconium acetate and silica sol were used as preferred additives, taking into account the combination of the conditions of high loading and low shedding rate required for the coating of the resulting honeycomb ceramic catalyst.
Example 9
Weighing mullite YMn 2 O 5 16.66g, 0.34g of alumina, 30.00g of glycerol, 12.00g of zirconium acetate and 42.61g of silica sol were placed in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, sweeping redundant slurry in a pore channel by using a dust blowing gun, drying the honeycomb ceramic in a low-temperature environment, and then putting the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The loading capacity of the obtained active coating is 11.98%, and the shedding rate is 3.01%. In comparison to example 1, the coating loading was not significantly increased without water in the slurry, but the rate of exfoliation increased to 3%, indicating that the presence of water in the slurry also slightly reduced the rate of exfoliation of the coating.
Example 10
Weighing mullite YMn 2 O 5 16.66g, alumina 0.34g, glycerin30.00g, 15.38g of water, 12.00g of zirconium acetate and 42.61g of silica sol were placed in a beaker to obtain a coating slurry.
And vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing redundant slurry in a pore channel by using a dust blowing gun, repeating the steps, coating once again, and finally placing the honeycomb ceramic in a muffle furnace for calcination to obtain the honeycomb ceramic catalyst containing the mullite compound surface active coating. The roughness of the surface of the honeycomb ceramic catalyst after being coated for one time is higher than that of the surface of uncoated honeycomb ceramic, and is more beneficial to loading coating slurry, so that the loading amount of the active coating obtained after being coated for two times is 28.36%, and the shedding rate is 2.15%.
Example 11
Weighing mullite YMn according to the mass ratio of 1:1 2 O 5 And perovskite type YMnO 3 The total of 16.66g of the material, 0.34g of alumina, 30.00g of glycerin, 15.38g of water, 12.00g of zirconium acetate and 42.61g of silica sol were placed in a beaker to obtain a coating slurry.
Vertically immersing the honeycomb ceramic into the slurry, taking out the honeycomb ceramic after immersion, blowing the redundant slurry in a pore channel by using a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the YMn containing mullite 2 O 5 And perovskite type YMnO 3 Compound surface active coating honeycomb ceramic catalyst. The loading of the obtained active coating is 10.95%, and the shedding rate is 2.13%, compared with example 1, which shows that the same coating effect can be achieved by using different active materials in combination.
Example 12
To illustrate the general applicability of the coating slurry formulation, the mullite-type material YMn in the slurry formulated in example 1 was used 2 O 5 Perovskite type YMnO 3 Replacing the material, vertically immersing the honeycomb ceramic into the slurry for immersion, taking out the honeycomb ceramic, blowing the redundant slurry in the pore passage by a dust blowing gun, and then placing the honeycomb ceramic in a muffle furnace for calcination to obtain the material containing perovskite type YMnO 3 A honeycomb ceramic catalyst of the material. The loading capacity of the obtained active coating is 10.27%, and the shedding rate is 2.13%, so that the universality of the coating slurry formula is proved, and the coating slurry is not only limited to the use of mullite compounds, but also can be used for other powder materials.
Example 13
In order to illustrate the universality of the coating slurry on other carriers, the foamed ceramic and the foamed nickel are respectively and vertically immersed into the slurry prepared according to the example 1, taken out, the redundant slurry in the pore channel is swept by a dust blowing gun, and then the mixture is placed in a muffle furnace to be calcined, so that the foamed ceramic catalyst and the foamed nickel catalyst containing the mullite compound surface active coating are respectively obtained. The loading of the active coating of the obtained foamed ceramic catalyst is 11.32%, the shedding rate is 2.07%, the loading of the active coating of the foamed nickel catalyst is 30.69%, and the shedding rate is 9.81%, which proves that the coating slurry of the honeycomb ceramic catalyst can be coated on a carrier except for honeycomb ceramic.
Example 14
The honeycomb ceramic catalyst prepared in example 1 was subjected to a volatile organic contaminant propane oxidation experiment. Honeycomb ceramic catalysts having a length, width and height of 10mm, 10mm and 18mm, respectively, were cut out and placed in a reaction tube having an inner diameter of 17mm, and an air stream containing propane at a concentration of 420ppm was introduced, and the conversion of propane was represented by the consumption rate of propane, and the test results are shown in fig. 2. The results show that the honeycomb ceramic catalyst can realize 90 percent conversion of propane at 360 ℃ and can completely purify the propane at 410 ℃.
Example 15
The honeycomb ceramic catalyst prepared in example 1 was subjected to a simulated mobile pollution source tail gas NO oxidation experiment. The honeycomb ceramic catalyst having a length, width and height of 10mm, 10mm and 50mm, respectively, was cut out and placed in a reaction tube having an inner diameter of 17mm, and an air stream having a concentration of 420ppm NO was introduced, and the NO conversion was represented by the NO consumption rate, and the test results are shown in FIG. 3. The result shows that the honeycomb ceramic catalyst can realize 75 percent conversion of NO at 300 ℃.
Example 16
The honeycomb ceramic catalysts prepared in examples 1 and 12 were subjected to an experiment simulating catalytic decomposition of hydrogen peroxide at room temperature. Cutting honeycomb ceramic catalyst with length, width and height of 10mm, 10mm and 50mm respectively, and mixing mullite type YMn 2 O 5 Honeycomb ceramic catalyst, perovskite type YMnO 3 Honeycomb ceramic catalyst and unsupported honeycomb ceramicRespectively placing the mixture in a container with the concentration of 10.26mol L -1 The volume of the solution in the beaker of hydrogen peroxide was 100ml, the reaction temperature was 25 ℃, the conversion of hydrogen peroxide was expressed by the consumption rate of hydrogen peroxide, and the test results are shown in Table 3. The results show that mullite-type YMn 2 O 5 The honeycomb ceramic catalyst can realize 100 percent conversion of hydrogen peroxide within 36 hours, the perovskite type honeycomb ceramic catalyst has poor performance of catalytic decomposition of the hydrogen peroxide, and the unsupported honeycomb ceramic has no catalytic activity on the hydrogen peroxide.
Example 17
The honeycomb ceramic catalyst prepared in example 1 was subjected to an experiment simulating catalytic decomposition of hydrogen peroxide at different ambient temperatures. Cutting honeycomb ceramic catalyst with length, width and height of 10mm, 10mm and 50mm respectively, and mixing mullite type YMn 2 O 5 The honeycomb ceramic catalysts are respectively placed in a reactor with the concentration of 10.26mol L -1 The volume of the solution in the beaker of hydrogen peroxide was 100ml, the reaction temperatures were 25 ℃, 50 ℃ and 80 ℃ respectively, and the conversion rate of hydrogen peroxide was represented by the consumption rate of hydrogen peroxide, and the test results are shown in Table 4. The results show that the catalytic decomposition rate of the mullite-type honeycomb ceramic catalyst for hydrogen peroxide becomes larger as the reaction temperature increases.
TABLE 1 influence of different formulations in the slurry on the coating effect of the honeycomb ceramics
TABLE 2 Effect of different active materials and carriers on coating effectiveness
TABLE 3 catalytic decomposition Performance of Honeycomb ceramic catalyst for Hydrogen peroxide at Room temperature
TABLE 4 catalytic decomposition Performance of mullite-type honeycomb ceramic catalyst for Hydrogen peroxide at various temperatures
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the mullite-type loaded honeycomb ceramic catalyst coating has the advantages of small coating loss, uniform dispersion of the coating and stable physicochemical property, the binding force between the coating and the carrier is strong, the coating is not easy to crack, and the obtained falling rate is less than 2.5%; meanwhile, the preparation method of the honeycomb ceramic catalyst is simple, green, environment-friendly and pollution-free, so that mass production can be carried out. The honeycomb ceramic catalyst can be widely applied to the field of energy environment, and has excellent future application and development prospects.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The honeycomb ceramic catalyst is characterized in that the catalyst takes a honeycomb ceramic material with high pore volume as a carrier, and the coating material comprises mullite composite oxide AM 2 O 5-x A is one or more of lanthanide series metal elements, Sm, Bi and Y, M is one or more of first transition series transition metal elements, and x is between 0 and 1.
2. The honeycomb ceramic catalyst according to claim 1, wherein the coating material for the surface of the honeycomb ceramic catalyst comprises the following components in percentage by mass: 1-70% of mullite composite oxide AM 2 O 5-x 1.5 to 3 percent of gamma-alumina and 20 to 30 percent of additive.
3. The honeycomb ceramic catalyst according to claim 1 or 2, wherein the additive comprises at least two of ethylene glycol, glycerol, methanol, polyvinyl alcohol, zirconium acetate, zirconium sol, aluminum sol, or silica sol, preferably glycerol, zirconium acetate, and silica sol.
4. The honeycomb ceramic catalyst according to claim 1 or 2, which is prepared by a method comprising the steps of:
first, the general formula AM 2 O 5-x Mixing a compound, gamma-alumina, an additive and water according to a certain proportion, and stirring for a period of time at room temperature to obtain coating slurry;
secondly, soaking the honeycomb ceramic in the coating slurry, then removing redundant slurry in the honeycomb ceramic pore channel by blowing a dust gun, and finally drying and calcining, wherein the coating step is carried out once, and the coating step is optionally repeated for 1-5 times to obtain the coating containing the general formula AM 2 O 5-x Compound surface active coating honeycomb ceramic catalyst.
5. The honeycomb ceramic catalyst according to claim 4, wherein the coating slurry is prepared in the first step of the coating slurry preparation step by using the general formula AM 2 O 5-x The compound has a particle size of 100 μm or less, and the slurry is stirred for at least 30 min.
6. The honeycomb ceramic catalyst according to claim 4, wherein in the second step of the coating slurry preparation step, when the carrier of the honeycomb ceramic catalyst is placed in the slurry containing the mullite-type composite oxide at an angle for dip coating, the angle is 70 to 90 °, preferably 90 °; taking out the impregnated slurry from the slurry, and reversely blowing the redundant slurry in the pore channel; the drying and calcining treatment is as follows: drying the mixture in a low-temperature environment, and then calcining the dried mixture in a muffle furnace for at least 1 h.
7. The honeycomb ceramic catalyst according to claim 4, wherein one or more of perovskite, molecular sieve, metal compound, metal oxide, carbon powder may be further used in the coating slurry of the honeycomb ceramic catalyst.
8. The honeycomb ceramic catalyst according to claim 4, wherein the coating slurry of the honeycomb ceramic catalyst is coated on a support other than honeycomb ceramic, preferably the support is a carbon material, a ceramic material, a foam material or a solid acidic material, more preferably ZrO 2 、TiO 2 、SiO 2 、WO 3 、Nb 2 O 5 、SnO 2 、Al 2 O 3 、Co 3 O 4 、CeO 2 、Fe 2 O 3 Activated carbon, graphene, clay, zeolite, organometallic frameworks, ceramic foams, cermet, foams, sponges.
9. Use of a honeycomb ceramic catalyst according to claim 1, characterized in that the general formula AM 2 O 5-x The compound-loaded honeycomb ceramic catalyst is applied to the fields of energy, environment, medical treatment and families, such as motor vehicle tail gas treatment, fixed source flue gas catalytic oxidation, volatile organic pollutant purification, indoor and outdoor air purification, odor purification, catalytic decomposition of ozone and hydrogen peroxide and water purification.
10. Use of the honeycomb ceramic catalyst according to claim 9, wherein the exhaust gas treatment comprises diesel exhaust, automobile exhaust, methanol fuel cell exhaust, industrial exhaust, etc.; the volatile organic contaminants are alkanesAromatic hydrocarbons, alkenes, halogenated hydrocarbons, esters, aldehydes, ketones and other organic compounds; the odor means H 2 S、NH 3 Acetic acid, methyl mercaptan, etc.; the object gas for indoor and outdoor air purification comprises NO, CO and CH 4 、NH 3 And other polluting gases; the catalytic decomposition of the ozone and the hydrogen peroxide is not only limited to the room temperature condition, but also can be applied to the high-temperature environment (40-110 ℃), and the ozone and the hydrogen peroxide can exist in any form; the purification of water includes any substances polluting the environment such as hydrogen peroxide, organic compounds and chlorine in the water.
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| CN113244754A (en) * | 2021-06-07 | 2021-08-13 | 南开大学 | General formula AM2O5Application of compound as catalyst for treating ozone at room temperature |
| CN114180614A (en) * | 2021-12-28 | 2022-03-15 | 南开大学 | General formula AM2O5-xApplication of compound to catalysis of hydrogen peroxide at room temperature |
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| CN103958027A (en) * | 2011-10-06 | 2014-07-30 | 巴斯夫公司 | Methods of applying a sorbent coating on a substrate, a support, and/or a substrate coated with a support |
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| CN113244754A (en) * | 2021-06-07 | 2021-08-13 | 南开大学 | General formula AM2O5Application of compound as catalyst for treating ozone at room temperature |
| CN114180614A (en) * | 2021-12-28 | 2022-03-15 | 南开大学 | General formula AM2O5-xApplication of compound to catalysis of hydrogen peroxide at room temperature |
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| CN117380255A (en) * | 2023-12-05 | 2024-01-12 | 河北华特汽车部件有限公司 | Preparation method and application of catalyst for purifying nitrogen oxides |
| CN117380255B (en) * | 2023-12-05 | 2024-02-27 | 河北华特汽车部件有限公司 | Preparation method and application of catalyst for purifying nitrogen oxides |
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