CN114433115A - Coating slurry and preparation method and application thereof - Google Patents
Coating slurry and preparation method and application thereof Download PDFInfo
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- CN114433115A CN114433115A CN202011107104.4A CN202011107104A CN114433115A CN 114433115 A CN114433115 A CN 114433115A CN 202011107104 A CN202011107104 A CN 202011107104A CN 114433115 A CN114433115 A CN 114433115A
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- cobalt
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- containing oxide
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- 239000006255 coating slurry Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 86
- 239000010941 cobalt Substances 0.000 claims abstract description 86
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 239000000084 colloidal system Substances 0.000 claims abstract description 44
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000003801 milling Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 62
- 238000000576 coating method Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 23
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 23
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 22
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 120
- 239000000243 solution Substances 0.000 description 67
- 239000007789 gas Substances 0.000 description 54
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 38
- 239000002002 slurry Substances 0.000 description 24
- 239000012298 atmosphere Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 238000000861 blow drying Methods 0.000 description 21
- 239000000919 ceramic Substances 0.000 description 21
- 239000011268 mixed slurry Substances 0.000 description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 21
- 239000004926 polymethyl methacrylate Substances 0.000 description 21
- 239000011148 porous material Substances 0.000 description 21
- 238000002791 soaking Methods 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 19
- 239000004327 boric acid Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004299 exfoliation Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
Classifications
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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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
-
- 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
-
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a doped cobalt-containing oxide, which comprises a cobalt-containing active component, a first doping auxiliary agent, a second doping auxiliary agent and a third doping auxiliary agent; wherein the first doping auxiliary metal is selected from at least one of B and Ga, the second doping auxiliary is selected from at least one of Zr and Ti, and the third doping auxiliary is selected from at least one of W and Mo; and the doped cobalt-containing oxide and the pseudo-boehmite/molecular sieve/adhesive are subjected to colloid milling to obtain coating slurry. The doped cobalt oxide with special components and proportion and the coating slurry for the catalyst prepared from the doped cobalt oxide have the advantages of good stability and difficulty in falling off from a carrier, and the preparation method is simple and easy to carry out and is suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to adsorption/catalysis coating slurry for waste gas treatment, and a preparation method and application thereof.
Background
The catalytic combustion method reduces the operation temperature to 280-450 ℃ by means of the action of the catalyst, greatly reduces the energy consumption, has safe and stable operation, low operation cost and no generation of nitrogen oxides, thereby not generating secondary pollution. Therefore, the catalytic combustion method is an ideal method for treating the organic waste gas.
Catalysts for organic exhaust gas treatment are often prepared by coating methods, i.e. by applying a coating slurry containing the desired active components to a support. However, the coating slurry still containing active components at present has insufficient viscosity and low binding degree with a carrier, so that the loading capacity is insufficient and the coating slurry is easy to fall off, and the performance of the industrial and chemical waste gas catalyst is influenced.
Disclosure of Invention
The invention provides a coating slurry for a catalyst, which is prepared from a doped cobalt-containing oxide, and aims to solve the technical problems that the viscosity of the coating slurry of an industrial chemical waste gas catalyst is insufficient, or the binding degree of the coating slurry and a carrier is not high, the coating slurry is easy to fall off and the like; wherein the content of the first and second substances,
the cobalt-containing active component comprises one or more of cobalt, a cobalt salt or an oxide thereof;
the first doping auxiliary metal is selected from at least one of B and Ga, and/or
The second doping auxiliary agent is selected from at least one of Zr and Ti, and/or
The third doping auxiliary is selected from at least one of W and Mo.
In one embodiment, the cobalt salt comprises a nitrate or sulfate, chloride, acetate salt of cobalt.
In one embodiment, the molar ratio of the first doping aid metal to cobalt is 0.01:1 to 0.03:1, the molar ratio of the second doping aid metal to cobalt is 0.05:1 to 0.25:1, and the molar ratio of the third doping aid metal to cobalt is 0.02:1 to 0.04: 1.
In one embodiment, the doped cobalt-containing oxide comprises Co3O4The spinel structure of (1).
In one embodiment, the XRD diffraction pattern of the doped cobalt-containing oxide comprises one or more characteristic peaks in 2 Θ selected from 31.164 ± 0.20, 36.764 ± 0.18, 44.692 ± 0.25, 55.578 ± 0.20, 59.253 ± 0.26 and 65.203 ± 0.15;
in a specific embodiment, the doped cobalt-containing oxide XRD diffraction pattern comprises one or more characteristic peaks in 2 Θ selected from 30.201 ± 0.20, 50.503 ± 0.15;
in a specific embodiment, the doped cobalt-containing oxide XRD diffraction pattern comprises one or more characteristic peaks in 2 θ selected from 25.301 ± 0.25, 48.051 ± 0.20.
Another object of the present invention is to provide a method for preparing the above doped cobalt-containing oxide, comprising the following steps: dissolving the cobalt-containing active component, the first doping auxiliary agent, the second doping auxiliary agent and the third doping auxiliary agent, adding a template agent to obtain sol, filtering the sol to obtain a solid, and drying and roasting to obtain the doped cobalt-containing oxide.
In one embodiment, the cobalt-containing active component in the method comprises one or more of cobalt, a cobalt salt, or an oxide thereof.
In a particular embodiment, the cobalt salt in the process comprises a nitrate or sulphate salt, chloride salt, acetate salt.
In one embodiment, the precursor metal of the first doping aid in the method is selected from at least one of B and Ga.
In one embodiment, the precursor metal of the second doping aid in the method is selected from at least one of Zr and Ti.
In one embodiment, the precursor metal of the third doping aid in the process is selected from at least one of W and Mo.
In one embodiment, the method comprises the steps of dissolving a cobalt-containing active component, a precursor of a first doping auxiliary agent, a second doping auxiliary agent and a third doping auxiliary agent in a solvent twice, dissolving the mixture by using polyethylene glycol and water, stirring the mixture to be transparent, adding methanol into the transparent solution, adding a template agent into the transparent solution to form sol, filtering and washing the sol, and drying and roasting the obtained solid to obtain the doped cobalt-containing oxide.
In one embodiment, the templating agent in the method comprises polymethylmethacrylate, polyvinyl alcohol, or polystyrene-polypropylene oxide copolymer.
In one embodiment, the method wherein calcining the solid comprises drying at 60 ℃ for 12 hours in O2/N2The mixture is calcined in an atmosphere of 1/99 at 200 ℃ for 2 hours and then in air at 500 ℃ for 4 hours to form the doped cobalt-containing oxide.
The invention also aims to provide coating slurry for a catalyst prepared from the doped cobalt-containing oxide, which comprises the following components in parts by weight:
a)12 to 25 parts of the doped cobalt-containing oxide according to any one of claims 1 to 3;
b) 15-30 parts of pseudo-boehmite;
c) 3-6 parts of a molecular sieve;
d) 1-3 parts of an adhesive;
e) 0.1-0.5 parts of a dispersant;
f) 0.5-1.5 parts of a pH regulator;
g) the balance being solvent.
In one embodiment, the molecular sieve is selected from one or both of SBA-15 and MCM-41.
In one embodiment, the adhesive comprises an aluminum sol, and preferably the adhesive comprises 20-40% of the aluminum sol by mass of alumina.
In one embodiment, the dispersant comprises one or more of polyacrylic acid, polyethylene glycol, tetrapropylammonium bromide.
In one embodiment, the pH adjusting agent comprises one or more of nitric acid, hydrochloric acid, or sulfuric acid.
In one embodiment, the solvent comprises one or more of tap water, deionized water, or high purity water.
In one embodiment, the coating slurry has a viscosity of 650 to 850mpa.s and a slurry particle size D97 of less than 22 μm.
Still another object of the present invention is to provide a method for preparing the above coating slurry for a catalyst, comprising the steps of: and (3) contacting the doped cobalt-containing oxide, pseudo-boehmite, a molecular sieve, an adhesive, a dispersant and a pH regulator with a solvent, stirring for 1-4 hours, and carrying out adhesive grinding to obtain coating slurry.
It is a further object of the present invention to provide the use of the above coating slurry for the preparation of industrial exhaust gas catalysts.
Compared with the prior art, the invention has the following beneficial effects:
(1) the doped cobalt oxide with special components and proportion has higher catalytic activity and higher adhesive force with the carrier;
(2) during preparation, the rubber grinding degree is controlled to obtain slurry with special viscosity and granularity, and the catalyst coated with the slurry has low falling rate and high stability.
(3) The doped cobalt oxide and the auxiliary agent endow the coating slurry with cohesive force and compatibility among all components, so that the overall viscosity and stability are improved, and a better technical effect is obtained.
The doped cobalt oxide with special components and proportion and the coating slurry for the catalyst prepared from the doped cobalt oxide have the advantages of good stability and difficulty in falling off from a carrier, and the preparation method is simple and easy to carry out and is suitable for large-scale production and application.
Drawings
Fig. 1 is an XRD diffractogram of a doped cobalt-containing oxide prepared according to an embodiment of the present invention.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The performance of the invention was determined as follows:
coating slurry viscosity test: measured by using a Bohler flying DV2T viscometer, the test method comprises the following steps: at 25 ℃, 50mL of the liquid to be measured is poured into the measuring cup, and the measuring time is 300 s.
And (3) testing the catalytic performance: and (3) carrying out catalytic reaction performance evaluation on the catalyst on a catalytic combustion reaction device of the fixed bed reactor under the same condition. The process conditions are as follows: in the air atmosphere, the reaction pressure is 0.05MPa-0.1MPa, the amount of tail gas treated by each gram of catalyst is 20L per hour, and the temperature is programmed to the reaction temperature until the catalyst is completely converted. The temperature rising procedure is as follows: raising the temperature from 20 ℃ to 100 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 0.5 hour, raising the temperature to 150 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 0.5 hour, raising the temperature to 160 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 5 minutes, raising the temperature to 165 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 5 minutes, raising the temperature to 170 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 5 minutes, and so on until the temperature is raised to 400 ℃.
Ultrasonic shedding rate test: the coating stability of the exhaust gas treatment catalyst is evaluated by an ultrasonic vibration test, a sample is put into an ultrasonic cleaner with water as a medium, the ultrasonic working frequency is 53KHz, and the falling rate is calculated after 30 minutes of ultrasonic treatment.
The ultrasonic shedding rate (total mass of the ultrasonic pre-catalyst-total mass of the ultrasonic post-catalyst)/(total mass of the ultrasonic pre-catalyst-mass of the honeycomb carrier before coating) is 100%.
[ example 1 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide. Fig. 1 shows XRD diffractograms of the doped cobalt-containing oxides obtained by the preparation, wherein the XRD diffractograms had 8 characteristic peaks at 2 θ of 30.201 ± 0.20, 31.164 ± 0.20, 36.764 ± 0.18, 44.692 ± 0.25, 50.503 ± 0.15, 55.578 ± 0.20, 59.253 ± 0.26 and 65.203 ± 0.15.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 650 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst A. The ultrasonic shedding rate was found to be 2.1%.
[ example 2 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.1854g of boric acid and 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% alumina sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 653.4 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst B. The ultrasonic shedding rate was found to be 2.03%.
[ example 3 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 10.733g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washingThe obtained solid is dried at room temperature and 60 ℃ for 12 hours in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 652.8 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst C. The ultrasonic exfoliation rate was measured to be 2.12%.
[ example 4 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate, and 1.014g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.8 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst D. The ultrasonic shedding rate was measured to be 1.98%.
[ example 5 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.256g of gallium nitrate, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% alumina sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is determined to be 655.2 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst E. The ultrasonic shedding rate was measured to be 1.95%.
[ example 6 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 0.945g of titanium tetrachloride and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sandiao, Utility Co., Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xiancheng nano materials science and technology Co., Ltd.), 1 part of 20% alumina sol (Jiangsu Sandiao, Utility Co., Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 r.p.m, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 651.8 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst F. The ultrasonic exfoliation rate was measured to be 2.08%.
[ example 7 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.1854g of boric acid, 2.146g of zirconium nitrate and 0.353g of ammonium heptamolybdate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 655.5 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100G/L, and thus obtaining the exhaust gas treatment catalyst G. The ultrasonic shedding rate was measured to be 1.96%.
[ example 8 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 9.6g of methanol so that the content of methanol was 5 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% alumina sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 657.5 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst H. The ultrasonic shedding rate was measured to be 1.92%.
[ example 9 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0..0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. 2g of polymethyl methacrylate template agent was added to the above clear solutionStirring for 1 hr, standing overnight to obtain sol, filtering, washing to obtain solid, air drying at room temperature, drying at 60 deg.C for 12 hr, and adding into O solution2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
25 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 659.6 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst I. The ultrasonic exfoliation rate was measured to be 1.88%.
[ example 10 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 30 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 665.8 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst J. The ultrasonic shedding rate was measured to be 1.82%.
[ example 11 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 6 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 663.2 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst K. The ultrasonic shedding rate was measured to be 1.85%.
[ example 12 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology Co., Ltd.), 3 parts of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 679.1 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst L. The ultrasonic exfoliation rate was measured to be 1.72%.
[ example 13 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.5 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.5 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst M. The ultrasonic shedding rate was measured to be 1.96%.
[ example 14 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 1.5 parts of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 656.8 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst N. The ultrasonic shedding rate was measured to be 1.95%.
[ example 15 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol to make the solution methanolThe content was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 40% alumina sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 680 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst O. The ultrasonic shedding rate was measured to be 1.71%.
[ example 16 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0309g of boric acid, 0.128g of gallium nitrate, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2Baking at 200 deg.C for 2 hr under 1/99 atmosphere, and baking at 500 deg.C in airAfter 4 hours of firing, the doped cobalt-containing oxide was obtained.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 653.8 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst P. The ultrasonic exfoliation rate was measured to be 2.01%.
[ example 17 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 1.073g of zirconium nitrate, 0.472g of titanium tetrachloride and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.3 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst Q. The ultrasonic shedding rate was measured to be 1.97%.
[ example 18 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate, 0.253g of ammonium tungstate, and 0.176g of ammonium heptamolybdate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.1 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst R. The ultrasonic shedding rate was measured to be 1.95%.
Comparative example 1
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate are dissolved in 200ml of deionized water, 2mol/L of sodium carbonate solution is added to the solution until the pH value is 9.5, the solution is stirred for 2 hours at 60 ℃, the solution is filtered and washed until the pH value is 7, the obtained precipitate is dried for 12 hours at 110 ℃, and then is roasted for 4 hours at 500 ℃ to obtain a doped cobalt-containing oxide;
contacting 12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite, 3 parts of SBA-15 molecular sieve, 1 part of 20% alumina sol, 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid with water, stirring at 3000 r for 1 hour, carrying out colloid milling on the uniformly mixed slurry in a colloid mill for 2 hours until the particle size is D97 less than 22 mu m, obtaining coating slurry, and measuring the viscosity of the coating slurry to be 530.1 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst S. The ultrasonic exfoliation rate was measured to be 6.15%.
Comparative example 2
Preparation of coating slurry:
29.103g of cobalt nitrate was dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol,so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2And (3) roasting at 200 ℃ for 2 hours in an atmosphere of 1/99, and then roasting at 500 ℃ for 4 hours in the air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 528.5 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on a honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst T. The ultrasonic shedding rate was measured to be 6.38%.
Comparative example 3
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.0618g of boric acid, 2.146g of zirconium nitrate and 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred for 2 hours to obtain a transparent solution. To the clear solution was added 5.76g of methanol so that the content of methanol was 3 mol/L. Adding 2g of polymethyl methacrylate template agent into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing the sol, drying the obtained solid at room temperature for 12 hours at 60 ℃, and drying in O2/N2Baking at 200 deg.C for 2 hr under 1/99 atmosphere, and baking at 500 deg.C in airAfter 4 hours of firing, the doped cobalt-containing oxide was obtained.
10 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanjie industries, Ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xifeng nanometer materials science and technology, Ltd.), 1 part of 20% aluminum sol (Jiangsu Sanjie industries, Ltd.), 0.1 part of tetrapropylammonium bromide and 0.5 part of nitric acid are contacted with water, stirred for 1 hour at 3000 revolutions, the uniformly mixed slurry is subjected to colloid milling in a colloid mill for 2 hours until the particle size D97 is smaller than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 625.5 mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting a cylindrical honeycomb carrier at 200 ℃ for 2 hours, soaking the treated carrier in the coating slurry for 0.5 hour, taking out the carrier, blow-drying the residual slurry in a pore channel, drying, roasting, weighing, repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic framework in unit volume is 50-100 g/L, and thus obtaining the exhaust gas treatment catalyst U. The ultrasonic shedding rate was measured to be 4.68%.
Test example 1
The catalysts A-U were subjected to catalytic reaction performance evaluation on a fixed bed reactor catalytic reaction apparatus under the same conditions, and the reaction results are shown in Table 1. In this test example, the exhaust gas containing organic matter was brought into contact with a catalyst to perform catalytic combustion, and the process conditions evaluated were as follows: in the air atmosphere, the reaction pressure is 0.05MPa-0.1MPa, the amount of tail gas treated by each gram of catalyst is 20L per hour, and the temperature is programmed to the reaction temperature until the catalyst is completely converted. The temperature rising procedure is as follows: raising the temperature from 20 ℃ to 100 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 0.5 hour, raising the temperature to 150 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 0.5 hour, raising the temperature to 160 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 5 minutes, raising the temperature to 165 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 5 minutes, raising the temperature to 170 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 5 minutes, and so on until the temperature is raised to 400 ℃.
The waste gas containing organic matters is simulation gas, and the carrier gas is nitrogen.
When a single organic matter component is evaluated, the organic matter concentrations in three waste gases containing a single organic matter are respectively as follows: 6000ppm of methyl acetate, 1000ppm of p-xylene and 300ppm of methylene bromide.
When the mixed sample is evaluated, the organic matter composition in the organic matter waste gas containing the mixed sample is as follows: 3000ppm of methyl acetate, 500ppm of p-xylene and 100ppm of dibromomethane.
The reaction activity of the catalyst takes the height of the reaction temperature of the complete conversion of the oxidation tail gas components as an evaluation standard, and the lower the complete conversion temperature is, the better the performance of the catalyst is. Wherein T99 for a single component represents the reaction temperature at which the purification rate of the component in the exhaust gas is 99%. The T99 of the mixed sample is represented as the reaction temperature at which the purification rate of all components in the exhaust gas reached 99%. 400(Tn) indicates that the purification rate of dibromomethane at 400 ℃ is n%, and when the mixed sample is treated, the purification rates of methyl acetate and p-xylene at this time are 99% or more.
TABLE 1
| DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION | Acetic acid methyl ester T99 | Para-xylene T99 | Bromomethane T99 | Mixed sample T99 |
| Example 1 | 240 | 280 | 320 | 335 |
| Example 2 | 245 | 275 | 320 | 340 |
| Example 3 | 240 | 275 | 325 | 340 |
| Example 4 | 245 | 270 | 325 | 340 |
| Example 5 | 240 | 285 | 325 | 345 |
| Example 6 | 245 | 275 | 315 | 335 |
| Example 7 | 235 | 275 | 325 | 340 |
| Example 8 | 245 | 285 | 325 | 350 |
| Example 9 | 240 | 280 | 315 | 335 |
| Example 10 | 230 | 290 | 320 | 345 |
| Example 11 | 235 | 285 | 315 | 340 |
| Example 12 | 235 | 275 | 320 | 335 |
| Example 13 | 240 | 290 | 320 | 345 |
| Example 14 | 245 | 280 | 320 | 345 |
| Example 15 | 240 | 275 | 320 | 340 |
| Example 16 | 245 | 275 | 320 | 340 |
| Example 17 | 235 | 285 | 315 | 335 |
| Example 18 | 240 | 285 | 320 | 340 |
| Comparative example 1 | 285 | 350 | 385 | 400 |
| Comparative example 2 | 315 | 355 | 390 | 400 |
| Comparative example 3 | 330 | 360 | 400(T85) | 400(T80) |
Note: t in Table 199All units are in DEG C.
Claims (10)
1. A doped cobalt-containing oxide is prepared from a cobalt-containing active component, a first doping auxiliary agent, a second doping auxiliary agent and a third doping auxiliary agent; wherein the content of the first and second substances,
the cobalt-containing active component comprises one or more of cobalt, a cobalt salt or an oxide thereof;
the first doping auxiliary metal is selected from at least one of B and Ga, and/or
The second doping auxiliary agent is selected from at least one of Zr and Ti, and/or
The third doping auxiliary is selected from at least one of W and Mo.
2. The doped cobalt-containing oxide according to claim 1, wherein the molar ratio of the first doping auxiliary metal to cobalt is 0.01:1 to 0.03:1, the molar ratio of the second doping auxiliary metal to cobalt is 0.05:1 to 0.25:1, and the molar ratio of the third doping auxiliary metal to cobalt is 0.02:1 to 0.04: 1.
3. The doped cobalt-containing oxide of claim 1 or 2, wherein the doped cobalt-containing oxide comprises Co3O4Of spinel structure, and/or
An XRD diffraction pattern of the doped cobalt-containing oxide has one or more characteristic peaks including 2 Θ selected from 31.164 ± 0.20, 36.764 ± 0.18, 44.692 ± 0.25, 55.578 ± 0.20, 59.253 ± 0.26 and 65.203 ± 0.15; preferably comprising one or more characteristic peaks having a 2 θ selected from 30.201 ± 0.20, 50.503 ± 0.15; more preferably one or more characteristic peaks having a 2 theta selected from 25.301 + -0.25, 48.051 + -0.20.
4. A preparation method of a doped cobalt-containing oxide comprises the following steps: dissolving the cobalt-containing active component, the first doping auxiliary agent, the second doping auxiliary agent and the third doping auxiliary agent, adding a template agent to obtain sol, filtering the sol to obtain a solid, and drying and roasting to obtain the doped cobalt-containing oxide.
5. The method according to claim 4, wherein the cobalt-containing active component comprises a cobalt salt, preferably comprising cobalt nitrate; and/or the precursor metal of the first doping auxiliary is selected from at least one of B and Ga, and/or the precursor metal of the second doping auxiliary is selected from at least one of Zr and Ti, and/or the precursor metal of the third doping auxiliary is selected from at least one of W and Mo.
6. A coating slurry for a catalyst comprises the following components in parts by weight:
a)12 to 25 parts of the doped cobalt-containing oxide according to any one of claims 1 to 3;
b) 15-30 parts of pseudo-boehmite;
c) 3-6 parts of a molecular sieve;
d) 1-3 parts of an adhesive;
e) 0.1-0.5 parts of a dispersant;
f) 0.5-1.5 parts of a pH regulator;
g) the balance being solvent.
7. The coating slip of claim 6, wherein the molecular sieve is selected from one or both of SBA-15 and MCM-41; and/or the adhesive comprises an aluminum sol, preferably the adhesive comprises 20-40% of the aluminum sol by mass percent of alumina; and/or the dispersant comprises one or more of polyacrylic acid, polyethylene glycol and tetrapropylammonium bromide; and/or the pH regulator comprises one or more of nitric acid and hydrochloric acid; and/or the solvent comprises one or more of tap water, deionized water or high-purity water.
8. The coating slip of claim 6 or 7, wherein the coating slip has a viscosity of 650-850mpa.s and a slip particle size D97 of less than 22 μm.
9. A preparation method of coating slurry for a catalyst comprises the following steps: the doped cobalt-containing oxide, pseudo-boehmite, molecular sieve, adhesive, dispersant and pH regulator as defined in any one of claims 1-3 are contacted with a solvent, stirred for 1-4 hours, and then subjected to colloid milling to obtain coating slurry.
10. Use of a coating slip according to any one of claims 6 to 8 for the preparation of industrial exhaust gas catalysts.
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| EP0882506A1 (en) * | 1997-05-22 | 1998-12-09 | Ecia - Equipements Et Composants Pour L'industrie Automobile | Process for producing a catalytic converter containing oxides |
| CN103055919A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Structured catalyst of propylene by steam cracking |
| CN103071481A (en) * | 2012-12-29 | 2013-05-01 | 烟台万华聚氨酯股份有限公司 | Fischer-Tropsch synthesis cobalt-based catalyst and preparation method thereof |
| US20140170032A1 (en) * | 2012-03-28 | 2014-06-19 | Hyundai Heavy Industries Co., Ltd. | Metal filter for purifying exhaust gas from ship, and preparation method thereof |
| CN111054360A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for catalytic combustion treatment of PTA tail gas |
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2020
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| US5238890A (en) * | 1990-10-31 | 1993-08-24 | Idemitsu Kosan Company Limited | Exhaust gas purifying catalyst and an exhaust gas purifying method using the catalyst |
| JPH0824648A (en) * | 1994-07-22 | 1996-01-30 | Nissan Motor Co Ltd | Exhaust gas purifying catalyst and preparation of the sam |
| EP0882506A1 (en) * | 1997-05-22 | 1998-12-09 | Ecia - Equipements Et Composants Pour L'industrie Automobile | Process for producing a catalytic converter containing oxides |
| CN103055919A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Structured catalyst of propylene by steam cracking |
| US20140170032A1 (en) * | 2012-03-28 | 2014-06-19 | Hyundai Heavy Industries Co., Ltd. | Metal filter for purifying exhaust gas from ship, and preparation method thereof |
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| CN111054360A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for catalytic combustion treatment of PTA tail gas |
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