CN114433115B - Coating slurry and preparation method and application thereof - Google Patents
Coating slurry and preparation method and application thereof Download PDFInfo
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- CN114433115B CN114433115B CN202011107104.4A CN202011107104A CN114433115B CN 114433115 B CN114433115 B CN 114433115B CN 202011107104 A CN202011107104 A CN 202011107104A CN 114433115 B CN114433115 B CN 114433115B
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- 239000006255 coating slurry Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 89
- 239000010941 cobalt Substances 0.000 claims abstract description 89
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000084 colloidal system Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 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
- 238000003801 milling Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 126
- 238000000576 coating method Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000002202 Polyethylene glycol Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 238000003756 stirring Methods 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
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 22
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 21
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 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
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel 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
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 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
- 239000000243 solution Substances 0.000 description 69
- 239000007789 gas Substances 0.000 description 49
- 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
- 239000012298 atmosphere Substances 0.000 description 23
- 239000002002 slurry Substances 0.000 description 23
- 239000000919 ceramic Substances 0.000 description 21
- 239000011268 mixed slurry Substances 0.000 description 21
- 239000011148 porous material Substances 0.000 description 21
- 239000011259 mixed solution Substances 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 19
- 239000002086 nanomaterial Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002912 waste gas Substances 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 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 238000011156 evaluation 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
- 239000005416 organic matter Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- 238000007598 dipping method Methods 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002244 precipitate Substances 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
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- GEEGFFDUNIISFE-UHFFFAOYSA-N [O-][N+]([Co])=O Chemical compound [O-][N+]([Co])=O GEEGFFDUNIISFE-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 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
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
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; the doped cobalt-containing oxide, pseudo-boehmite/molecular sieve/adhesive and the like are subjected to colloid milling to obtain coating slurry. The doped cobalt oxide with special components and the proportion and the coating slurry for the catalyst prepared by the doped cobalt oxide have the advantages of good stability and difficult 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/catalytic coating slurry for waste gas treatment, and a preparation method and application thereof.
Background
In the petrochemical production process, waste gas containing volatile organic compounds is often generated, the catalytic combustion method reduces the operation temperature to 280-450 ℃ by means of the action of a catalyst, the energy consumption is greatly reduced, the operation is safe and stable, the operation cost is low, nitrogen oxides are not generated, and therefore secondary pollution is not generated. Therefore, catalytic combustion processes are ideal for treating organic waste gases.
Catalysts for the treatment of organic waste gases are often prepared by a coating process, i.e. by coating a support with a coating slurry containing the desired active components. However, the existing coating slurry containing active components is insufficient in viscosity and low in combination degree with a carrier, so that the coating slurry is insufficient in load and easy to fall off, and the performance of the industrial chemical waste gas catalyst is affected.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the coating slurry of the industrial chemical waste gas catalyst has insufficient viscosity or the coating slurry has low combination degree with a carrier and is easy to fall off, and the like, and the invention provides the coating slurry for the catalyst prepared by doping cobalt-containing oxide, namely the first aim of the invention is to provide the doping cobalt-containing oxide which comprises cobalt-containing active components, a first doping auxiliary agent, a second doping auxiliary agent and a third doping auxiliary agent; wherein,
the cobalt-containing active component comprises one or more of cobalt, cobalt salts or oxides 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 auxiliary metal to cobalt is 0.01:1-0.03:1, the molar ratio of the second doping auxiliary metal to cobalt is 0.05:1-0.25:1, and the molar ratio of the third doping auxiliary metal to cobalt is 0.02:1-0.04:1.
In one embodiment, the doped cobalt-containing oxide comprises Co 3 O 4 Is a spinel structure of (a).
In one embodiment, the XRD diffraction pattern of the doped cobalt-containing oxide comprises one or more characteristic peaks of 2θ 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 of 2θ 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 of 2θ selected from 25.301 ±0.25, 48.051 ±0.20.
Another object of the present invention is to provide a method for preparing the doped cobalt-containing oxide, comprising the steps of: 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 solid, drying and roasting to obtain the doped cobalt-containing oxide.
In one embodiment, the cobalt-containing active component of the process comprises one or more of cobalt, cobalt salts or oxides thereof.
In a specific embodiment, the cobalt salt in the method comprises nitrate or sulfate, chloride, acetate.
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 method is selected from at least one of W and Mo.
In one embodiment, the cobalt-containing active component, the precursor of the first doping auxiliary agent, the second doping auxiliary agent and the third doping auxiliary agent are dissolved twice by a solvent, the method comprises the steps of dissolving polyethylene glycol and water, stirring until the solution is 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 process comprises polymethyl methacrylate, polyvinyl alcohol, or polystyrene-polypropylene oxide copolymer.
In one embodiment, calcining the solid in the process comprises drying at 60℃for 12 hours, at O 2 /N 2 Firing for 2 hours at 200 ℃ in an atmosphere of =1/99 and then for 4 hours in air at 500 ℃ to form the doped cobalt-containing oxide.
A further object of the present invention is to provide a coating slurry for a catalyst prepared from the above doped cobalt-containing oxide, comprising the following components in parts by weight:
a) 12-25 parts of a doped cobalt-containing oxide according to any one of claims 1-3;
b) 15-30 parts of pseudo-boehmite;
c) 3-6 parts of molecular sieve;
d) 1-3 parts of adhesive;
e) 0.1 to 0.5 part of dispersant;
f) 0.5 to 1.5 parts of 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 alumina sol, preferably the adhesive comprises 20-40% alumina sol by mass.
In one embodiment, the dispersing agent comprises one or more of polyacrylic acid, polyethylene glycol and tetrapropylammonium bromide.
In one embodiment, the pH adjuster 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 650-850mpa.s and a slurry particle size D97 of less than 22 μm.
It is still another object of the present invention to provide a method for preparing the above-mentioned coating slurry for a catalyst, comprising the steps of: the doped cobalt-containing oxide, pseudo-boehmite, a molecular sieve, an adhesive, a dispersing agent and a pH regulator are contacted with a solvent, stirred for 1-4 hours, and then glued and ground to obtain coating slurry.
It is a further object of the present invention to provide the use of the coating slurry described above for the preparation of an industrial exhaust gas catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) The doped cobalt oxide with special components and proportions has higher catalytic activity and higher adhesion with the carrier;
(2) The catalyst prepared by coating the slurry has the advantages of reduced falling rate and good stability.
(3) The doped cobalt oxide and the auxiliary agent endow the coating slurry with cohesive force and compatibility among the 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 the proportion and the coating slurry for the catalyst prepared by the doped cobalt oxide have the advantages of good stability and difficult 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 diffraction pattern of a doped cobalt-containing oxide prepared in accordance with one embodiment of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The performance of the invention is measured according to the following method:
coating slurry viscosity test: the measurement is carried out by using a Bowler-femto DV2T viscometer, and the test method comprises the following steps: 50mL of the liquid to be measured was poured into a measuring cup at 25℃for 300s.
Catalytic performance test: the catalyst was subjected to catalytic reaction performance evaluation under the same conditions on a fixed bed reactor catalytic combustion reaction apparatus. The process conditions are as follows: under the air atmosphere, the reaction pressure is 0.05MPa-0.1MPa, the tail gas amount treated per gram of catalyst is 20L per hour, and the temperature is programmed to the reaction temperature until the complete conversion is achieved. The temperature-raising program is as follows: raising the temperature from 20 ℃ to 100 ℃ at a heating rate of 10 ℃/min, holding for 0.5 hours, raising the temperature to 150 ℃ at a heating rate of 10 ℃/min, holding for 0.5 hours, raising the temperature to 160 ℃ at a heating rate of 5 ℃/min, holding for 5 minutes, raising the temperature to 165 ℃ at a heating rate of 5 ℃/min, holding for 5 minutes, raising the temperature to 170 ℃ at a heating rate of 5 ℃/min, holding for 5 minutes, and so on until the temperature reaches 400 ℃.
Ultrasonic shedding rate test: the stability of the coating of the exhaust gas treatment catalyst was evaluated by ultrasonic vibration test, and the sample was put into an ultrasonic cleaner in which the medium was water, the ultrasonic operating frequency was 53KHz, and the shedding rate was calculated after 30 minutes of ultrasonic treatment.
The ultrasonic shedding rate= (total mass of catalyst before ultrasonic-total mass of catalyst after ultrasonic)/(total mass of catalyst before ultrasonic-mass of honeycomb carrier before coating) ×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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/L. Adding 2g of polymethyl methacrylate template into the transparent solution, and stirring for 1 hourStanding overnight to obtain sol, filtering and washing to obtain solid, air drying at room temperature, drying at 60deg.C for 12 hr, and adding water to O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide. Fig. 1 shows XRD diffractograms of the doped cobalt-containing oxides obtained by preparation, wherein the XRD diffractograms have 8 characteristic peaks of 2θ 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 Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Xianfeng nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 650mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst A. The ultrasonic shedding rate was measured to be 2.1%.
[ example 2 ]
Preparation of coating slurry:
29.103g of cobalt nitrate, 0.1854g 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/L. Adding 2g polymethyl methacrylate template into the transparent solution, stirring for 1 hour, standing overnight to obtain sol, filtering and washing to obtain solid, air drying at room temperature, and drying at 60 deg.CDrying for 12 hours, at O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clay nanomaterial Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 653.4mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst B. The ultrasonic shedding rate was measured 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, and the viscosity of the coating slurry is measured to be 652.8mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst C. The ultrasonic shedding 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, 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.8mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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, 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is 655.2mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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 are dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and the mixture is stirred for 2 hours to obtain a transparent solution. To the transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 651.8mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the waste gas treatment catalyst F. The ultrasonic shedding rate was measured to be 2.08%.
[ example 7 ]
Preparation of coating slurry:
29.103g of NitroCobalt acid, 0.1854g boric acid, 2.146g zirconium nitrate, 0.353g ammonium heptamolybdate were dissolved in a mixed solution of 10ml polyethylene glycol and 50ml water, and stirred for 2 hours to obtain a transparent solution. To the transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is 655.5mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100G/L, thus preparing the waste 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. 9.6g of methanol was added to the transparent solution so that the methanol content was 5mol/L. Adding 2g polymethyl methacrylate template into the transparent solution, stirring for 1 hour, and standing overnight to obtainFiltering and washing the obtained solid until sol is obtained, airing the obtained solid at room temperature, drying the solid at 60 ℃ for 12 hours, and drying the solid at O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, and the viscosity of the coating slurry is 657.5mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
25 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, and the viscosity of the coating slurry is 659.6mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then the carrier is taken out, the slurry remained in the pore canal is dried, then the carrier is weighed after drying and baking, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst I. The ultrasonic shedding 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 30 parts of pseudo-boehmite (Jiangsu Sanjia Ultrafiltration Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanjia Feng nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanjia Ultrafiltration 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so that coating slurry is obtained, and the viscosity of the coating slurry is measured to be 665.8mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 6 parts of SBA-15 molecular sieve (Jiangsu Santa Clay nanomaterial Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 663.2mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then the carrier is taken out, the slurry remained in the pore canal is dried, then the carrier is weighed after drying and baking, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the waste 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 3 parts of 20% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 679.1mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst L. The ultrasonic shedding 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanzhu Co., 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, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.5mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/L. 2g of polymethyl methacrylate templateAdding the agent into the transparent solution, stirring for 1 hr, standing overnight to obtain sol, filtering and washing to obtain solid, air drying at room temperature, drying at 60deg.C for 12 hr, and adding into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji Utility Co., 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 colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, and the viscosity of the coating slurry is measured to be 656.8mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting the cylindrical honeycomb carrier for 2 hours at 200 ℃, dipping the treated carrier in the coating slurry for 0.5 hour, taking out, drying the slurry remained in the pore channels, drying, roasting, weighing, and repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic skeleton per unit volume is 50-100 g/L, thereby preparing 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 1 part of 40% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 680mpa.s.
Preparation of exhaust gas treatment catalyst:
roasting the cylindrical honeycomb carrier for 2 hours at 200 ℃, dipping the treated carrier in the coating slurry for 0.5 hour, taking out, drying the slurry remained in the pore channels, drying, roasting, weighing, and repeating the coating process for at least 3 times until the coating amount on the honeycomb ceramic skeleton per unit volume is 50-100 g/L, thereby preparing 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, 0.507g of ammonium tungstate were dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and stirred to obtain a transparent solution for 2 hours. To the transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clay nanomaterial Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 653.8mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst P. The ultrasonic shedding 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 are dissolved in a mixed solution of 10ml of polyethylene glycol and 50ml of water, and the solution is stirred for 2 hours to obtain a transparent solution. To the transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clary nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.3mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the waste 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 the obtained solution was stirred for 2 hours to obtain a transparent solution. To the transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 654.1mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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 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 at 110 ℃ for 12 hours, and then the precipitate is roasted at 500 ℃ for 4 hours to obtain doped cobalt-containing oxide;
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 are contacted with water, stirred for 1 hour at 3000 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 530.1mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the waste gas treatment catalyst S. The ultrasonic shedding 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
12 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanzhu Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Sanzhun nano material science and technology Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanzhu 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 528.5mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing 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 transparent solution, 5.76g of methanol was added so that the methanol content was 3mol/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, airing the obtained solid at room temperature, drying at 60 ℃ for 12 hours, and adding the solid into O 2 /N 2 Roasting for 2 hours at 200 ℃ in an atmosphere of 1/99 and roasting for 4 hours at 500 ℃ in air to obtain the doped cobalt-containing oxide.
10 parts of doped cobalt-containing oxide, 15 parts of pseudo-boehmite (Jiangsu Sanji Utility Co., ltd.), 3 parts of SBA-15 molecular sieve (Jiangsu Santa Clay nanomaterial Co., ltd.), 1 part of 20% alumina sol (Jiangsu Sanji 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 revolutions, and the uniformly mixed slurry is colloid-milled in a colloid mill for 2 hours until the particle size D97 is less than 22 mu m, so as to obtain coating slurry, and the viscosity of the coating slurry is measured to be 625.5mpa.s.
Preparation of exhaust gas treatment catalyst:
the cylindrical honeycomb carrier is baked for 2 hours at 200 ℃, the treated carrier is immersed in the coating slurry for 0.5 hour, then taken out, the slurry remained in the pore canal is dried, then dried, baked and weighed, and the coating process is repeated for at least 3 times until the coating amount on the honeycomb ceramic skeleton in unit volume is 50-100 g/L, thus preparing the exhaust gas treatment catalyst U. The ultrasonic shedding rate was measured to be 4.68%.
Test example 1
Catalysts A to U were subjected to catalytic reaction performance evaluation under the same conditions on a fixed bed reactor catalytic reaction apparatus, and the reaction results are shown in Table 1. In this test example, the exhaust gas containing the organic matter was brought into contact with a catalyst to perform catalytic combustion, and the process conditions were evaluated as follows: under the air atmosphere, the reaction pressure is 0.05MPa-0.1MPa, the tail gas amount treated per gram of catalyst is 20L per hour, and the temperature is programmed to the reaction temperature until the complete conversion is achieved. The temperature-raising program is as follows: raising the temperature from 20 ℃ to 100 ℃ at a heating rate of 10 ℃/min, holding for 0.5 hours, raising the temperature to 150 ℃ at a heating rate of 10 ℃/min, holding for 0.5 hours, raising the temperature to 160 ℃ at a heating rate of 5 ℃/min, holding for 5 minutes, raising the temperature to 165 ℃ at a heating rate of 5 ℃/min, holding for 5 minutes, raising the temperature to 170 ℃ at a heating rate of 5 ℃/min, holding for 5 minutes, and so on until the temperature reaches 400 ℃.
The waste gas containing organic matters is simulated gas, and the carrier gas is nitrogen.
When evaluating the single organic matter component, the concentrations of the organic matters in the three waste gases containing the single organic matters are respectively as follows: 6000ppm of methyl acetate, 1000ppm of paraxylene and 300ppm of dibromomethane.
In the evaluation of the mixed sample, the organic matter composition in the organic matter exhaust gas containing the mixed sample was: 3000ppm of methyl acetate, 500ppm of paraxylene and 100ppm of dibromomethane.
The reactivity of the catalyst takes the reaction temperature of the complete conversion of the oxidized tail gas component as an evaluation standard, and the lower the complete conversion temperature is, the better the performance of the catalyst is. Wherein T99 of a single component represents the reaction temperature at which the purification rate of the component in the exhaust gas is 99%. T99 of the mixed sample is expressed as the reaction temperature at which the purification rate of all components in the exhaust gas reaches 99%. 400 (Tn) represents that the purification rate of dibromomethane is n% at 400 ℃, and when the mixed sample is processed, the purification rate of methyl acetate and paraxylene is 99% or more.
TABLE 1
| DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION | Methyl acetate T 99 | Para-xylene T 99 | Bromomethane T 99 | Mixed sample T 99 |
| 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 that: t in Table 1 99 The units of (C) are "°C".
Claims (12)
1. The coating slurry for the catalyst is characterized by comprising the following components in parts by weight:
a) 12-25 parts of doped cobalt-containing oxide;
b) 15-30 parts of pseudo-boehmite;
c) 3-6 parts of molecular sieve;
d) 1-3 parts of an adhesive;
e) 0.1-0.5 part of dispersing agent;
f) 0.5-1.5 parts of pH regulator;
g) The rest is solvent;
the doped cobalt-containing oxide comprises a cobalt-containing active component, a first doping auxiliary agent, a second doping auxiliary agent and a third doping auxiliary agent; wherein,
the cobalt-containing active component comprises one or more of cobalt, cobalt salts or oxides thereof;
the first doping auxiliary is selected from at least one of B and Ga,
the second doping auxiliary agent is selected from at least one of Zr and Ti,
the third doping auxiliary agent is selected from at least one of W and Mo;
the preparation method of the doped cobalt-containing oxide comprises the following steps: dissolving cobalt-containing active component, precursor of first doping auxiliary agent, precursor of second doping auxiliary agent and precursor of third doping auxiliary agent twice by using solvent, including dissolving polyethylene glycol and water, stirring to transparent, adding methanol into transparent solution, adding template agent into the transparent solution to form sol, filtering and washing sol, drying and roasting the obtained solid to obtain doped cobalt-containing oxide;
The template agent comprises polymethyl methacrylate, polyvinyl alcohol or polystyrene-polypropylene oxide copolymer.
2. The coating slurry of claim 1, wherein the molar ratio of the first doping aid to cobalt is 0.01:1-0.03:1, the molar ratio of the second doping aid metal to cobalt is 0.05:1-0.25:1, and the molar ratio of the third doping aid metal to cobalt is 0.02:1-0.04:1.
3. The coating slurry of claim 1 or 2, wherein the doped cobalt-containing oxide comprises Co 3 O 4 Spinel structure of (C), and/or
The XRD diffraction pattern of the doped cobalt-containing oxide has one or more characteristic peaks comprising 2θ 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.
4. The coating slurry of claim 1 or 2, wherein the XRD diffraction pattern of the doped cobalt-containing oxide comprises one or more characteristic peaks of 2Θ selected from 30.201 ± 0.20, 50.503 ± 0.15.
5. The coating slurry of claim 1 or 2, wherein the XRD diffraction pattern of the doped cobalt-containing oxide comprises one or more characteristic peaks of 2Θ selected from 25.301 ± 0.25, 48.051 ± 0.20.
6. The coating slurry of claim 1 or 2, wherein the cobalt-containing active component comprises a cobalt salt; 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.
7. The coating slurry of claim 6, wherein the cobalt-containing active component comprises cobalt nitrate.
8. The coating slurry of claim 1 or 2, wherein the molecular sieve is selected from one or both of SBA-15 and MCM-41; and/or the adhesive comprises an aluminum sol; and/or the dispersing agent 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.
9. The coating slurry of claim 8, wherein the adhesive comprises 20-40% alumina sol by mass.
10. The coating slip of claim 1 or 2, wherein the coating slip has a viscosity of 650-850mpa.s and a slip particle size D97 of less than 22 μm.
11. A method for preparing the coating slurry for a catalyst according to any one of claims 1 to 10, comprising the steps of: and (3) contacting the doped cobalt-containing oxide, pseudo-boehmite, a molecular sieve, an adhesive, a dispersing agent and a pH regulator with a solvent, stirring for 1-4 hours, and performing colloid milling to obtain coating slurry.
12. Use of a coating slurry according to any one of claims 1-10 for the preparation of an industrial exhaust gas catalyst.
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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 |
| 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 |
| 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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| KR101907147B1 (en) * | 2012-03-28 | 2018-10-12 | 현대중공업 주식회사 | Metallic filter for exhaust gas of marine |
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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 |
| 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 |
| 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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