CN111298802A - Preparation method of flue gas denitration catalyst - Google Patents
Preparation method of flue gas denitration catalyst Download PDFInfo
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- CN111298802A CN111298802A CN201811514523.2A CN201811514523A CN111298802A CN 111298802 A CN111298802 A CN 111298802A CN 201811514523 A CN201811514523 A CN 201811514523A CN 111298802 A CN111298802 A CN 111298802A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000003546 flue gas Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000919 ceramic Substances 0.000 claims abstract description 30
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 29
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 15
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 15
- 238000007664 blowing Methods 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 amide compound Chemical class 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002791 soaking Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- 229910001593 boehmite Inorganic materials 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 claims description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 238000011068 loading method Methods 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- SKHGCOGHICVSIW-UHFFFAOYSA-N [W].[Sn].[Ce] Chemical compound [W].[Sn].[Ce] SKHGCOGHICVSIW-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a preparation method of a flue gas denitration catalyst, which comprises the following steps: uniformly mixing aluminum salt, polyethylene glycol, alumina sol, an amide compound and a low-carbon alcohol aqueous solution, then adding propylene oxide and/or pyridine, and uniformly mixing; immersing the pretreated cordierite honeycomb ceramic substrate into the mixture for treatment, taking out, blowing off residual liquid, aging for a period of time, immersing an aging product in a low-carbon alcohol aqueous solution, then carrying out solid-liquid separation, carrying out heat treatment on a solid phase by an ammonium bicarbonate solution, and then drying and roasting to obtain a cordierite honeycomb ceramic carrier loaded with a coating; and (3) impregnating the carrier with an impregnation liquid containing an active component, drying and roasting to obtain a final product. The denitration catalyst coating prepared by the method disclosed by the invention contains more macropores, the macropores are uniformly distributed, a certain mechanical strength can be ensured, the denitration catalyst coating has good denitration activity, the preparation process is simple, and the denitration catalyst coating is suitable for industrial application.
Description
Technical Field
The invention relates to a preparation method of a flue gas denitration catalyst.
Background
The denitration catalyst is the core of the SCR technology, and is generally of an integral structure due to the large amount of flue gas in power plants, industrial boilers and the like. CN101380543A discloses a flue gas denitration composite catalyst, which uses aluminum-based or silicon-based ceramic as a first carrier, silicon-aluminum composite oxide as a second carrier, and cerium-zirconium composite metal oxide as an active component. CN101961656A discloses a denitration catalyst which is loaded with TiO2-SiO2The cordierite honeycomb ceramic of the coating is taken as a carrier, and the active component is V2O5、WO3、MoO3、SO4 2-Two or more of (1) and (b). CN102008952A discloses a denitration composite oxide catalyst, which uses honeycomb ceramics as a carrier, uses a Ti-Zr composite oxide as a carrier coating, and uses a tin-cerium-tungsten composite oxide as an active component. CN101357328A discloses a denitration catalyst, which takes silicon-based ceramic as a carrier and active SiO2Is used as a second carrier, and a proper amount of transition metal is added into the cerium oxide as an active component. CN1593752A discloses a catalyst for SCR denitration of power station flue gas. The catalyst is loaded with Al on cordierite honeycomb2O3For the carrier coating, carrying V2O5And WO3Is an active component. CN101234345A discloses a denitration catalyst, which takes aluminum-based ceramic as a carrier and active Al2O3As a second carrier, CeO2Adding a proper amount of metal oxide as an active component. CN101053838A discloses a denitration catalyst, which takes cordierite as a carrier and loads Al2O3After coating, loading CuO as an active component. CN201611002419.6 discloses a preparation method of a denitration catalyst, which comprises performing surface pore expansion by using modified carbon black powder.
In the process of preparing the coating sol or slurry, 2-5% of chemical pore-forming agent is generally added, so that the number of pore channels of the surface coating is increased, the specific surface area is increased, the denitration reaction is facilitated, and fly ash in flue gas, ammonium bisulfate generated in the reaction and the like are continuously deposited in the pore channels to block the pore channels, and finally the catalyst is inactivated. Therefore, the amount of macropores in the coating is further increased, the reaction space of the catalyst and the capability of resisting fly ash and salt poisoning can be improved, the mechanical strength of the catalyst coating is certainly influenced by the increase of the amount of macropores, and meanwhile, the distribution of macropores of the alumina obtained by the mode of adding the pore-forming agent through mechanical mixing is not uniform. How to obtain an alumina coating with a certain amount of macropores, uniform distribution and good mechanical strength is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the flue gas denitration catalyst, the denitration catalyst coating prepared by the method contains more macropores, the macropores are uniformly distributed, a certain mechanical strength can be ensured, the denitration activity is good, the preparation process is simple, and the method is suitable for industrial application.
The preparation method of the flue gas denitration catalyst comprises the following steps:
(1) uniformly dispersing boehmite powder in water to obtain a boehmite suspension, slowly adding a peptizing agent into the boehmite powder suspension, and after the addition is finished, heating and aging for a certain time to obtain clear alumina sol;
(2) uniformly mixing inorganic aluminum salt, polyethylene glycol, the alumina sol obtained in the step (1), an amide compound and a low-carbon alcohol aqueous solution, then adding propylene oxide and/or pyridine, and uniformly mixing;
(3) immersing the pretreated cordierite honeycomb ceramic substrate into the mixture obtained in the step (2) for treatment, taking out, blowing off residual liquid, aging for a period of time, soaking an aging product by using a low-carbon alcohol aqueous solution, then carrying out solid-liquid separation, and drying and roasting a solid phase to obtain a cordierite honeycomb ceramic carrier loaded with a coating;
(4) mixing the cordierite honeycomb ceramic carrier with the load coating obtained in the step (3), ammonium bicarbonate and water, then carrying out sealing heat treatment, and drying and roasting a product after the heat treatment;
(5) and (4) impregnating the carrier obtained in the step (4) with an impregnation liquid containing an active component, drying and roasting to obtain a final product.
In the method, the solid content of the suspension liquid in the step (1) is 1-15 wt%.
In the method, the step (1) is carried out under the condition of stirring, and the aging is carried out in a heating reflux mode, wherein the reflux temperature is 70-95 ℃, and the reflux time is 1-12 hours.
In the method, the peptizing agent in the step (1) is a commonly used peptizing agent in the preparation process of the aluminum sol, and can be one or more of hydrochloric acid, nitric acid, sulfuric acid, formic acid or acetic acid. The peptizing agent in the step (1) contains H+H in terms of Al element contained in boehmite powder+The mol ratio of Al to Al is 0.05-1.
In the method, based on the weight of the mixture obtained in the step (2), the adding amount of the lower alcohol aqueous solution is 10-80 wt%, the adding amount of the inorganic aluminum salt is 5-30 wt%, the adding amount of the aluminum sol is 1-10 wt%, and the adding amount of the polyethylene glycol is 0.1-3.0 wt%, preferably 0.2-2.0 wt%; the addition amount of the amide compound is 0.1-5.0 wt%; wherein the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.5; the viscosity average molecular weight of the polyethylene glycol is 10000-.
In the method of the present invention, the inorganic aluminum salt in step (2) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
In the process of the present invention, the lower alcohol used in the steps (2) and (3) is generally C5The alcohol is preferably one or more of methanol, ethanol, n-propanol and isopropanol, and most preferably ethanol and/or propanol.
In the method, the amide compound in the step (2) is one or more of formamide, acetamide, N-dimethylformamide, N-methylacetamide, benzamide and 2-phenylacetamide.
In the method of the present invention, the propylene oxide and/or pyridine and Al described in the step (2)3+(not including Al in the alumina sol) in a molar ratio of 1.5 to 9.5, preferably 3.0 to 7.5. The propylene oxide and pyridine may be mixed in any proportion.
In the method, the treatment time in the step (3) is 1-120 minutes, preferably 3-60 minutes, and after the treatment time is taken out, the redundant liquid in the gaps of the matrix is blown off by compressed air.
In the method of the invention, the aging conditions in the step (3) are as follows: aging at 20-80 deg.C for 12-120 hr.
In the method, the soaking conditions in the step (3) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 12-60 hours.
In the method, the mass concentration of the low-carbon alcohol aqueous solution used for soaking in the step (3) is not less than 50 wt%; after soaking treatment, taking out the substrate, and blowing off redundant liquid in gaps of the substrate by using compressed air.
In the method, the drying in the step (3) is ordinary normal pressure drying, the drying temperature is not more than 120 ℃, preferably 20-100 ℃, and the drying is carried out until the product is not obviously reduced. The roasting is carried out at 400-700 ℃ for 1-24 hours, preferably at 500-650 ℃ for 2-12 hours.
In the method, the pore diameter of the coating macropore in the step (3) is 50-1000nm, preferably 100-500 nm, the pores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macropore to the corresponding wall thickness is 0.5-4.5, preferably 1-4.
In the method of the invention, the solid-liquid separation can adopt conventional modes such as filtration, centrifugation and the like.
In the method of the present invention, the pretreated cordierite honeycomb ceramic substrate is an acid-treated activated cordierite honeycomb ceramic substrate.
In the method, the ammonium bicarbonate and the cordierite honeycomb ceramic carrier loaded with the coating in the step (4) are mixed with Al2O3The mass ratio of the ammonium bicarbonate solution to the water is 5-20:1:20-100, the ammonium bicarbonate can be added independently or mixed with the water in advance in the form of an ammonium bicarbonate solutionAdding the compound shown in the formula (II).
In the method of the present invention, the sealing heat treatment conditions in step (4) are as follows: the temperature is 120-160 ℃, and the constant temperature treatment time is 4-10 hours.
In the method of the invention, the drying temperature in the step (4) is 100-160 ℃, and the drying time is 4-20 hours. The roasting temperature is 400-750 ℃, and the roasting time is 4-10 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
In the method, the active component in the step (5) is one or more of Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce, V or Ti.
In the method of the invention, the impregnation process in the step (5) adopts a method of over-volume impregnation, equal-volume impregnation or spray impregnation and the like, the impregnation time is 1-5 hours, and the over-volume impregnation is preferred. Wherein, the preparation of the impregnating solution selects soluble compounds of active components, and the specific concentration of the impregnating solution can be determined according to the content of active metals on the final catalyst.
In the method, the roasting temperature in the step (5) is 400-600 ℃, preferably 500-600 ℃, the roasting time is 2-10 hours, and the roasting is carried out in an oxygen-containing atmosphere, generally an air atmosphere.
In the method of the invention, the drying temperature in the step (5) is 60-150 ℃, preferably 80-120 ℃, the drying time is 3-12 hours, preferably 6-10 hours,
in the method, the mixing process adopts modes of stirring, ultrasound or high shear and the like.
Compared with the prior art, the denitration catalyst has the following characteristics:
the alumina coating is prepared in situ on the honeycomb substrate, the coating firstly obtains three-dimensionally through and uniformly distributed macropores through the sol-gel reaction characteristic of inorganic aluminum salt, the addition of the amide compound can inhibit the generation of super macropores, so that the macropores are more uniformly concentrated, the stress effect caused by nonuniform pore sizes is favorably eliminated, in addition, the coating is further subjected to heat treatment by ammonium bicarbonate solution, fibrous alumina formed in the macropores is mutually crossed to form loose through pore channels, the deposition of dust and metal impurities in flue gas on the outer surface of the coating is favorably prevented from blocking the pore channels, the catalyst has excellent permeability and higher impurity capacity, and the influence on the internal pore structure of the coated alumina is reduced. Compared with the size of the pore diameter of the macropore, the pore wall of the macropore of the macroporous alumina prepared by the invention is equivalent to or larger than the pore diameter of the macropore, and the relatively thick pore wall ensures that the material has higher crushing strength, thereby better meeting the harsh application requirements in industry. The denitration catalyst has better mass transfer efficiency of flue gas denitration, the pore channel of the catalyst is not easy to be blocked by fly ash and sulfate, and the service life of the catalyst is prolonged.
Drawings
FIG. 1 is an electron microscope image of the alumina coating prepared in step (3) of example 1.
Fig. 2 is an electron microscope image of the alumina coating prepared in step (4) of example 1.
Detailed Description
The technical solution of the present invention is described in more detail by the following specific examples, and the examples should not be construed as limiting the scope of the present invention. The cordierite honeycomb ceramics used in the examples were square carriers each having a cross section of 50mm in length, width and height. And observing the coating macropore and the three-dimensional penetration condition thereof by using a scanning electron microscope. The crystalline state was tested by XRD. The average pore diameter of the macropores of the coating is characterized and tested by mercury intrusion method. The boehmite powder is a product sold in the market or manufactured by self.
Cordierite pretreatment: completely immersing cordierite honeycomb ceramic into 5wt% nitric acid solution for 1 hour, taking out, washing with deionized water for 3-5 times, placing into an oven, and drying for 10 hours at 130 ℃ to obtain the cordierite honeycomb ceramic carrier with the activated surface.
The preparation of the active ingredient impregnation solution is well known to those skilled in the art, and generally a soluble compound of the active ingredient, usually a nitrate, is selected, and the specific concentration of the impregnation solution can be determined according to the active metal content on the final catalyst.
Example 1
(1) Mixing boehmite powder and water to form a suspension (solid content is 3 wt%), dropwise adding hydrochloric acid under the stirring condition, wherein the acid/aluminum molar ratio is 0.07, and after dropwise adding, heating to 85 ℃ and refluxing for 5 hours to form clear alumina sol;
(2) uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol, aluminum sol and formamide at room temperature (about 25 ℃), and then adding pyridine, wherein the mixture comprises the following components in parts by weight: 22% of water, 21% of ethanol, 18% of aluminum chloride, 0.3% of polyethylene glycol (with the viscosity average molecular weight of 100 ten thousand), 5% of alumina sol, 1% of formamide and 32.7% of pyridine, and uniformly mixing;
(3) immersing the pretreated cordierite honeycomb ceramic substrate into the mixture obtained in the step (2) for treatment for 10 minutes, taking out, blowing off residual liquid, continuing aging for 48 hours at 40 ℃, soaking the aged mixture for 48 hours by using 55wt% of ethanol water solution, blowing off the residual liquid after the soaking is finished, drying at 40 ℃ until the product is not obviously reduced, and then roasting for 3 hours at 550 ℃ to obtain a carrier loaded with a coating; the average pore diameter of macropores of the coated alumina is 440nm, the macropores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macropores to the corresponding wall thickness is 0.7;
(4) adding the carrier loaded with the coating, ammonium bicarbonate and water (the mass ratio of the carrier to the ammonium bicarbonate to the water is 5: 1: 20) into an autoclave, carrying out sealing heat treatment for 8 hours at 120 ℃, carrying out solid-liquid separation, drying a solid phase at 130 ℃ for 6 hours, and roasting at 500 ℃ for 4 hours;
(5) and (3) impregnating the cordierite honeycomb ceramic matrix obtained in the step (3) with an impregnation solution containing Mn and Fe active components, drying at 120 ℃ for 8 hours, and roasting the dried material at 550 ℃ for 5 hours in an air atmosphere to obtain a catalyst A, wherein the loading amount of Mn in the catalyst is 8wt%, and the loading amount of Fe in the catalyst is 2 wt%.
Example 2
(1) The same as in example 1.
(2) Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol, aluminum sol and acetamide at room temperature (about 25 ℃), and then adding propylene oxide, wherein the mixture comprises the following components in parts by weight: 23% of water, 20% of ethanol, 22% of aluminum chloride, 0.5% of polyethylene glycol (viscosity-average molecular weight is 100 ten thousand), 2% of alumina sol, 2.0% of formamide and 30.5% of propylene oxide, and uniformly mixing;
(3) immersing the pretreated cordierite honeycomb ceramic substrate into the mixture obtained in the step (2) for treatment for 10 minutes, taking out, blowing off residual liquid, continuing aging for 48 hours at 40 ℃, soaking the aged mixture for 48 hours with ethanol, blowing off the residual liquid after the soaking is finished, drying at 40 ℃ until the product is not obviously reduced any more, and then roasting for 5 hours at 450 ℃ to obtain a carrier loaded with a coating; the average pore diameter of macropores of the coated alumina is 210nm, the macropores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macropores to the corresponding wall thickness is 1.5;
(4) adding the carrier loaded with the coating, ammonium bicarbonate and water (the mass ratio of the carrier to the ammonium bicarbonate to the water is 10: 1: 60) into an autoclave, carrying out sealing heat treatment for 6 hours at 130 ℃, carrying out solid-liquid separation, drying a solid phase at 125 ℃ for 8 hours, and roasting at 550 ℃ for 5 hours;
(5) and (3) impregnating the cordierite honeycomb ceramic matrix obtained in the step (3) with an impregnation solution containing Mn and Fe active components, drying at 110 ℃ for 8 hours, and roasting the dried material at 550 ℃ for 6 hours in an air atmosphere to obtain a catalyst B, wherein the loading amount of Mn in the catalyst is 10wt%, and the loading amount of Fe in the catalyst is 3 wt%.
Example 3
(1) Mixing boehmite powder and distilled water to form a suspension (solid content is 1.5 wt%), dropwise adding acetic acid under the condition of continuous stirring to meet the acid/aluminum molar ratio of 0.1, and heating to 90 ℃ after the dropwise adding is finished, and refluxing for 10 hours to form clear sol;
(2) uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol, aluminum sol and N, N-dimethylformamide at room temperature (about 25 ℃), and then adding pyridine, wherein the mixture comprises the following components in parts by weight: 20% of water, 20% of ethanol, 22% of aluminum chloride, 0.5% of polyethylene glycol (viscosity-average molecular weight is 100 ten thousand), 5% of alumina sol, 2.5% of formamide and 30.0% of pyridine, and the components are uniformly mixed;
(3) immersing the pretreated cordierite honeycomb ceramic substrate into the mixture obtained in the step (2) for treatment for 10 minutes, taking out, blowing off residual liquid, continuing aging for 48 hours at 40 ℃, soaking the aged mixture for 48 hours with ethanol, blowing off the residual liquid after the soaking is finished, drying at 40 ℃ until the product is not obviously reduced any more, and then roasting for 3 hours at 700 ℃ to obtain a carrier loaded with a coating; the average pore diameter of macropores of the coated alumina is 184nm, the macropores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macropores to the corresponding wall thickness is 1.2;
(4) adding the carrier loaded with the coating, ammonium bicarbonate and water (the mass ratio of the carrier to the ammonium bicarbonate to the water is 18:1: 100) into an autoclave, carrying out sealing heat treatment for 5 hours at 140 ℃, carrying out solid-liquid separation, drying a solid phase at 100 ℃ for 6 hours, and roasting at 500 ℃ for 6.5 hours;
(5) and (3) impregnating the cordierite honeycomb ceramic matrix obtained in the step (3) with an impregnating solution containing Mn and Ce active components, drying at 120 ℃ for 10 hours, and roasting the dried material at 500 ℃ for 8 hours in an air atmosphere to obtain a catalyst C, wherein the loading amount of Mn in the catalyst is 5wt%, and the loading amount of Ce in the catalyst is 2 wt%.
Comparative example 1
(1) Mixing boehmite powder and water to form a suspension (solid content is 3 wt%), dropwise adding hydrochloric acid under the stirring condition, wherein the acid/aluminum molar ratio is 0.07, and after dropwise adding, heating to 85 ℃ and refluxing for 5 hours to form clear alumina sol;
(2) immersing the pretreated cordierite honeycomb ceramic substrate into the mixture obtained in the step (2) for treatment for 10 minutes, taking out, blowing off residual liquid, continuing aging for 48 hours at 40 ℃, soaking the aged mixture for 48 hours by using 55wt% of ethanol water solution, blowing off the residual liquid after the soaking is finished, drying at 40 ℃ until the product is not obviously reduced, and then roasting for 3 hours at 550 ℃ to obtain a carrier loaded with a coating; no obvious macroporous distribution of the coated alumina;
(3) and (3) impregnating the cordierite honeycomb ceramic matrix obtained in the step (3) with an impregnation solution containing Mn and Fe active components, drying at 120 ℃ for 8 hours, and roasting the dried material at 550 ℃ for 5 hours in an air atmosphere to obtain a catalyst D, wherein the loading amount of Mn in the catalyst is 8wt%, and the loading amount of Fe in the catalyst is 2 wt%.
Comparative example 2
(1) The same as example 1;
(2) adding 5wt% of carbon black powder into the alumina sol obtained in the step (1), and uniformly mixing the alumina sol and the carbon black powder by taking the mass of the alumina sol as a reference to obtain coating slurry;
(3) immersing the pretreated cordierite honeycomb ceramic substrate into the coating slurry for 10 minutes, taking out, blowing off residual liquid, drying at 120 ℃ for 9 hours, and then treating at 450 ℃ for 5 hours to obtain the cordierite honeycomb ceramic substrate loaded with the coating; the macropores of the coated alumina are not uniformly distributed and are not three-dimensionally communicated;
(4) catalyst E was obtained in the same manner as in example 1.
Example 4
The denitration catalysts A-E are subjected to activity evaluation, and the simulated flue gas comprises the following components: NOxConcentration of 800ppm, O2Is 2.5% by volume, SO2The concentration is 200ppm, the dust content is 400mg/Nm3. The evaluation conditions were: NH (NH)3/NOx1.1:1 (molar ratio) and the space velocity of 4000h-1The results of the long-cycle operation at 230 ℃ are shown in Table 1.
Table 1230 ℃ long run test results.
| Numbering | A | B | C | D | E |
| Denitration rate after 500 hours% | 97.8 | 96.8 | 98.3 | 78.5 | 79.7 |
Through test comparison, the catalyst disclosed by the invention is high in removal efficiency of nitrogen oxides in flue gas and has good denitration activity. After the catalyst is continuously operated for 500 hours, the high denitration efficiency is still maintained, which shows that the catalyst is not easy to block, has good stability and long operation life.
Claims (14)
1. A preparation method of a flue gas denitration catalyst comprises the following steps: (1) uniformly dispersing boehmite powder in water to obtain a boehmite suspension, slowly adding a peptizing agent into the boehmite powder suspension, and after the addition is finished, heating and aging for a certain time to obtain clear alumina sol; (2) uniformly mixing inorganic aluminum salt, polyethylene glycol, the alumina sol obtained in the step (1), an amide compound and a low-carbon alcohol aqueous solution, then adding propylene oxide and/or pyridine, and uniformly mixing; (3) immersing the pretreated cordierite honeycomb ceramic substrate into the mixture obtained in the step (2) for treatment, taking out, blowing off residual liquid, aging for a period of time, soaking an aging product by using a low-carbon alcohol aqueous solution, then carrying out solid-liquid separation, and drying and roasting a solid phase to obtain a cordierite honeycomb ceramic carrier loaded with a coating; (4) mixing the cordierite honeycomb ceramic carrier with the load coating obtained in the step (3), ammonium bicarbonate and water, then carrying out sealing heat treatment, and drying and roasting a product after the heat treatment; (5) and (4) impregnating the carrier obtained in the step (4) with an impregnation liquid containing an active component, drying and roasting to obtain a final product.
2. The method of claim 1, wherein: the solid content of the suspension liquid in the step (1) is 1-15 wt%.
3. The method of claim 1, wherein: the step (1) is carried out under the condition of stirring, and the aging is carried out in a heating reflux mode, wherein the reflux temperature is 70-95 ℃, and the reflux time is 1-12 hours.
4. The method of claim 1, wherein: the peptizing agent in the step (1) is one or more of hydrochloric acid, nitric acid, sulfuric acid, formic acid or acetic acid; the peptizing agent is used in the amount of H+H calculated by the amount of boehmite powder in terms of Al contained+The mol ratio of Al to Al is 0.05-1.
5. The method of claim 1, wherein: based on the weight of the mixture obtained in the step (2), the adding amount of the lower alcohol aqueous solution is 10-80 wt%, the adding amount of the inorganic aluminum salt is 5-30 wt%, the adding amount of the aluminum sol is 1-10 wt%, and the adding amount of the polyethylene glycol is 0.1-3.0 wt%; the addition amount of the amide compound is 0.1-5.0 wt%; the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.5; the viscosity average molecular weight of polyethylene glycol is 10000-.
6. The method of claim 1, wherein: the lower alcohol in the steps (2) and (3) is C5The following alcohols.
7. The method of claim 1, wherein: the amide compound in the step (2) is one or more of formamide, acetamide, N-dimethylformamide, N-methylacetamide, benzamide and 2-phenylacetamide.
8. The method of claim 1, wherein: the propylene oxide and/or pyridine and Al in the step (2)3+Is 1.5 to 9.5, and does not contain Al in the alumina sol.
9. The method of claim 1, wherein: and (4) the treatment time in the step (3) is 1-120 minutes, and after the treatment time is taken out, the redundant liquid in the gaps of the matrix is blown off by compressed air.
10. The method of claim 1, wherein: the aging condition in the step (3) is as follows: aging at 20-80 deg.C for 12-120 hr.
11. The method of claim 1, wherein: the soaking conditions in the step (3) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 12-60 hours; the mass concentration of the low-carbon alcohol aqueous solution used for soaking is not less than 50 wt%; after soaking treatment, taking out the substrate, and blowing off redundant liquid in gaps of the substrate by using compressed air.
12. The method of claim 1, wherein: in the step (4), the ammonium bicarbonate and the cordierite honeycomb ceramic carrier loaded with the coating are mixed with Al2O3The mass ratio of the water to the water is 5-20:1: 20-100.
13. The method of claim 1, wherein: the sealing heat treatment conditions in the step (4) are as follows: the temperature is 120-160 ℃, and the constant temperature treatment time is 4-10 hours.
14. The method of claim 1, wherein: and (5) the active component is one or more of Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce, V or Ti.
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| CN115739074A (en) * | 2022-12-29 | 2023-03-07 | 华电青岛环保技术有限公司 | High-activity yellow smoke-eliminating denitration catalyst for gas engine and preparation method thereof |
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| CN114644351A (en) * | 2020-12-17 | 2022-06-21 | 中国石油化工股份有限公司 | Superfine alumina spherical particles and preparation method thereof |
| CN114644352A (en) * | 2020-12-17 | 2022-06-21 | 中国石油化工股份有限公司 | Double-hole distribution alumina spherical particle and preparation method thereof |
| CN114644352B (en) * | 2020-12-17 | 2024-02-13 | 中国石油化工股份有限公司 | Double-pore distribution alumina spherical particle and preparation method thereof |
| CN114644351B (en) * | 2020-12-17 | 2024-02-13 | 中国石油化工股份有限公司 | Superfine alumina spherical particles and preparation method thereof |
| CN115739074A (en) * | 2022-12-29 | 2023-03-07 | 华电青岛环保技术有限公司 | High-activity yellow smoke-eliminating denitration catalyst for gas engine and preparation method thereof |
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