CN116393137B - Catalyst for high-humidity sintering flue gas and preparation method and application thereof - Google Patents
Catalyst for high-humidity sintering flue gas and preparation method and application thereof Download PDFInfo
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- CN116393137B CN116393137B CN202310314260.5A CN202310314260A CN116393137B CN 116393137 B CN116393137 B CN 116393137B CN 202310314260 A CN202310314260 A CN 202310314260A CN 116393137 B CN116393137 B CN 116393137B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003546 flue gas Substances 0.000 title claims abstract description 76
- 238000005245 sintering Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 18
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 77
- 239000000919 ceramic Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims description 44
- 230000003197 catalytic effect Effects 0.000 claims description 43
- 229910052684 Cerium Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 22
- -1 cerium ion Chemical class 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- 229910001431 copper ion Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 44
- 229910001868 water Inorganic materials 0.000 abstract description 9
- 238000002791 soaking Methods 0.000 abstract description 7
- 238000002474 experimental method Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- SYBFKRWZBUQDGU-UHFFFAOYSA-N copper manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Cu++] SYBFKRWZBUQDGU-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 238000005453 pelletization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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)
- Health & Medical Sciences (AREA)
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- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a catalyst for high-humidity sintering flue gas, a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: pretreating a carrier, preparing an active component solution, soaking mullite honeycomb ceramics, drying and roasting. The catalyst for the high-humidity sintering flue gas is applied to selective oxidation removal of CO in the sintering flue gas, wherein the volume content of water vapor in the sintering flue gas is 8-20 vol% and the volume content of CO is 0.3-1.2 vol%. According to the invention, high-efficiency stable removal of CO in flue gas is realized under the conditions of high humidity and low CO, and experiments prove that the catalyst can still maintain higher and stable CO conversion rate under the conditions of water content of 8-20 vol%, the CO conversion rate at 125 ℃ is not lower than 60%, the CO conversion rate at 150 ℃ is not lower than 71%, and the CO conversion rate at 175 ℃ is not lower than 94%.
Description
Technical Field
The invention relates to the technical field of sintering flue gas treatment, in particular to a catalyst for high-humidity sintering flue gas, a preparation method and application thereof.
Background
The pollution to the atmosphere in the steel industry mainly comes from the sintering/pelletizing process, and about 4000m 3~8000m3 flue gas is generated per ton of sintered ore, and the sintering flue gas generally contains 100mg/Nm 3~400mg/Nm3 of NO, 400mg/Nm 3~2000mg/Nm3 of SO 2, 8-20 vol% of water vapor, 14-18 vol% of O 2 and 0.3-1.2 vol% of CO.
In 2019, the environment department, the development and reform commission, the industry and informatization department, the financial department, the transportation department and the like jointly issue 'opinion about ultra-low emission of the steel industry of propulsion implementation' on the recent days, in the opinion, the emission amount of dust and SO 2、NOx in the sintering flue gas is greatly reduced, the emission amount of the dust is respectively lower than 10 mg/m 3、O2 and lower than 35 mg/m 3、NOx and lower than 50 mg/m 3, but the problem of the emission amount of CO in the flue gas is gradually revealed, and the CO content in the steel sintering flue gas can reach 6000-10000 mg/m 3. The concentration of CO in the concentrated areas of partial iron and steel enterprises exceeds 30-50% of the primary air quality standard, and the concentrated areas become main air pollutants in local areas. Environmental protection departments such as an yang, a handan, a Changzhou, a Tangshan, etc. have clearly demanded control of the amount of CO emissions in sintering flue gas.
At present, a sintering plant of an iron and steel enterprise generally cooperatively controls CO emission from a low-carbon sintering and related technology for regulating and controlling a sintering combustion process, the complexity of the sintering process is added, great CO emission reduction cannot be realized, the great CO emission reduction can only be realized by means of tail end flue gas treatment, the mature treatment process for reducing CO emission of sintering waste gas is less, and among a plurality of methods, a catalytic oxidation method is considered to be the most effective method because the catalytic oxidation method has the characteristics of low operation temperature, high combustion efficiency, environmental friendliness and the like.
The main active components of the CO catalytic oxidation catalyst commonly used in the market at present are noble metals such as platinum Pt, rhodium Rh, palladium Pt and the like, the price is high, the technology is mostly a coating technology, the active components are coated on the surface of a cordierite honeycomb carrier or a metal carrier to form a thinner active layer, and as the smoke components are complex and contain a large amount of solid particles with different sizes, the abrasion of the smoke on the surface of the CO catalytic oxidation catalyst is obvious before CO catalytic oxidation equipment is arranged in SCR equipment, and the catalytic activity of the CO catalytic oxidation catalyst prepared by the coating technology is obviously reduced after the surface active layer is abraded and disappears after the CO catalytic oxidation catalyst is used for a period of time. And the particulate catalyst adopted in the traditional flue gas purification has the problems of large piezoresistance, easy heat accumulation, insufficient strength, pulverization and the like. Therefore, the development of the monolithic catalyst for the catalytic oxidation of the flue gas CO has important significance, wherein the monolithic catalyst is low in cost and long in catalytic life.
Currently, commonly used CO catalysts can be largely divided into two main classes, noble metal and non-noble metal catalysts. The active components of the traditional noble metal catalysts are Pd, pt, rh, au and the like, and the noble metal catalysts have high catalytic efficiency, good water resistance and stability in the reaction process, but are high in price and unsuitable for flue gas treatment. The common non-noble metal catalysts such as copper-manganese oxide (MnO x-CuOy) have better catalytic effect under the condition of dry flue gas, but the catalytic efficiency of the catalysts can be greatly reduced under the condition of higher water content of the flue gas. Therefore, for the flue gas with high water content and low CO content, it is necessary to develop a catalyst with long-term and stable catalytic efficiency.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a catalyst for high-humidity sintering flue gas, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
The catalyst takes mullite honeycomb ceramics as a carrier, and copper oxide and cerium oxide serving as catalytic active components are loaded on the carrier.
The mullite honeycomb ceramic is zirconium-containing mullite honeycomb ceramic with the zirconium content of 0.5% -1.2%, the porosity of the mullite honeycomb ceramic is 60%, and the specific surface area is 1290m 2/m3.
The inner hole of the mullite honeycomb ceramic is a square hole, the aperture is 2mm, and the wall thickness between holes is 1.1mm.
The preparation method of the catalyst for the high-humidity sintering flue gas is characterized by comprising the following steps of:
S1, pretreatment of a carrier
Washing mullite with deionized water for 3-5 times, placing the washed mullite into a muffle furnace for roasting, firstly heating to 120-130 ℃, keeping the temperature for 1-1.5 h, then heating to 350-600 ℃, keeping the temperature for 1-2.5 h, and cooling to room temperature along with the furnace;
S2, preparing an active component solution
Cu (NO 3)2·6H2 O and deionized water are used for preparing a copper ion aqueous solution with the concentration of 1 mol/L-3 mol/L, ce (NO 3)3·6H2 O and cerium ion aqueous solution with the concentration of 1 mol/L-6 mol/L are prepared in deionized water; the copper ion aqueous solution and the cerium ion aqueous solution are mixed into an active component solution according to a proportion, and the mixing volume ratio of the copper ion aqueous solution to the cerium ion aqueous solution is 1:7-1:1);
S3, mullite honeycomb ceramic impregnation
Immersing the pretreated mullite honeycomb ceramic into the active component solution, stirring and immersing for 10 hours, and filtering to take out the mullite honeycomb ceramic;
s4, drying and roasting
And drying and roasting the impregnated honeycomb ceramic mullite, and cooling to room temperature to obtain the catalyst for high-humidity sintering flue gas.
In the step S2, the mixing volume ratio of the copper ion aqueous solution to the cerium ion aqueous solution is 1:3.
In the step S3, the mass-volume ratio of the mullite honeycomb ceramic to the active component solution is 100 g/L-1000 g/L.
The specific step of the step S4 is to heat the impregnated mullite honeycomb ceramic to 100-120 ℃ under the protection of N2 or Ar atmosphere, keep the temperature for 2-3 h, heat the mullite honeycomb ceramic to 300-350 ℃ and keep the temperature for 3-4 h, and cool the mullite honeycomb ceramic to room temperature to obtain the catalyst for high-humidity sintering flue gas.
The roasting temperature is 350 ℃ and the roasting time is 4 hours.
The catalyst for the high-humidity sintering flue gas is applied to the selective oxidation removal of CO in the sintering flue gas. The volume content of water vapor in the sintering flue gas is 8-20 vol% and the volume content of CO is 0.3-1.2 vol%.
By adopting the technical scheme, the invention has the following technical progress:
The invention provides a catalyst for high-humidity sintering flue gas, a preparation method and application thereof, which realize efficient and stable removal of CO in the flue gas under the conditions of high humidity and low CO content, and experiments prove that the catalyst can still maintain higher and stable CO conversion rate under the conditions of water content of 8-20 vol%, the CO conversion rate at 125 ℃ is not lower than 60%, the CO conversion rate at 150 ℃ is not lower than 71%, and the CO conversion rate at 175 ℃ is not lower than 94%. The catalyst disclosed by the invention is simple in preparation process, low in raw material cost, longer in catalytic life and wide in application prospect in the aspect of sintering flue gas end treatment.
The main active components Cu and Ce are loaded on the pretreated mullite honeycomb ceramic in an oxide form through an impregnation method to obtain the monolithic catalyst loaded with copper oxide and cerium oxide, and then the monolithic catalyst is dried, roasted and cooled to have higher specific surface area and mass transfer speed, so that the catalytic activity on CO is further improved. Compared with the catalyst of the coating process, the catalyst has the advantages of simple and mature process, more uniform distribution of active ingredients in the holes of the carrier and more suitability for industrial application.
The mullite honeycomb ceramic used in the invention is used as a catalyst carrier, has a regular framework structure and a larger specific surface area, and can uniformly load active ingredients on the surface of the framework, thereby ensuring the uniformity and high efficiency of the catalytic effect of each part. The invention further limits the inner hole of the mullite honeycomb ceramic to be a square hole, accurately limits the pore diameter, kong Jian wall thickness and porosity, ensures that the carrier has larger specific surface area, increases the loading amount of active components and improves the CO catalytic efficiency.
The invention also defines that the zirconium content in the mullite honeycomb ceramic is 0.5% -1.2%. The moderate zirconium content plays two important roles in the carrier, one is that when the zirconium oxide is converted from tetragonal phase to monoclinic phase, the volume of the zirconium oxide is correspondingly changed, microcracks smaller than the critical dimension are formed around converted particles, and the microcracks and residual stress can toughen and strengthen the honeycomb mullite ceramic, so that the toughness of the honeycomb mullite ceramic is doubled, and the brittleness is reduced; the other is that the zirconium is used as a carrier component for supporting copper and is often used for CO oxidation reaction, because zirconium has a higher work function than copper, so that zirconium is easy to give electrons, metallic copper has a tendency of positive charge (electrons outside the metallic copper are influenced), the reduction temperature of Cu 2+ is lowered, and the metallic copper is easy to be reduced, and the adsorption capacity of the copper on CO is improved.
The catalyst disclosed by the invention uses Cu and Ce with relatively low price as the active ingredients of the catalyst, so that the catalytic effect is ensured, the production cost of the catalyst is obviously reduced, and the catalyst is favorable for industrial popularization.
Drawings
FIG. 1 is a graph of the CO conversion for example 3 at various temperatures;
FIG. 2 is a graph of CO conversion for example 3 at various moisture levels;
fig. 3 is a graph of the stability of the CO catalytic efficiency 720 h.
Detailed Description
The present invention will be described in detail with reference to examples.
In the following examples, the mullite honeycomb ceramics used were zirconium-containing mullite honeycomb ceramics having a zirconium content of 1.0%, a porosity of 60% and a specific surface area of 1290m 2/m3, and had square pores with a pore diameter of 2mm and a wall thickness between the pores of 1.1mm.
Example 1
A catalyst for high-humidity sintering flue gas uses mullite honeycomb ceramics as a carrier, and copper oxide and cerium oxide serving as catalytic active components are loaded on the carrier. The porosity of the mullite honeycomb ceramic carrier is 60%.
The catalyst for the high-humidity sintering flue gas is prepared by the following steps:
S1, pretreatment of a carrier
Washing mullite with deionized water for 3 times, putting the washed mullite into a muffle furnace for roasting, heating to 130 ℃, keeping the temperature for 1.5 hours, heating to 600 ℃ and keeping the temperature for 2.5 hours; cooling to room temperature along with the furnace;
S2, preparing an active component solution
Preparing copper ion aqueous solution with the concentration of 1mol/L by using Cu (NO 3)2·6H2 O and deionized water, preparing cerium ion aqueous solution with the concentration of 1mol/L by using Ce (NO 3)3·6H2 O and deionized water; mixing the copper ion aqueous solution and the cerium ion aqueous solution into active component solution according to the volume ratio of 1:1, wherein the ratio of copper to cerium in the active component solution is 1:1;
S3, mullite honeycomb ceramic impregnation
Adding the pretreated mullite honeycomb ceramic obtained in the step 1 into an active component solution, wherein the addition amount is 1000g/L; stirring and soaking for 10 hours, and filtering to obtain mullite honeycomb ceramic;
s4, drying and roasting
Heating the impregnated honeycomb ceramic mullite to 100 ℃ under the protection of nitrogen atmosphere, keeping the temperature for 3 hours, heating to 300 ℃, keeping the temperature for 4 hours, and cooling to room temperature to obtain the catalyst for high-humidity sintering flue gas.
Example 2
A catalyst for high-humidity sintering flue gas uses mullite honeycomb ceramics as a carrier, and copper oxide and cerium oxide serving as catalytic active components are loaded on the carrier. The porosity of the mullite honeycomb ceramic carrier is 60%.
The catalyst for the high-humidity sintering flue gas is prepared by the following steps:
S1, pretreatment of a carrier
Washing mullite with deionized water for 3 times, putting the washed mullite into a muffle furnace for roasting, heating to 130 ℃, keeping the temperature for 1.5 hours, heating to 600 ℃ and keeping the temperature for 2.5 hours; cooling to room temperature along with the furnace; s2, preparing an active component solution
Preparing copper ion aqueous solution with the concentration of 1mol/L by using Cu (NO 3)2·6H2 O and deionized water, preparing cerium ion aqueous solution with the concentration of 2mol/L by using Ce (NO 3)3·6H2 O and deionized water; mixing the copper ion aqueous solution and the cerium ion aqueous solution into active component solution according to the volume ratio of 1:1, wherein the ratio of copper to cerium in the active component solution is 1:2;
S3, mullite honeycomb ceramic impregnation
Adding the pretreated mullite honeycomb ceramic obtained in the step 1 into an active component solution, wherein the addition amount is 1000g/L; stirring and soaking for 10 hours, and filtering to obtain mullite honeycomb ceramic;
s4, drying and roasting
Heating the impregnated honeycomb ceramic mullite to 100 ℃ under the protection of nitrogen atmosphere, keeping the temperature for 3 hours, heating to 300 ℃, keeping the temperature for 4 hours, and cooling to room temperature to obtain the catalyst for high-humidity sintering flue gas.
Example 3
A catalyst for high-humidity sintering flue gas uses mullite honeycomb ceramics as a carrier, and copper oxide and cerium oxide serving as catalytic active components are loaded on the carrier. The porosity of the mullite honeycomb ceramic carrier is 60%.
The catalyst for the high-humidity sintering flue gas is prepared by the following steps:
S1, pretreatment of a carrier
Washing mullite with deionized water for 3 times, putting the washed mullite into a muffle furnace for roasting, heating to 130 ℃, keeping the temperature for 1.5 hours, heating to 600 ℃ and keeping the temperature for 2.5 hours; cooling to room temperature along with the furnace; s2, preparing an active component solution
Preparing copper ion aqueous solution with the concentration of 2mol/L by using Cu (NO 3)2·6H2 O and deionized water, preparing cerium ion aqueous solution with the concentration of 6mol/L by using Ce (NO 3)3·6H2 O and deionized water; mixing the copper ion aqueous solution and the cerium ion aqueous solution into active component solution according to the volume ratio of 1:1, wherein the ratio of copper to cerium in the active component solution is 1:3;
S3, mullite honeycomb ceramic impregnation
Adding the pretreated mullite honeycomb ceramic obtained in the step 1 into an active component solution, wherein the addition amount is 1000g/L; stirring and soaking for 10 hours, and filtering to obtain mullite honeycomb ceramic;
s4, drying and roasting
Heating the impregnated honeycomb ceramic mullite to 100 ℃ under the protection of nitrogen atmosphere, keeping the temperature for 3 hours, heating to 350 ℃, keeping the temperature for 4 hours, and cooling to room temperature to obtain the catalyst for high-humidity sintering flue gas.
Example 4
A catalyst for high-humidity sintering flue gas uses mullite honeycomb ceramics as a carrier, and copper oxide and cerium oxide serving as catalytic active components are loaded on the carrier. The porosity of the mullite honeycomb ceramic carrier is 60%.
The catalyst for the high-humidity sintering flue gas is prepared by the following steps:
S1, pretreatment of a carrier
Washing mullite with deionized water for 3 times, putting the washed mullite into a muffle furnace for roasting, heating to 130 ℃, keeping the temperature for 1.5 hours, heating to 600 ℃ and keeping the temperature for 2.5 hours; cooling to room temperature along with the furnace; s2, preparing an active component solution
Preparing copper ion aqueous solution with the concentration of 1mol/L by using Cu (NO 3)2·6H2 O and deionized water, preparing cerium ion aqueous solution with the concentration of 3mol/L by using Ce (NO 3)3·6H2 O and deionized water; mixing the copper ion aqueous solution and the cerium ion aqueous solution into active component solution according to the volume ratio of 1:1, wherein the ratio of copper to cerium in the active component solution is 1:3;
S3, mullite honeycomb ceramic impregnation
Adding the pretreated mullite honeycomb ceramic obtained in the step 1 into an active component solution, wherein the addition amount is 1000g/L; stirring and soaking for 10 hours, and filtering to obtain mullite honeycomb ceramic;
s4, drying and roasting
Heating the impregnated honeycomb ceramic mullite to 100 ℃ under the protection of nitrogen atmosphere, keeping the temperature for 3 hours, heating to 300 ℃, keeping the temperature for 4 hours, and cooling to room temperature to obtain the catalyst for high-humidity sintering flue gas.
The advantageous effects of the present invention will be described below using comparative examples.
Comparative example 1
This comparative example is that of example 3, and the preparation steps and parameter control are substantially identical to those of example 3, except that: in the step S2, the concentration of the prepared copper ion aqueous solution is 0.5mol/L, and the concentration of the cerium ion aqueous solution is 1.5mol/L; the mixing ratio of the copper ion aqueous solution and the cerium ion aqueous solution is 1:1, and the copper-cerium ratio is 1:3.
Comparative example 2
This comparative example is that of example 3, and the preparation steps and parameter control are substantially identical to those of example 1, except that: in step S4, the drying and baking process is performed under an air atmosphere.
Comparative example 3
This comparative example is the comparative example of example 3, used to control the effect of mullite honeycomb ceramic specifications on catalytic effect.
The comparative example preparation procedure and parameter control were substantially identical to example 3, with the difference from example 3 that: the pore diameter of the mullite honeycomb ceramic is 8mm, the wall thickness is 1mm, and the porosity is 70%.
Comparative example 4
The comparative example is a comparative example of the existing catalyst product, and is prepared by adopting a method disclosed in China patent ZL202111214834.9, a denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof.
The preparation method comprises the following steps:
(1) Soaking the mullite honeycomb carrier in water for 24 hours, and then drying and weighing at 80 ℃ for later use;
(2) 241.6 g of Cu (NO 3)2·3H2 O and 2896.25 g of Ce (NO 3)2·6H2 O are added into 2000g of deionized water, stirred until the Cu is dissolved, metal salt solution is obtained, 1mol/L of sodium hydroxide solution is added to adjust the pH to 10-11, stirred for 4 hours, then the mixture is kept stand for 24 hours, purified water is used for suction filtration to neutrality, ethanol is used for suction filtration for 30 minutes, the solid after suction filtration is dried at 80 ℃, and crushed and sieved to 100 meshes of catalyst precursor for standby;
(3) 4333g of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 253.97 g of polyethylene glycol (the molar mass is 6000), 253.97 g of sodium carboxymethylcellulose (the viscosity is 600-3000), 317.46 g of acidic silica sol (the mass fraction is 30%), 31.75 g of tween-20 are sequentially taken and mixed, each substance is dissolved until the substance is dissolved in the adding process, and then the next substance is added. Finally, 1kg of catalyst precursor is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 30% and the pH was 4.1.
(4) Placing the mullite honeycomb carrier into a mould with the thickness of 20cm and the thickness of 20cm, pouring the prepared slurry into a mould box, and soaking for 2 hours;
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
And (3) performing a simulated sintering flue gas CO catalytic oxidation experiment on the finished catalysts prepared in examples 1-4 and comparative examples 1-4, wherein inlet flue gas comprises: 1vol% CO, 16vol% O 2, 8vol% water vapor, 0.02vol% NO, 7vol% CO 2, and N 2 as a carrier gas.
The specific experimental process is as follows:
The activity experiments were performed on a home-made catalyst test platform, and the CO conversion at 3 temperature points of 100 ℃, 175 ℃, 250 ℃ and the like were measured for the flue gas of GHSV (gas space velocity per hour) =6000 h -1. When the temperature of the reactor is stabilized to a certain temperature point, simulated flue gas is introduced, after the reaction is carried out for 30min, the concentration of CO in the gas before and after the reaction is measured by using a flue gas analyzer, the continuous measurement time of each temperature point is 10min, the average value is taken, and the CO conversion rate is calculated according to the following formula.
CO conversion= [ (CO in－COout)/COin ]. Times.100%)
The simulated sintering flue gas CO catalytic oxidation experiment adopts a fixed bed quartz reactor with temperature programming control to carry out catalytic activity test, and the detection means uses a VARIO PLUS flue gas analyzer of Germany MRU company to analyze the tail gas components after reaction.
The reaction conditions and the activity results of examples 1 to 4 are shown in Table 1, and the reaction conditions and the activity results of comparative examples 1 to 4 are shown in Table 2.
TABLE 1 CO conversion of catalysts with different copper-cerium ratios and impregnating solution concentrations
As shown in the first table, when the temperature of the flue gas exceeds 250 ℃, the catalytic conversion rate of the catalysts with different copper-cerium ratios to CO can reach 100%; however, when the temperature of the flue gas is reduced, the CO conversion rate is reduced to different degrees. Wherein, the CO conversion rate of the embodiment 1 is reduced to below 85% at 175 ℃, and the CO conversion rate of the embodiment 2-embodiment 4 still keeps above 90% at 175 ℃, wherein, the CO conversion rate of the embodiment 3 and the embodiment 4 with the copper-cerium ratio of 1:3 can reach above 98%. The CO conversion of example 3, example 4 was still significantly higher than that of example 1, example 2 when the flue gas temperature was 100 ℃. By comparing the data, it can be determined that the copper-cerium ratio has a great influence on the activity of the finished catalyst in the preparation process, the optimal copper-cerium ratio is 1:3, the best CO removal performance is achieved, and the catalyst preparation of the subsequent comparative example takes example 3 as a reference.
Example 3 differs from example 4 in that the concentration of the impregnation liquid of example 3 is doubled, which also slightly improves the CO removal rate of the finished catalyst.
Table 2 CO conversion of catalysts prepared with different parameters
As can be seen from the CO conversion data of comparative example 1, even if the copper-cerium ratio is within a reasonable range, the concentration of the copper ion aqueous solution and the cerium ion aqueous solution is too low, so that the content of the active ingredient in the catalyst is low, and the CO removal efficiency is remarkably reduced.
As can be seen from the CO conversion data of comparative example 2, the control of the atmosphere in the roasting process of the catalyst also obviously affects the catalytic effect, and the roasting under the atmosphere of N 2 can uniformly distribute active substance grains on the surface of the carrier and slow down the growth speed of the crystals, so that the generation of sintering and caking phenomena of active components on the surface of the catalyst is reduced, fine grains are firmly combined with the carrier and are not easy to fall off, and the catalytic effect of the catalyst can be obviously improved.
The specification of the mullite honeycomb ceramic is defined as 2mm aperture, square hole and 60% porosity. As can be seen from the CO conversion data of comparative example 3, after the pore diameter of the carrier is increased, the specific surface area of the carrier is reduced, and the contact sites between CO and the catalyst surface active substances are reduced, so that the removal of CO is not facilitated; similarly, a decrease in porosity also results in a decrease in the specific surface area of the support.
The comparative example 4 is a copper cerium mullite honeycomb catalyst prepared by a coating method, the catalytic effect of the catalyst is slightly better than that of the method provided by the patent, but the preparation process is relatively complicated in comparison with the method, the catalyst powder is prepared by a coprecipitation method and is prepared into slurry, a binder is used, the steps are complicated, and the catalyst is not beneficial to industrial preparation and application.
In order to more specifically understand the catalytic performance of the catalyst of the present invention, the catalyst of example 3 was tested in a laboratory for activity and water resistance, and then subjected to stability testing on site in an enterprise, as a preferred example 3.
FIG. 1 is a graph of the CO conversion at various temperatures for example 3, showing that example 3 achieves nearly 50% CO conversion at 100deg.C; the temperature range of the sintering flue gas is 100-130 ℃, and the CO removal rate of about 60% can be realized without heating; the CO catalytic rate reaches 100% at 175-250 ℃, so that CO emission lower than 2000mg/m 3 can be realized completely, which is half of the most strict standard 4000mg/m 3 of the current CO emission limit.
FIG. 2 is a graph showing the effect of moisture content on CO conversion. It can be seen from fig. 2 that the CO conversion overall tends to decrease with increasing moisture content, but does not cause a significant decrease in CO conversion by the catalyst, and that the adverse effect of moisture on CO conversion is significantly reduced with increasing reaction temperature. At 125 ℃ of sintering flue gas, as the water vapor content increases from 0 to 20vol%, the CO conversion rate decreases from 73% to 60%, and decreases by about 13%; at 150 ℃ of sintering flue gas temperature, the CO conversion rate is reduced from 85% to 71% by about 14% as the water vapor content is increased from 0 to 20 vol%; at 175 ℃ of sintering flue gas temperature, the CO conversion rate was reduced from 100% to 94% by about 6% as the moisture content increased from 0 to 20 vol%.
The similar experimental conditions (the reaction temperature is 180 ℃, the temperature is 240 ℃, the water vapor content is 0-30%) are adopted in the Studies of optimizing the removal treatment of low-concentration CO of sintering flue gas published in Cheng Yi and Zhou, the CO conversion rate of two catalysts of the Pt-coated honeycomb metal/Ce modified Fe 2O3 used in the papers is reduced by approximately 20% within the water vapor content range of 0-20%, the catalytic efficiency of the catalyst is not obviously changed along with the temperature rise, the reduction value of the CO conversion rate is 6% within the water vapor content range of 0-20% higher than that of the embodiment 3 of the invention, and the CO conversion rate is obviously increased along with the temperature rise; this demonstrates that the catalyst of example 3 of the present invention has very good water resistance.
To verify the practical applicability of example 3, the in-situ stability test of sintering flue gas was performed, and the catalyst of example 3 was subjected to the CO catalytic stability test by using sintering flue gas actually subjected to desulfurization and denitrification in a certain steel mill. The smoke component is ：0.6%～0.7%CO、12%～15%H2O、14%O2、4%CO2、NOx＜10mg·Nm3、SO2≤5mg·Nm3、N2( residual gas), the inlet temperature of the reactor is 180 ℃, and the airspeed is 6000h –1. FIG. 3 is a graph showing the catalytic efficiency of the whole process over time, wherein the CO catalytic efficiency can be maintained to be more than 98% in the initial stage (0-60 h); then a downward trend is exhibited; after 360 hours, the catalytic efficiency tends to be stable and is maintained at more than 86 percent until the 720 hours experiment is finished.
In the performance comparison of the Pt-coated honeycomb metal and Ce modified Fe 2O3 for catalyzing CO (journal of engineering science, zhou, cheng Yi, zhou Mingxi, ni Yuguo, etc., 2020, 42 (1): 70-77), under the approximate sintering flue gas conditions (0.45% CO, 11.7% H 2O、7077h–1 airspeed, 180 ℃ air inlet temperature), the catalytic efficiency of the two catalysts of the Pt-coated honeycomb metal/Ce modified Fe 2O3 is 63.9% and 34.9%, respectively, which are lower than the stable efficiency (more than 86%) obtained by the invention after 720h catalysis.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. A catalyst for high-humidity sintering flue gas, which is characterized in that: the catalyst takes mullite honeycomb ceramics as a carrier, and copper oxide and cerium oxide serving as catalytic active components are loaded on the carrier; the mullite honeycomb ceramic is zirconium-containing mullite honeycomb ceramic with the zirconium content of 0.5% -1.2%, and the porosity of the mullite honeycomb ceramic is 60%; the inner hole of the mullite honeycomb ceramic is a square hole, the aperture is 2mm, and the wall thickness between holes is 1.1mm;
The active component solution for loading the catalytic active component on the carrier is a mixed solution of a copper ion aqueous solution and a cerium ion aqueous solution, wherein the copper ion aqueous solution is Cu (prepared from NO 3)2·6H2 O and deionized water with the concentration of 1 mol/L-3 mol/L, the cerium ion aqueous solution is Ce (prepared from NO 3)3·6H2 O and deionized water with the concentration of 1 mol/L-6 mol/L, and the mixed volume ratio of the copper ion aqueous solution to the cerium ion aqueous solution is 1:7-1:1).
2. The method for preparing the catalyst for high-humidity sintering flue gas according to claim 1, characterized by comprising the following steps:
S1, pretreatment of a carrier
Washing mullite with deionized water for 3-5 times, placing the washed mullite into a muffle furnace for roasting, firstly heating to 120-130 ℃, keeping the temperature for 1-1.5 h, then heating to 350-600 ℃, keeping the temperature for 1-2.5 h, and cooling to room temperature along with the furnace;
S2, preparing an active component solution
Cu (NO 3)2·6H2 O and deionized water are used for preparing a copper ion aqueous solution with the concentration of 1 mol/L-3 mol/L, ce (NO 3)3·6H2 O and cerium ion aqueous solution with the concentration of 1 mol/L-6 mol/L are prepared in deionized water; the copper ion aqueous solution and the cerium ion aqueous solution are mixed into an active component solution according to a proportion, and the mixing volume ratio of the copper ion aqueous solution to the cerium ion aqueous solution is 1:7-1:1);
S3, mullite honeycomb ceramic impregnation
Immersing the pretreated mullite honeycomb ceramic into the active component solution, stirring and immersing for 10 hours, and filtering to take out the mullite honeycomb ceramic;
s4, drying and roasting
And drying and roasting the impregnated honeycomb ceramic mullite, and cooling to room temperature to obtain the catalyst for high-humidity sintering flue gas.
3. The method for preparing the catalyst for high-humidity sintering flue gas according to claim 2, wherein: in the step S2, the mixing volume ratio of the copper ion aqueous solution to the cerium ion aqueous solution is 1:3.
4. The method for preparing the catalyst for high-humidity sintering flue gas according to claim 2, wherein: in the step S3, the mass-volume ratio of the mullite honeycomb ceramic to the active component solution is 100 g/L-1000 g/L.
5. The method for preparing the catalyst for high-humidity sintering flue gas according to claim 2, wherein: the specific step of the step S4 is that the impregnated mullite honeycomb ceramic is heated to 100-120 ℃ under the protection of N 2 or Ar atmosphere, kept for 2-3 h, then heated to 300-350 ℃ and kept for 3-4 h, cooled to room temperature, and the catalyst for high-humidity sintering flue gas is obtained.
6. The method for preparing the catalyst for high-humidity sintering flue gas according to claim 5, wherein: the roasting temperature is 350 ℃ and the roasting time is 4 hours.
7. The use of the high-humidity sintering flue gas catalyst according to claim 1, wherein: the catalyst for the high-humidity sintering flue gas is used for selective oxidation removal of CO in the sintering flue gas.
8. The use of the high-humidity sintering flue gas catalyst according to claim 7, wherein: the volume content of water vapor in the sintering flue gas is 8-20 vol% and the volume content of CO is 0.3-1.2 vol%.
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