CN116726938B - SCR denitration catalyst for synergetically removing CO and preparation method thereof - Google Patents
SCR denitration catalyst for synergetically removing CO and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 210000001161 mammalian embryo Anatomy 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 13
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 9
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
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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
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- B01D2258/0283—Flue gases
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Abstract
The invention relates to the technical field of catalysis, in particular to an SCR denitration catalyst for synergetically removing CO and a preparation method thereof, and aims to develop a high-performance water-resistant and sulfur-resistant catalyst for synergetically removing NO and CO. The preparation method comprises the following steps: s1, surface modification of anatase titanium dioxide; s2, mixing the raw materials such as modified titanium dioxide, copper nitrate, ammonium metatungstate, nickel acetate, ammonium metavanadate solution and the like; s3, preparing pug, and S4, preparing wet embryo; s5, drying; and S6, calcining to obtain the SCR denitration catalyst for CO-removal. The high-performance water-resistant and sulfur-resistant catalyst for the synergistic removal of NO and CO prepared by the invention has excellent CO removal and NO removal x Efficiency and strong SO resistance 2 Capability.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to an SCR denitration catalyst for synergetically removing CO and a preparation method thereof.
Background
The steel industry is the pillar industry of the whole national economy, and makes great contribution to the construction of the infrastructure and the industrial development of China. With the increasingly strict requirements of the country on pollutant emission, the ultra-low emission of pollutants in the steel industry starts to advance gradually. In the steel refining process, the sintering process is the process with the largest air pollution emission ratio. Incomplete combustion of coal during steel sintering can emit high concentrations of CO (about 1%). The Handan and Tangshan in 2017 and 2018 control CO in sintering flue gas successively, and the integrated treatment implementation scheme (trial) of CO in the steel industry in the Fenfen city in 2020 is formulated and issued in the Fenfen city in 2020, and CO treatment work in the steel industry is started. The removal of carbon monoxide at low concentrations in sintering flue gas is an urgent endeavor. In the CO purification technology, catalytic oxidation is the most efficient, energy-saving and secondary pollution-free purification mode, and chemical heat released by complete CO oxidation can supplement heat for SCR denitration. At present, an SCR denitration catalyst is commonly adopted in the steel industry to remove NO, and the used reducing agent is NH 3 . The CO in the flue gas discharged by sintering steel is NO x Is 160 times as much as a potential reducing agent, can reduce NH 3 Reducing the amount of ammonium sulfate produced and reducing the probability of catalyst plugging, it is therefore necessary to develop a catalyst that synergistically removes NO and CO.
Most researchers aim at the synergistic removal of NO and CO and research mainly uses Fe 2 O 3 、Al 2 O 3 、CeO 2 Etc. as carriers, which are less useful in commercial catalysts and are not conducive to industrial applications. The carrier commonly used for commercial catalysts is anatase titanium dioxide, with W and Mo added as adjuvants. The SCR reaction produces water, in this environment SO 2 And NH 3 The combination of the ammonium sulfate to form the catalyst is blocked, and the CO used as the reducing agent can reduce or even replace NH 3 The water resistance and the sulfur resistance of the catalyst are improved, and the service life of the catalyst is prolonged. Therefore, development of a high-performance water-resistant sulfur-resistant catalyst for synergetic removal of NO and CO is imperative.
Disclosure of Invention
Therefore, the invention aims to provide an SCR denitration catalyst for synergetically removing CO and a preparation method thereof, so as to develop a high-performance water-resistant and sulfur-resistant catalyst for synergetically removing NO and CO.
Based on the above purpose, the invention provides a preparation method of an SCR denitration catalyst for synergetically removing CO, which comprises the following specific preparation steps:
s1: adding sucrose and anatase titanium dioxide into a mixed solution of ethanol and deionized water, stirring for 40-60min, then adding butyl phosphate titanate and industrial ammonia water, stirring for 10-20min, performing hydrothermal reaction at 180-200 ℃ for 12-18h, centrifuging, washing, drying, and calcining at 450-550 ℃ for 3-5h to obtain modified titanium dioxide;
s2: adding modified titanium dioxide, copper nitrate, ammonium metatungstate, nickel acetate, ammonium metavanadate solution, industrial ammonia water and deionized water into a mixing mill, stirring for 40-60min, adding lactic acid and stearic acid, and stirring for 50-70min after the temperature is raised to 70-90 ℃ to obtain a mixture;
s3: adding dendritic polyamidoamine, carboxymethyl cellulose, polyoxyethylene, paper pulp and glass fiber into the mixture, stirring until the water content is 20-30wt%, adding deionized water, and stirring at 60-80 ℃ until the water content is 28-30wt% to obtain pug;
s4: placing the pug into a mixing mill for ageing for 24-36h, then pre-extruding in a pre-extruder to remove impurities, and finally extruding and molding in the extruder, wherein the extrusion pressure is 3.5-4.5Mpa, so as to obtain a catalyst wet blank with 25 holes;
s5: drying the wet catalyst embryo in a drying room, wherein the initial drying temperature is 30-40 ℃, the humidity is 75-85%, the final drying temperature is 50-60 ℃, the humidity is 10-15%, and the drying time is 10-12d, so as to obtain a dry catalyst embryo;
s6: calcining the catalyst dry embryo in a kiln, heating from room temperature to 550-600 ℃ for 14-18h, calcining at constant temperature for 4-8h, and cooling to room temperature for 10-14h to obtain the SCR denitration catalyst for CO-removal.
Preferably, the specific surface area of the anatase titanium dioxide in the step S1 is 80-100m 2 And/g, the particle diameter D50 is 0.8-1.2 mu m.
Preferably, in the step S1, the mass ratio of the anatase titanium dioxide, the sucrose, the ethanol, the deionized water, the butyl phosphate titanate and the industrial ammonia water is 500-700:20-30:400-600:2000-3000:160-240:40-60.
Preferably, in the step S2, the mass ratio of the modified titanium dioxide, copper nitrate, ammonium metatungstate, nickel acetate, ammonium metavanadate solution, industrial ammonia water, deionized water, anatase titanium dioxide, lactic acid and stearic acid is 500-700:20-120:18-21:20-75:24-32:25-35:300-500:6-10:6-10.
Preferably, the preparation method of the ammonium metavanadate solution in the step S2 is as follows: mixing ammonium metavanadate, monoethanolamine and deionized water according to a mass ratio of 1:1:3 at 70-80 ℃ under stirring.
Preferably, in the step S3, the mass ratio of the dendritic polyamidoamine, the carboxymethyl cellulose, the polyoxyethylene, the paper pulp, the glass fiber and the mixture is 20-40:3-5:3-5:30-70:50-70:700-1000:200-350.
Preferably, the viscosity of the Polyoxyethylene (PEO) in step S3 is in the range of 250-350 mPa.s.
Preferably, the pulp in the step S3 is obtained by soaking paper fibers in deionized water for 30-50min, and the mass ratio of the paper fibers to the deionized water is 1:20-40.
Preferably, the glass fiber in the step S3 has a length of 5-7mm and a diameter of 5-7 μm.
The SCR denitration catalyst for CO-removal is obtained according to the preparation method of the SCR denitration catalyst for CO-removal
The invention has the beneficial effects that:
the invention provides an SCR denitration catalyst for synergetic CO removal and a preparation method thereof, and discloses a Cu-Ni-V-W-Ti honeycomb catalyst taking anatase titanium dioxide as a raw material, wherein the surface of the anatase titanium dioxide is modified and Cu with a proper proportion is introduced 2 O, niO the denitration catalyst has the capability of catalyzing and oxidizing CO, improves the capability of cooperatively removing multiple pollutants of the catalyst, introduces dendritic polyamidoamine, adopts a secondary concentration method to uniformly disperse the dendritic polyamidoamine on the surface of the active site of the catalyst, and cooperates with modified titanium dioxide to improve SO resistance of the catalyst 2 Capability.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The sources or properties of the raw materials of the examples and comparative examples of the present invention are as follows:
the ammonium metavanadate solution is prepared by stirring and mixing ammonium metavanadate, monoethanolamine and deionized water according to a mass ratio of 1:1:3 at 75 ℃; the specific surface area of the anatase titanium dioxide is 85 m 2 /g, particle size D50 of 1.1 μm; dendritic polyamidoamine is purchased from the new molecular materials of the Wihai morning source, inc., model CYD-110A; the paper pulp is obtained by mixing paper fiber and deionized water for 45min according to the mass ratio of 1:20, and the paper fiber is purchased from the glass fiber products limited company of salt city, salt and Xingjing; the glass fibers had a length of 5.5mm and a diameter of 6.2. Mu.m.
Example 1
S1: adding 20g of sucrose and 500g of anatase titanium dioxide into a mixed solution of 400g of ethanol and 2000g of deionized water, stirring for 40min, then adding 160g of butyl titanate phosphate and 40g of industrial ammonia water, stirring for 10min, performing hydrothermal reaction at 180 ℃ for 12h, centrifuging, washing, drying, and calcining at 450 ℃ for 3h to obtain modified titanium dioxide;
s2: 500g of modified titanium dioxide, 20g of copper nitrate, 18g of ammonium metatungstate, 20g of nickel acetate, 24-32g of ammonium metavanadate solution, 25g of industrial ammonia water and 300g of deionized water are added into a mixing roll, stirring is carried out for 40min, then 6g of lactic acid and 6g of stearic acid are added, and stirring is carried out for 50min after the temperature is raised to 70 ℃ to obtain a mixture;
s3: adding 20g of dendritic polyamidoamine, 3g of carboxymethyl cellulose, 3g of polyoxyethylene, 30g of paper pulp and 50g of glass fiber into 700g of mixture, stirring until the water content is 20wt%, adding 200g of deionized water, and stirring until the water content is 28wt% at 60 ℃ to obtain pug;
s4: placing the pug into a mixing mill for ageing for 24 hours, then pre-extruding the pug in a pre-extruder to remove impurities, finally extruding and molding the pug in the extruder, wherein the extrusion pressure is 3.5Mpa, and obtaining a catalyst wet blank with 25 holes;
s5: drying the wet catalyst embryo in a drying room, wherein the initial drying temperature is 30 ℃, the humidity is 75%, the final drying temperature is 60 ℃, the humidity is 10%, and the drying time is 10d, so as to obtain a dry catalyst embryo;
s6: calcining the catalyst dry embryo in a kiln, heating from room temperature to 550 ℃ for 14h, calcining at constant temperature for 4h, and cooling to room temperature for 10h to obtain the SCR denitration catalyst for CO-removal.
Example 2
S1: adding 25g of sucrose and 600g of anatase titanium dioxide into a mixed solution of 500g of ethanol and 2500g of deionized water, stirring for 50min, then adding 200g of butyl titanate phosphate and 50g of industrial ammonia water, stirring for 15min, performing hydrothermal reaction at 190 ℃ for 15h, centrifuging, washing, drying, and calcining at 500 ℃ for 4h to obtain modified titanium dioxide;
s2: 600g of modified titanium dioxide, 70g of copper nitrate, 19.5g of ammonium metatungstate, 45g of nickel acetate, 28g of ammonium metavanadate solution, 30g of industrial ammonia water and 400g of deionized water are added into a mixing roll, and are stirred for 50min, 8g of lactic acid and 8g of stearic acid are added, and then the mixture is obtained after the temperature is raised to 80 ℃ and is stirred for 60 min;
s3: adding 30g of dendritic polyamidoamine, 4g of carboxymethyl cellulose, 4g of polyoxyethylene, 50g of paper pulp and 60g of glass fiber into 850g of mixture, stirring until the water content is 25wt%, adding 280g of deionized water, and stirring until the water content is 29wt% at 70 ℃ to obtain pug;
s4: placing the pug into a mixing mill for aging for 30 hours, then pre-extruding the pug in a pre-extruder to remove impurities, finally extruding and molding the pug in the extruder, wherein the extrusion pressure is 4Mpa, and obtaining a catalyst wet blank with 25 holes;
s5: drying the wet catalyst embryo in a drying room, wherein the initial drying temperature is 35 ℃, the humidity is 80%, the final drying temperature is 55 ℃, the humidity is 12%, and the drying time is 11d, so as to obtain a dry catalyst embryo;
s6: calcining the catalyst dry embryo in a kiln, heating from room temperature to 600 ℃ for 16h, calcining at constant temperature for 6h, and cooling to room temperature for 12h to obtain the SCR denitration catalyst for CO-removal.
Example 3
S1: adding 30g of sucrose and 700g of anatase titanium dioxide into a mixed solution of 600g of ethanol and 3000g of deionized water, stirring for 60min, then adding 240g of butyl titanate phosphate and 60g of industrial ammonia water, stirring for 20min, performing hydrothermal reaction at 200 ℃ for 18h, centrifuging, washing, drying, and calcining at 550 ℃ for 5h to obtain modified titanium dioxide;
s2: 700g of modified titanium dioxide, 120g of copper nitrate, 21g of ammonium metatungstate, 75g of nickel acetate, 32g of ammonium metavanadate solution, 35g of industrial ammonia water and 500g of deionized water are added into a mixing roll, stirring is carried out for 60min, then 10g of lactic acid and 10g of stearic acid are added, and stirring is carried out for 70min after the temperature is raised to 90 ℃ to obtain a mixture;
s3: adding 40g of dendritic polyamidoamine, 5g of carboxymethyl cellulose, 5g of polyoxyethylene, 70g of paper pulp and 70g of glass fiber into 1000g of mixture, stirring until the water content is 30wt%, adding 200-350g of deionized water, and stirring at 80 ℃ until the water content is 30wt% to obtain pug;
s4: placing the pug into a mixing mill for aging for 36 hours, then pre-extruding the pug in a pre-extruder to remove impurities, finally extruding and molding the pug in the extruder, wherein the extrusion pressure is 4.5Mpa, and obtaining a catalyst wet blank with 25 holes;
s5: drying the wet catalyst embryo in a drying room, wherein the initial drying temperature is 40 ℃, the humidity is 85%, the final drying temperature is 60 ℃, the humidity is 15%, and the drying time is 12d, so as to obtain a dry catalyst embryo;
s6: calcining the catalyst dry embryo in a kiln, heating from room temperature to 600 ℃ for 18h, calcining at constant temperature for 8h, and cooling to room temperature for 14h to obtain the SCR denitration catalyst for CO-removal.
Comparative example 1 differs from example 2 in that: and (3) replacing the modified titanium dioxide in the step (S2) with anatase titanium dioxide.
Comparative example 2 differs from example 2 in that: in step S3, the amount of the glass fiber added was changed to 90g without adding the dendritic polyamidoamine.
Comparative example 3 differs from example 2 in that: the modified titanium dioxide in the step S2 is replaced by anatase titanium dioxide, dendritic polyamidoamine is not added in the step S3, and the addition amount of the glass fiber is 90g.
Comparative example 4 differs from example 2 in that: step S3 is modified, and the modification is as follows;
step S3: dendritic polyamidoamine, carboxymethyl cellulose, polyoxyethylene, paper pulp and glass fiber are added into the mixture, and stirred at 70 ℃ until the water content is 29wt% to obtain pug.
Comparative example 5 differs from example 2 in that: copper nitrate and nickel acetate are not added in step S2.
Comparative example 6 differs from example 2 in that: in step S2, no nickel acetate was added, and the amount of copper nitrate added was 115g.
The catalysts prepared in the examples and the comparative examples are subjected to specific surface area, pore volume and pore diameter, denitration performance and SO resistance according to national standard GBT 31587-2015 honeycomb flue gas denitration catalyst 2 Is a test of (2).
Specific surface area and pore volume aperture: the specific surface area adopts a BET calculation method, the pore volume adopts a BJH method, and the detection instrument is a BSD-PS2 specific surface and pore diameter analyzer manufactured by Bei Shide instrument technology (Beijing) limited company. The microscopic specific surface area and pore volume and pore diameter test results of the samples are shown in table 1.
TABLE 1 results of specific surface area measurements
Data analysis: it can be seen from examples 1-3 that the CO-removal SCR denitration catalyst prepared by the present invention has a higher specific surface area and a larger pore volume, which results in higher denitration efficiency.
Denitration performance: the prepared catalysts of examples and comparative examples are cut into test samples with the same size, 4 multiplied by 4 and 40cm length, and the test samples are put into a reactor for denitration test under the following conditions: the temperature of the reaction system is 250-420 ℃, and the airspeed of the mixed gas is 5000h -1 Mixed gas content: NO (NO) x 400ppm，CO 1000ppm，O 2 16％，SO 2 50ppm，NH 3 400ppm，N 2 As carrier gas, all the gases except the reducing agent ammonia are mixed by a mass flowmeter and then are heated by a mixing preheater to enter the reactor, and the ammonia is directly introduced into the reactor. Collecting and analyzing gas at the sampling port by using a testo 350-EPA portable smoke analyzer, and calculating CO and NO x Removal rate, each sample was specific to CO, NO x The removal performance is shown in table 2.
Table 2 denitration performance test results
Data analysis: as can be seen from examples 1-3, the SCR denitration catalyst for CO-removal prepared by the invention has excellent CO removal and NO removal x Efficiency it can be seen from example 2 and comparative examples 1-3 that the surface modification of anatase titanium dioxide has a significant effect on the efficiency of removing CO, probably due to the stronger adsorption capacity of modified anatase titanium dioxide on CO, and from example 2 and comparative examples 5, 6 that the introduction of copper significantly improves the efficiency of removing CO, and the introduction of nickel further promotes the efficiency of removing CO.
SO resistance 2 Performance: to test for SO resistance 2 Performance, the temperature in the test condition of the denitration performance is fixed to be 250 ℃, and the catalyst is filled into a reactor for the first time SO resistance 2 Testing of NO x Maximum removal rate eta max NO and x working time t when the removal rate is lower than 50%, when NO x After the removal rate is lower than 50%, N is used 2 Purging the catalyst for 2 hours and loading the catalyst into the reactor for a second SO resistance 2 Testing of NO x Maximum removal rate eta max NO and x working time t when the removal rate is lower than 50%, when NO x After the removal rate is lower than 50%, N is used 2 Purging the catalyst for 2 hours and loading the catalyst into the reactor for a third SO resistance 2 Testing, testing the maximum removal rate eta max NO and x the result of the working time t when the removal rate was less than 50% is shown in Table 3.
TABLE 3 SO resistance 2 Performance test results
Data analysis: as can be seen from example 2, the SCR denitration catalyst for CO-removal prepared by the invention has stronger SO resistance 2 Performance and can still maintain stronger SO resistance in the recycling process 2 Performance it can be seen from example 2 and comparative examples 1-3 that the surface modification of anatase titanium dioxide and the incorporation of hyperbranched polyamidoamine synergistically improved the SO resistance of the catalyst 2 The performance is probably due to the reduction of SO by the formation of a composite of modified titanium dioxide and hyperbranched polyamidoamine after calcination 2 Adsorption and reaction on the active sites reduced sulfate deposition on the active sites, as can be seen from example 2 and comparative example 4, the secondary concentration process is resistant to SO on the catalyst 2 The performance has an acceleration effect mainly because the secondary concentration contributes to the more equally distributed dispersion and more stable combination of hyperbranched polyamidoamine on the surface of the modified titanium dioxide.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (7)
1. The preparation method of the SCR denitration catalyst for synergetically removing CO is characterized by comprising the following specific preparation steps:
s1: adding sucrose and anatase titanium dioxide into a mixed solution of ethanol and deionized water, stirring for 40-60min, then adding butyl phosphate titanate and industrial ammonia water, stirring for 10-20min, performing hydrothermal reaction at 180-200 ℃ for 12-18h, centrifuging, washing, drying, and calcining at 450-550 ℃ for 3-5h to obtain modified titanium dioxide;
s2: adding modified titanium dioxide, copper nitrate, ammonium metatungstate, nickel acetate, ammonium metavanadate solution, industrial ammonia water and deionized water into a mixing mill, stirring for 40-60min, adding lactic acid and stearic acid, and stirring for 50-70min after the temperature is raised to 70-90 ℃ to obtain a mixture;
s3: adding dendritic polyamidoamine, carboxymethyl cellulose, polyoxyethylene, paper pulp and glass fiber into the mixture, stirring until the water content is 20-30wt%, adding deionized water, and stirring at 60-80 ℃ until the water content is 28-30wt% to obtain pug;
s4: placing the pug into a mixing mill for ageing for 24-36h, then pre-extruding in a pre-extruder to remove impurities, and finally extruding and molding in the extruder, wherein the extrusion pressure is 3.5-4.5Mpa, so as to obtain a catalyst wet blank with 25 holes;
s5: drying the wet catalyst embryo in a drying room, wherein the initial drying temperature is 30-40 ℃, the humidity is 75-85%, the final drying temperature is 50-60 ℃, the humidity is 10-15%, and the drying time is 10-12d, so as to obtain a dry catalyst embryo;
s6: calcining the catalyst dry embryo in a kiln, heating from room temperature to 550-600 ℃ for 14-18h, calcining at constant temperature for 4-8h, and cooling to room temperature for 10-14h to obtain the SCR denitration catalyst for CO-removal.
2. The method for preparing the CO-removal SCR denitration catalyst according to claim 1, wherein the specific surface area of the anatase titanium dioxide in the step S1 is 80-100m 2 And/g, the particle diameter D50 is 0.8-1.2 mu m.
3. The method for preparing the CO-removal SCR denitration catalyst according to claim 1, wherein the method for preparing the ammonium metavanadate solution in the step S2 is as follows: mixing ammonium metavanadate, monoethanolamine and deionized water according to a mass ratio of 1:1:3 at 70-80 ℃ under stirring.
4. The method for preparing a CO-removal SCR denitration catalyst according to claim 1, wherein the viscosity of Polyoxyethylene (PEO) in step S3 is in the range of 250 to 350 mPa-S.
5. The method for preparing the CO-removal SCR denitration catalyst according to claim 1, wherein the pulp in the step S3 is obtained by soaking paper fibers in deionized water for 30-50min, and the mass ratio of the paper fibers to the deionized water is 1:20-40.
6. The method for preparing the CO-removal SCR denitration catalyst according to claim 1, wherein the glass fiber in the step S3 has a length of 5 to 7mm and a diameter of 5 to 7 μm.
7. An SCR denitration catalyst for CO-removal, characterized in that it is obtained by the method for preparing an SCR denitration catalyst for CO-removal according to any one of claims 1 to 6.
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| CN102962055A (en) * | 2012-11-22 | 2013-03-13 | 中节能六合天融环保科技有限公司 | Molybdenum-based low-temperature denitration catalyst and preparation thereof |
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