CN113908842A - Denitration catalyst for CO-SCR flue gas denitration and preparation method thereof - Google Patents
Denitration catalyst for CO-SCR flue gas denitration and preparation method thereof Download PDFInfo
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- CN113908842A CN113908842A CN202111214834.9A CN202111214834A CN113908842A CN 113908842 A CN113908842 A CN 113908842A CN 202111214834 A CN202111214834 A CN 202111214834A CN 113908842 A CN113908842 A CN 113908842A
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- catalyst
- mullite
- denitration
- carrier
- slurry
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 161
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 161
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 238000001354 calcination Methods 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002791 soaking Methods 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 229920000620 organic polymer Polymers 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 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 claims description 18
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 18
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 16
- 230000004584 weight gain Effects 0.000 claims description 15
- 235000019786 weight gain Nutrition 0.000 claims description 15
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 11
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 11
- 150000000703 Cerium Chemical class 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims 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 description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 28
- 239000011248 coating agent Substances 0.000 abstract description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 92
- 238000003756 stirring Methods 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000008213 purified water Substances 0.000 description 30
- 238000000967 suction filtration Methods 0.000 description 25
- 239000012266 salt solution Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- -1 comprise two methods Chemical compound 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—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
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/204—Carbon monoxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof. A preparation method of a denitration catalyst for CO-SCR flue gas denitration comprises the following steps: (1) preparing catalyst powder; (2) adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is inorganic binder, organic polymer solution and surfactant; (3) and (3) soaking the pretreated honeycomb-shaped mullite carrier in the slurry, drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration. According to the denitration catalyst for CO-SCR flue gas denitration and the preparation method thereof, the powder catalyst and the additive with adhesiveness are mixed, so that the adhesiveness of the catalyst coating on the mullite carrier is enhanced, and the coated catalyst with low cost and high adhesiveness is obtained.
Description
Technical Field
The invention belongs to the technical field of CO-SCR flue gas denitration, and particularly relates to a denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof.
Background
When the fossil energy such as coal, oil and natural gas is used, a lot of nitrogen oxides harmful to the environment and human body are generated, such as common nitrous oxide, Nitric Oxide (NO) and nitrogen dioxide (NO)2) And the like. The existence of a large amount of nitrogen oxides in the environment not only can affect animals and plants, but also can reduce the visibility of air, seriously affect the safety of people when going out, simultaneously can destroy the ozone layer, form acid rain to pollute the environment, can harm the immune system, the respiratory system, the cardiovascular system and the like of a human body when the content of the nitrogen oxides in the air is too high, and can possibly cause the death of the human body when the content of the nitrogen oxides in the air is too high.
More than 95% of nitrogen oxides in the air are produced by people, and mainly comprise flue gas emissions of power plants, cement kilns and the like. The selective catalytic reduction method is widely used for removing NO because it can remove nitrogen oxides at a relatively low temperature and requires a relatively small amount of reducing agent. CO is used as one of the components of the tail gas, the CO-SCR flue gas denitration can save the production, transportation and storage cost, and harmless N can be generated by a selective catalytic reduction method2And CO2。
The existing preparation methods of the monolithic catalyst applied to the denitration of factory flue gas mainly comprise two methods, namely preparing a honeycomb monolithic denitration catalyst by loading active components on the surface of a cordierite carrier, and preparing the honeycomb monolithic denitration catalyst by adopting an extrusion molding method. When the monolithic denitration catalyst is prepared by adopting a method of loading the active component on the surface of the cordierite carrier, the active component has poor adhesion and is easy to fall off, and the denitration efficiency is reduced. By adopting the extrusion molding method, the amount of the required active components is too much, the production cost is high, the honeycomb monolithic catalyst is easy to crack during calcination, the honeycomb monolithic catalyst is difficult to prepare and has high cost, and the catalyst cannot achieve higher low-temperature denitration efficiency.
In view of the above, the invention provides a novel denitration catalyst for denitration of CO-SCR flue gas and a preparation method thereof, and the denitration catalyst has the advantages of strong adhesion and low cost.
Disclosure of Invention
The invention aims to provide a preparation method of a denitration catalyst for CO-SCR flue gas denitration, which is characterized in that a powder catalyst with active components and an additive with adhesiveness are mixed and then coated on a mullite carrier, so that the adhesiveness is improved, and simultaneously, the problem that the mullite carrier is easy to crack in a low-temperature calcination process is solved, and the production cost is reduced.
In order to realize the purpose, the adopted technical scheme is as follows:
a preparation method of a denitration catalyst for CO-SCR flue gas denitration comprises the following steps:
(1) preparing catalyst powder;
(2) adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is inorganic binder, organic polymer solution and surfactant;
(3) and (3) soaking the pretreated honeycomb-shaped mullite carrier in the slurry, drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration.
Further, in the step (1), catalyst powder is prepared by adopting a coprecipitation method;
the slurry obtained in the step (2) comprises the following components in percentage by mass: 50-70% of water, 10-20% of additive and 20-40% of catalyst powder;
the pretreatment in the step (3) is as follows: and soaking the cleaned mullite carrier in a mixed solution containing urea and aluminum salt for 24 hours, drying at 80 ℃, and calcining.
Still further, in the step (1), cerium salt and copper salt are used as raw materials, and the molar ratio of Ce to Cu is 6.67: 1;
in the step (2), the binder is acid silica sol, the organic polymer comprises polyethylene glycol and sodium carboxymethylcellulose, and the surfactant is tween-20;
in the step (3), the aluminum salt is aluminum nitrate or aluminum sulfate.
Still further, in the step (1), the copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate;
in the step (2), the mass ratio of the polyethylene glycol, the acidic silica gel, the sodium carboxymethylcellulose and the tween-20 is 8: 10: 8: 1;
in the mixed solution in the step (3), the concentration of urea is 3.335mol/L, and the concentration of aluminum nitrate is 1 mol/L.
Still further, in the step (1), the cerium salt is cerium nitrate, and the copper salt is copper nitrate;
in the step (2), the mass fraction of the slurry is 30-40%;
in the step (3), the slurry is immersed for 2 hours.
Still further, in the step (2), the mass fraction of the slurry is 30%;
in the step (3), the drying temperature is 80 ℃ and the time is 48 hours; the calcination temperature is 550 ℃ and the calcination time is 4 h.
Further, in the step (2), the mixing temperature is 60-70 ℃;
in the step (3), the weight gain of the pretreated mullite carrier is not less than 5% of the weight of the carrier which is not pretreated;
the mass of the denitration catalyst is 110-130% of that of the pretreated mullite carrier.
The invention also aims to provide a denitration catalyst for CO-SCR flue gas denitration, which is prepared by the method and has the advantages of low cost, difficult shedding and good low-temperature denitration performance.
Still another object of the present invention is to provide use of the above denitration catalyst for performing CO selective catalytic reduction reaction.
Further, the temperature of the CO selective catalytic reduction reaction is 150-300 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the cerium-based catalyst prepared by the invention has high denitration activity at the temperature of 150-.
2. The denitration catalyst has the advantages that the loading rate of the active components of the catalyst on the carrier is high, the airflow resistance strength of the coating is high, and the mechanical strength of the carrier is high.
3. The preparation method is simple, convenient to operate and low in production cost.
4. According to the technical scheme, the powder catalyst with the active component and the additive with the adhesion are mixed and then coated on the mullite carrier, so that the adhesion is improved, and the problem that the mullite is easy to crack in the low-temperature calcination process (lower than 600 ℃) when the mullite is used as the carrier is solved, the mullite is used as the integral catalyst carrier, and the production cost can be reduced.
Detailed Description
In order to further illustrate the denitration catalyst for denitration of CO-SCR flue gas and the preparation method thereof according to the present invention, and achieve the intended purpose of the invention, the following detailed description will be made on the denitration catalyst for denitration of CO-SCR flue gas and the preparation method thereof according to the present invention, and the detailed implementation manner, structure, characteristics and efficacy thereof will be described below. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The denitration catalyst for denitration of CO-SCR flue gas and the preparation method thereof according to the present invention will be further described in detail with reference to the following specific examples:
the invention relates to a method for coating a powder catalyst on a mullite honeycomb carrier and application thereof. The preparation method comprises the step of coating a powder catalyst with active components on a mullite honeycomb carrier with the thickness of 15cm x 15cm under the action of slurry to obtain a formed denitration carrier with active components of oxides such as copper, cerium, aluminum and the like attached to holes and a surface layer. The preparation process needs to carry out pretreatment on the mullite carrier; then, preparing slurry by using polyethylene glycol, sodium carboxymethylcellulose, acidic silica gel, tween-20 and a powder catalyst, and finally carrying out dip coating by using a mould. The integral type molded catalyst has strong mechanical strength and airflow blowing strength after being dried and calcined, and the powder catalyst prepared by adopting cerium nitrate and copper nitrate through a coprecipitation method is coated on a mullite carrier and then applied to CO-SCR, so that the integral type molded catalyst has excellent low-temperature denitration performance.
The technical scheme of the invention is as follows:
a preparation method of a denitration catalyst for CO-SCR flue gas denitration comprises the following steps:
(1) preparing catalyst powder;
(2) adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is inorganic binder, organic polymer solution and surfactant;
(3) and (3) soaking the pretreated honeycomb-shaped mullite carrier in the slurry, drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration.
Preferably, in the step (1), a coprecipitation method is adopted to prepare catalyst powder;
the slurry obtained in the step (2) comprises the following components in percentage by mass: 50-70% of water, 10-20% of additive and 20-40% of catalyst powder;
the pretreatment in the step (3) is as follows: and soaking the cleaned mullite carrier in a mixed solution containing urea and aluminum salt for 24 hours, drying at 80 ℃, and calcining.
Further preferably, in the step (1), cerium salt and copper salt are used as raw materials, and the molar ratio of Ce to Cu is 6.67: 1;
in the step (2), the binder is acid silica sol serving as an inorganic binder, the organic polymer comprises polyethylene glycol and sodium carboxymethylcellulose serving as a mixing agent and a tackifier respectively, and the surfactant is tween-20 serving as a surfactant;
in the step (3), the aluminum salt is aluminum nitrate or aluminum sulfate.
Further preferably, in the step (1), the copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate;
in the step (2), the mass ratio of the polyethylene glycol, the acidic silica gel, the sodium carboxymethylcellulose and the tween-20 is 8: 10: 8: 1;
in the mixed solution in the step (3), the concentration of urea is 3.335mol/L, and the concentration of aluminum nitrate is 1 mol/L.
Further preferably, in the step (1), the cerium salt is cerium nitrate, and the copper salt is copper nitrate;
in the step (2), the mass fraction of the slurry is 30-40%;
in the step (3), the slurry is immersed for 2 hours.
Further preferably, in the step (2), the mass fraction of the slurry is 30%;
in the step (3), the drying temperature is 80 ℃ and the time is 48 hours; the calcination temperature is 550 ℃ and the calcination time is 4 h.
Further preferably, in the step (2), the mixing temperature is 60-70 ℃;
in the step (3), the weight gain of the pretreated mullite carrier is not less than 5% of the weight of the carrier which is not pretreated;
the mass of the denitration catalyst is 110-130% of that of the pretreated mullite carrier.
Example 1.
The specific operation steps are as follows:
(1) dissolving Cu salt and Ce salt in water to form metal salt solution, preparing catalyst powder by a coprecipitation method, crushing the catalyst powder to more than 100 meshes by a crusher, and sieving the crushed catalyst powder for later use.
The copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate, and the molar ratio of Ce to Cu is 6.67: 1.
In preparing the catalyst powder by the coprecipitation method: stirring the metal salt solution, then dropwise adding a precipitator (the precipitator adopts one of sodium hydroxide and ammonia water) until the pH value is 9-11, stirring, standing for precipitation, performing suction filtration, drying and calcining to obtain the powder catalyst.
Preferably, the catalyst prepared by cerium nitrate and copper nitrate has the best catalytic performance and is the optimal choice.
(2) And (3) uniformly mixing the additive and water, and adding the catalyst powder to obtain slurry. The slurry comprises the following components in percentage by mass: 50-70%, additive: 10-20%, catalyst: 20-40%, and the total of the components is 100%.
The additive is inorganic binder, organic polymer solution and surfactant.
Preferably, the binder is acid silica sol, the organic polymer comprises polyethylene glycol and sodium carboxymethylcellulose, the surfactant is tween-20, and the water is purified water.
The adding sequence is as follows: sequentially adding polyethylene glycol, acidic silica gel, sodium carboxymethylcellulose and tween-20 into a constant-temperature interlayer stirring pot filled with a certain amount of purified water at 60-70 ℃, uniformly stirring, adding a certain amount of powder catalyst, and stirring for 6h for later use; in the adding process, each substance is stirred for 30min after entering, and the next substance is added after dissolving.
The slurry concentration is 30-40 wt%.
Further preferably, the mass ratio of the polyethylene glycol, the acidic silica gel, the sodium carboxymethylcellulose and the tween-20 is 8: 10: 8: 1.
(3) and washing the mullite carrier by ultrasonic water for more than 30min, drying, soaking in a mixed solution containing urea and aluminum salt for 24h, drying at 80 ℃, and calcining to obtain the pretreated mullite honeycomb carrier.
The aluminum salt may be at least one of aluminum nitrate and aluminum sulfate.
The mixed solution is formed by mixing a urea solution and an aluminum salt solution according to the volume ratio of 1:1, and the mixing process needs to be stirred for 6 hours at normal temperature so as to achieve the purpose of fully dissolving and uniformly mixing.
The coating mass of the mullite carrier after drying and calcining is not less than 5 wt% of the mullite carrier. Namely, the weight gain of the mullite carrier after pretreatment is not less than 5 percent of the weight of the carrier without pretreatment.
Preferably, the aluminum salt is aluminum nitrate;
the mixed solution contained 3.335mol/L of urea and 1mol/L of aluminum nitrate.
(4) And (3) putting the pretreated mullite honeycomb carrier into a 20cm by 20cm iron mould box, injecting the prepared slurry into the iron mould box, covering the mullite carrier, soaking for 2 hours, drying for 48 hours at 80 ℃, and calcining for 4 hours at 550 ℃ to obtain the honeycomb-shaped denitration catalyst carrier.
The mass of the denitration catalyst is 110-130% of that of the pretreated mullite carrier.
Example 2.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. And adding 1mol/L sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4h, standing for 24h, performing suction filtration by using purified water until the solution is neutral, performing suction filtration by using ethanol for 30min, drying the solid after suction filtration at 80 ℃, calcining the solid at 550 ℃ for 4h by using a muffle furnace, crushing and sieving the calcined solid to 100 meshes to obtain the powder catalyst.
(3) 6kg of purified water is put into a sandwich stirring pot, the oil bath is heated to 70 ℃, then the stirring is started, 148.15g of polyethylene glycol (with the molar mass of 6000), 148.15g of sodium carboxymethylcellulose (with the viscosity of 600-3000), 185.19g of acidic silica sol (with the mass fraction of 30%) and 18.52g of tween-20 are sequentially mixed, and in the adding process, each substance is added until the next substance is dissolved. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry, wherein the concentration of the slurry is 20 percent, and the pH value is 3.6.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours;
(5) and drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight gain of the mullite after coating is 15 percent (namely the mass of the denitration catalyst is 115 percent of the mass of the pretreated mullite carrier).
Example 3.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. And adding 1mol/L sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4h, standing for 24h, performing suction filtration by using purified water until the solution is neutral, performing suction filtration by using ethanol for 30min, drying the solid after suction filtration at 80 ℃, calcining the solid at 550 ℃ for 4h by using a muffle furnace, crushing and sieving the calcined solid to 100 meshes to obtain the powder catalyst.
(3) 4926g of purified water is put into a jacketed stirring pot, the oil bath is heated to 70 ℃, then the stirring is started, 197.53g of polyethylene glycol (with the molar mass of 6000), 197.53g of sodium carboxymethylcellulose (with the viscosity of 600-. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry, wherein the concentration of the slurry is 25 percent, and the pH value is 4.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the coated mullite is increased by 17 percent (namely the mass of the denitration catalyst is 117 percent of the mass of the pretreated mullite carrier).
Example 4.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust pH to 10-11, stirring for 4 hr, standing for 24 hr, vacuum filtering with purified water to neutrality, vacuum filtering with ethanol for 30min, and vacuum filtering to obtain solidDrying at 80 ℃, finally calcining for 4 hours at 550 ℃ by using a muffle furnace, crushing and sieving to 100 meshes to obtain the powder catalyst.
(3) 4334g of purified water is put into a jacketed stirring pot, the oil bath is heated to 70 ℃, then the stirring is started, 253.97g of polyethylene glycol (with the molar mass of 6000), 253.97g of sodium carboxymethylcellulose (with the viscosity of 600-. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry, wherein the concentration of the slurry is 30 percent, and the pH value is 4.1.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the coated mullite is increased by 24 percent (namely the mass of the denitration catalyst is 124 percent of the mass of the pretreated mullite carrier).
Example 5.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Then adding 1mol/L sodium hydroxide solution for regulationAnd (2) keeping the pH value at 10-11, stirring for 4h, standing for 24h, performing suction filtration with purified water to neutrality, performing suction filtration with ethanol for 30min, drying the solid obtained after suction filtration at 80 ℃, calcining for 4h at 550 ℃ by using a muffle furnace, crushing and sieving to 100 meshes to obtain the powder catalyst.
(3) 3857g of purified water is put into a jacketed stirring pot, the oil bath is heated to 70 ℃, then the stirring is started, 319.09g of polyethylene glycol (with the molar mass of 6000), 319.09g of sodium carboxymethylcellulose (with the viscosity of 600-. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 35% and the pH was 4.2.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the coated mullite is increased by 22 percent (namely the mass of the denitration catalyst is 122 percent of the mass of the pretreated mullite carrier).
Example 6.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. And adding 1mol/L sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4h, standing for 24h, performing suction filtration by using purified water until the solution is neutral, performing suction filtration by using ethanol for 30min, drying the solid after suction filtration at 80 ℃, calcining the solid at 550 ℃ for 4h by using a muffle furnace, crushing and sieving the calcined solid to 100 meshes to obtain the powder catalyst.
(3) 3.5kg of purified water is put into a jacketed stirring pot, the stirring is started after the oil bath is heated to 70 ℃, 395.06g of polyethylene glycol (with the molar mass of 6000), 395.06g of sodium carboxymethylcellulose (with the viscosity of 600-. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 40% and the pH was 4.1.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight gain of the mullite after coating is 23 percent (namely the mass of the denitration catalyst is 123 percent of the mass of the pretreated mullite carrier).
Example 7.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2Adding O into 2000g of purified water, stirring until the O is dissolved to obtain a metal salt solution, adding 1mol/L of sodium hydroxide solution to adjust the pH value to 10-11, and stirring for 4 hours to obtain an impregnation solution.
Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared impregnation liquid into a mold box, and soaking for 2 hours.
(3) And drying the impregnated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the coated mullite is increased by 12 percent (namely the mass of the denitration catalyst is 112 percent of the mass of the pretreated mullite carrier).
Example 8.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)2·6H2Adding O into 2000g of purified water, stirring until dissolving to obtain a metal salt solution, adding 1mol/L of sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4 hours, standing for 24 hours, performing suction filtration with purified water until the solution is neutral, performing suction filtration with ethanol for 30 minutes, drying the solid after suction filtration at 80 ℃, crushing and sieving to obtain a catalyst precursor with 100 meshes for later use;
(3) 4333g of purified water is put into a jacketed stirring pot, the oil bath is heated to 70 ℃, then the stirring is started, 253.97g of polyethylene glycol (with the molar mass of 6000), 253.97g of sodium carboxymethylcellulose (with the viscosity of 600-. And finally, adding 1kg of catalyst precursor, and stirring for 4 hours at constant temperature to obtain slurry. The slurry concentration was 30% and the pH was 4.1.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the coated mullite is increased by 21 percent (namely the mass of the denitration catalyst is 121 percent of the mass of the pretreated mullite carrier).
Example 9.
The specific operation steps are as follows:
(1) soaking a mullite honeycomb carrier in water for 24 hours, and drying and weighing the mullite honeycomb carrier at 80 ℃ for later use;
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)2·6H2Adding O into 2000g of purified water, stirring until dissolving to obtain a metal salt solution, adding 1mol/L of sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4 hours, standing for 24 hours, performing suction filtration with purified water until the solution is neutral, performing suction filtration with ethanol for 30 minutes, drying the solid after suction filtration at 80 ℃, crushing and sieving to obtain a catalyst precursor with 100 meshes for later use;
(3) 4333g of purified water is put into a jacketed stirring pot, the oil bath is heated to 70 ℃, then the stirring is started, 253.97g of polyethylene glycol (with the molar mass of 6000), 253.97g of sodium carboxymethylcellulose (with the viscosity of 600-. And finally, adding 1kg of catalyst precursor, and stirring for 4 hours at constant temperature to obtain slurry. The slurry concentration was 30% and the pH was 4.1.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours;
(5) and drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the coated mullite is increased by 12 percent (namely the mass of the denitration catalyst is 112 percent of the mass of the pretreated mullite carrier).
Example 10.
The specific operation steps are as follows:
(1) soaking the mullite honeycomb carrier in water for 24h, drying at 80 ℃ and weighing for later use.
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. And adding 1mol/L sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4h, standing for 24h, performing suction filtration by using purified water until the solution is neutral, performing suction filtration by using ethanol for 30min, drying the solid after suction filtration at 80 ℃, calcining the solid at 550 ℃ for 4h by using a muffle furnace, crushing and sieving the calcined solid to 100 meshes to obtain the powder catalyst.
(3) 3.5kg of purified water is put into an interlayer stirring pot, the stirring is started after the oil bath is heated to 70 ℃, 1kg of powder catalyst is added, and the stirring is carried out for 4 hours at constant temperature.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared powder slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, then heating to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, the weight of the coated mullite is increased by 10 percent (namely the mass of the denitration catalyst is 110 percent of the mass of the pretreated mullite carrier), and the phenomena that the honeycomb mullite cracks and is decomposed into uneven blocks and large-area catalyst powder falls off are found.
Example 11.
The specific operation steps are as follows:
(1) using Al (NO)3)3·9H2Preparing 1L and 2mol/L aluminum salt solution by using O, preparing 1L and 6.67mol/L urea solution, adding the two solutions into a sandwich stirring pot, and stirring for 4 hours at normal temperature. And then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm by 20cm, soaking the mullite honeycomb carrier for 24 hours, drying the mullite honeycomb carrier at the temperature of 80 ℃, and calcining the mullite honeycomb carrier to obtain the pretreated mullite carrier (the weight gain of the pretreated mullite carrier is not less than 5 percent of the mass of the mullite carrier which is not pretreated).
(2) 241.6g of Cu (NO)3)2·3H2O and 2896.25g of Ce (NO)3)3·6H2O is added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. And adding 1mol/L sodium hydroxide solution to adjust the pH value to 10-11, stirring for 4h, standing for 24h, performing suction filtration by using purified water until the solution is neutral, performing suction filtration by using ethanol for 30min, drying the solid after suction filtration at 80 ℃, calcining the solid at 550 ℃ for 4h by using a muffle furnace, crushing and sieving the calcined solid to 100 meshes to obtain the powder catalyst.
(3) 3.5kg of purified water is put into a jacketed stirring pot, the stirring is started after the oil bath is heated to 70 ℃, 395.06g of polyethylene glycol (with the molar mass of 6000), 395.06g of sodium carboxymethylcellulose (with the viscosity of 600-. And finally, adding 1kg of powder catalyst, and stirring for 4 hours at constant temperature to obtain slurry. The slurry concentration was 40% and the pH was 4.1.
(4) Putting the mullite honeycomb carrier into a mold with the thickness of 20cm by 20cm, pouring the prepared slurry into a mold box, and soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24h, coating the mullite honeycomb carrier again in the slurry in the embodiment, drying the mullite honeycomb carrier again, heating the mullite honeycomb carrier to 550 ℃ in a muffle furnace at the speed of 10 ℃/min, and calcining the mullite honeycomb carrier for 4h to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, the weight of the coated mullite is increased by 135 percent (namely the mass of the denitration catalyst is 135 percent of the mass of the pretreated mullite carrier), but the mullite cracks and is decomposed into four uneven small blocks, and the phenomenon of catalyst powder falling off occurs.
Example 12.
The procedure of example 12 was the same as that of example 10 except for the pretreatment of the mullite support. The pretreatment step for mullite in example 12 is the same as the pretreatment step for the mullite support in example 11.
The mass before and after mullite coating was weighed and the weight gain after coating was greater than that of example 10. However, in the calcination process, the honeycomb mullite is cracked and decomposed into uneven blocks, and the large-area catalyst powder falls off.
The molded catalysts obtained in examples 2 to 11 were used for low-temperature denitration of CO, and the reaction conditions and the activity results are shown in Table 1.
Comparison of the Performance of the shaped catalyst: the activity experiment is carried out on a self-made catalyst test platform, wherein the carbon-nitrogen ratio is 2:1, and O is2The concentration is 0 percent (V/V), and GHSV (gas space velocity per hour) is 3333.33h-1The NO conversion rate of the flue gas of (1) was measured at 3 points of 100 ℃, 200 ℃, 300 ℃ and the like. And when the temperature of the reactor is stabilized to a certain temperature point, starting to introduce simulated flue gas, reacting for 30min, measuring the concentration of NO in the gas before and after the reaction by using a flue gas analyzer, continuously measuring for 10min at each temperature point, averaging, and calculating the NO conversion rate according to the formula 3.
NO conversion [ (NO)in-NOout)/NOin]×100％(3)
Table 1. the low temperature CO-SCR denitration efficiency of mullite honeycomb supported catalyst with different slurry concentrations is as follows:
table 2. the low-temperature CO-SCR denitration efficiency of the mullite honeycomb supported catalyst prepared by different coating methods is as follows:
as can be seen by combining the results in Table 1, the comparison of comparative examples 2 to 6 and 9 shows that the coating effect can be enhanced and the denitration efficiency can be improved after the mullite honeycomb carrier is pretreated in the preparation process; simultaneously, suitable thick liquid concentration also can increase the coating effect, promotes denitration efficiency, and when thick liquid concentration was too big, the load can promote, but the powder catalyst obscission can appear. Further, multiple coating increases the catalyst loading, but too much loading results in cracking of the mullite honeycomb support (example 11). Therefore, the mullite honeycomb carrier is pretreated, the formed catalyst is prepared by using 30% of slurry concentration, and when the weight increase is not more than 25%, higher denitration efficiency can be achieved.
And the mullite carrier is not pretreated, and when coating is carried out without using slurry, the loading capacity of the carrier is extremely low, and the carrier is easy to break during calcination, so that the loading capacity can be increased by adopting the method to pretreat the carrier and coating the carrier with the slurry, and the problem that the carrier is unstable and easy to crack under the low-temperature calcination (lower than 600 ℃) of the mullite carrier can be solved.
As can be seen from table 2, the direct solution impregnation method and the co-precipitation coating method have been compared to find that the catalyst precursor and the catalyst powder are coated at a higher coating amount and have better denitration performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a denitration catalyst for CO-SCR flue gas denitration is characterized by comprising the following steps:
(1) preparing catalyst powder;
(2) adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is inorganic binder, organic polymer solution and surfactant;
(3) and (3) soaking the pretreated honeycomb-shaped mullite carrier in the slurry, drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration.
2. The production method according to claim 1,
in the step (1), catalyst powder is prepared by adopting a coprecipitation method;
the slurry obtained in the step (2) comprises the following components in percentage by mass: 50-70% of water, 10-20% of additive and 20-40% of catalyst powder;
the pretreatment in the step (3) is as follows: and soaking the cleaned mullite carrier in a mixed solution containing urea and aluminum salt for 24 hours, drying at 80 ℃, and calcining.
3. The production method according to claim 2,
in the step (1), cerium salt and copper salt are used as raw materials, and the molar ratio of Ce to Cu is 6.67: 1;
in the step (2), the binder is acid silica sol, the organic polymer comprises polyethylene glycol and sodium carboxymethylcellulose, and the surfactant is tween-20;
in the step (3), the aluminum salt is aluminum nitrate or aluminum sulfate.
4. The production method according to claim 3,
in the step (1), the copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate;
in the step (2), the mass ratio of the polyethylene glycol, the acidic silica gel, the sodium carboxymethylcellulose and the tween-20 is 8: 10: 8: 1;
in the mixed solution in the step (3), the concentration of urea is 3.335mol/L, and the concentration of aluminum nitrate is 1 mol/L.
5. The production method according to claim 4,
in the step (1), the cerium salt is cerium nitrate, and the copper salt is copper nitrate;
in the step (2), the mass fraction of the slurry is 30-40%;
in the step (3), the slurry is immersed for 2 hours.
6. The production method according to claim 5,
in the step (2), the mass fraction of the slurry is 30%;
in the step (3), the drying temperature is 80 ℃ and the time is 48 hours; the calcination temperature is 550 ℃ and the calcination time is 4 h.
7. The production method according to claim 2,
in the step (2), the mixing temperature is 60-70 ℃;
in the step (3), the weight gain of the pretreated mullite carrier is not less than 5% of the weight of the carrier which is not pretreated;
the mass of the denitration catalyst is 110-130% of that of the pretreated mullite carrier.
8. A denitration catalyst for denitration of CO-SCR flue gas, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The use of the denitration catalyst of claim 8, wherein the denitration catalyst is subjected to a CO selective catalytic reduction reaction.
10. Use according to claim 9,
the temperature of the CO selective catalytic reduction reaction is 150-300 ℃.
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