CN116020574A - Integral carbon monoxide purifying catalyst with protective agent and preparation method and application thereof - Google Patents
Integral carbon monoxide purifying catalyst with protective agent and preparation method and application thereof Download PDFInfo
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- CN116020574A CN116020574A CN202211739169.XA CN202211739169A CN116020574A CN 116020574 A CN116020574 A CN 116020574A CN 202211739169 A CN202211739169 A CN 202211739169A CN 116020574 A CN116020574 A CN 116020574A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003223 protective agent Substances 0.000 title claims abstract description 68
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 50
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- 239000003546 flue gas Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
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- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 7
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 7
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 7
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 7
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000012216 bentonite Nutrition 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
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- 235000019698 starch Nutrition 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- 231100000614 poison Toxicity 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000002574 poison Substances 0.000 abstract description 4
- 238000009851 ferrous metallurgy Methods 0.000 abstract description 2
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- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
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- 239000010959 steel Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
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- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to the technical field of flue gas treatment in the ferrous metallurgy industry, in particular to an integral carbon monoxide purifying catalyst with long service life, and a preparation method and application thereof. The catalyst of the present invention can be prepared by two methodsThe preparation method comprises the following steps: (1) Coating a protective agent layer and a CO oxidation catalytic active layer on the honeycomb carrier in a segmented manner; (2) Is formed by combining two reaction blocks with protective agent and CO oxidation catalytic function. The CO purifying catalyst of the invention not only can effectively reduce SO 2 The negative influence on the catalyst can also reduce the poison of oil and heavy metal elements in the flue gas to the catalyst, and obviously improve the service life of the catalyst.
Description
Technical Field
The invention relates to the technical field of flue gas treatment in the ferrous metallurgy industry, in particular to an integral carbon monoxide purifying catalyst with long service life, and a preparation method and application thereof.
Background
The steel production in China is mainly carried out in a long process, and occupies more than 90% of the total national steel production. The sintering process is an indispensable step in long-flow steel smelting, and the generated atmospheric pollutants are always important in the environmental protection field. The amount of carbon monoxide (CO) generated during sintering is enormous, and its emission control is a difficulty. With the sequential requirements of CO emission limits set forth in multiple provinces, development and application of related emission reduction and purification technologies are urgently needed.
End treatment techniques are considered to be the most effective means of controlling sintering flue gas CO. Wherein the CO is oxidized to CO by using a catalyst 2 The method can eliminate CO and has small influence on the sintering process, and is the sintering flue gas CO control technology with the most application prospect at present. The CO oxidation catalyst is the core of the technology, the development of a high-efficiency and long-service-life catalyst becomes a key, and the poisoning and deactivation of the catalyst are the biggest problems encountered at present. In the process of treating the tail end of sintering flue gas, although the flue gas is subjected to desulfurization treatment, residual SO still exists in the actual flue gas 2 (0～35mg/Nm 3 ) Poisoning of the catalyst, especially great damage to the service life of non-noble metal catalysts. In addition, some oils, heavy metals and alkaline earth elements in the sintering flue gas are also easily deposited on the surface of the catalyst, reducing the performance of the catalyst.
In order to improve the poisoning resistance of the catalyst, researchers optimize the catalyst mainly through means such as doping auxiliary agents, designing a core-shell structure and the like, and the main principle is that SO in flue gas is reduced 2 Contact with the active sites of the catalyst to reduce the poisoning degree of the catalyst. Although these methods are designed to alleviate the SO of the catalyst to some extent 2 Poisoning, but the production process is complex and the cost is excessive in the industrialized production of the catalystThe high and finished catalyst can not meet the original design requirement, and the actual use effect is not ideal. In addition, other toxic substances in the flue gas can still have a poisoning effect on the catalyst.
Disclosure of Invention
The invention aims to solve the problem that the existing CO oxidation catalyst is easy to poison in the sintering flue gas treatment process, and provides an integral CO oxidation catalyst with a protective agent, wherein the protective agent is used for preventing the CO oxidation catalyst from being poisoned by SO 2 Reacts with the toxic substances in the flue gas, and not only can effectively reduce SO 2 The negative influence on the catalyst can also reduce the poison of oil and heavy metal elements in the flue gas to the catalyst, and obviously improve the service life of the catalyst.
The CO oxidation catalyst with the protective agent consists of two parts, wherein one part is used for treating SO in flue gas 2 And other harmful impurities, and the other is a catalytically active portion for purifying CO. The catalyst of the invention can be formed by two sections of coating layers with different functions on the same honeycomb carrier, and can also be formed by combining two reaction blocks with protective agents and catalytic functions respectively. The types, coating amounts and lengths of the two parts can be flexibly modulated according to the concentration of pollutant components in actual flue gas and control requirements.
The protective agent is one or more of calcium hydroxide, sodium hydroxide, calcium oxide, manganese dioxide, cerium dioxide, zinc oxide, magnesium oxide and copper oxide; the CO oxidation catalytic active component is one or more of titanium dioxide supported transition metal and carbon metal, or one or more of alumina supported carbon metal and transition metal.
When the integral catalyst is formed by two sections of coating layers with different functions on the same honeycomb carrier, the protective agent and the catalytic active part are coated on the honeycomb carrier by adopting a vacuum coating method. Uniformly mixing the protective agent substance and the binder, grinding the mixture on a grinder (the grinding rotating speed is 500-800 r/min and the time is 1-3 hours), adding the additive after finishing grinding to obtain slurry for coating, coating the slurry (the coating amount is 20-120 g/L) on a part of the area of the honeycomb carrier by using a vacuum coating machine, and drying and calcining to obtain the protective agent part, wherein the coating length of the part occupies 1/4-1/2 of the carrier. The precursor of the CO oxidation catalytic active component and the binder are uniformly mixed and then ground on a grinder (the grinding rotating speed is 800-1200 r/min and the time is 0.5-2 hours), the additive is added after the grinding is finished, the slurry for coating is obtained, the slurry is coated on the residual area of the honeycomb carrier by a vacuum coating machine (the coating amount is 60-120 g/L), and the coating length of the part occupies 1/2-3/4 of the carrier.
Further, the carrier is honeycomb cordierite or honeycomb titanium dioxide. The number of holes of the carrier is 20-70 holes.
Further, the protective agent substance is one or more of calcium hydroxide, sodium hydroxide, calcium oxide, manganese dioxide, cerium dioxide, zinc oxide, magnesium oxide and copper oxide.
Further, the precursor of the CO oxidation catalytic active component is one or more of chloride, nitrate, sulfate and acetate of platinum, palladium, gold, copper, cerium, tin or iron, and is formed by combining one or two of titanium dioxide powder and active alumina powder.
Further, the binder is silica sol or alumina sol.
Further, the additive is one or more of hydroxypropyl methylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, isopropanol, nitric acid, acetic acid and polyethylene glycol.
Further, in the process of the partial coating of the protective agent, the mass ratio of the protective agent substance to the binder to the additive is 10-20: 1 to 5:0 to 2.
Further, in the process of coating the CO oxidation catalytic active part, the mass ratio of the precursor of the CO oxidation catalytic active component to the binder to the additive is 0.1-10: 1 to 5:0 to 3.
Further, the protective agent is partially dried by hot air, the drying temperature is 80-110 ℃, and the drying time is 0.1-0.5 hour.
Further, the partial calcination temperature of the protective agent is 300-450 ℃, and the calcination time is 0.5-4 hours.
Further, the CO oxidation catalytic active layer is dried by hot air, the drying temperature is 80-110 ℃, and the drying time is 0.1-0.5 hour.
Further, the calcination temperature of the CO oxidation catalytic active layer is 300-500 ℃ and the calcination time is 1-5 hours.
When the integral catalyst is formed by combining two reaction blocks with a protective agent and a catalytic function respectively, the protective agent is extruded and molded by a vacuum extruder, and a catalytic active part is coated on the surface of a honeycomb carrier (honeycomb cordierite or honeycomb titanium dioxide) by adopting a vacuum coating method. And (3) uniformly mixing and stirring the protective agent substance, the binder and the additive, extruding the mixture into a honeycomb shape through a vacuum extruder, and drying and calcining the extrudate to obtain the honeycomb protective agent block. The precursor of the CO oxidation catalytic active component and the binder are uniformly mixed and then ground on a grinder (the grinding rotating speed is 800-1200 r/min and the time is 0.5-2 hours), additives are added after the grinding is finished, the slurry for coating is obtained, and the slurry is coated on the surface of the honeycomb carrier (the coating amount is 60-120 g/L) by a vacuum coating machine, so that the honeycomb CO oxidation catalyst block is obtained. The lengths of the two blocks with different functions can be combined arbitrarily according to actual conditions, and the integral catalyst is obtained after the two blocks are combined.
Further, the number of holes of the extruded honeycomb protective agent block is 20 to 70 holes.
Further, the number of holes of the honeycomb CO oxidation catalyst block is 20 to 70 holes.
Further, the protective agent substance is one or more of calcium hydroxide, sodium hydroxide, calcium oxide, manganese dioxide, cerium dioxide, zinc oxide, magnesium oxide and copper oxide.
Further, the precursor of the CO oxidation catalytic active component is one or more of chloride, nitrate, sulfate and acetate of platinum, palladium, gold, copper, cerium, tin or iron, and is formed by combining one or two of titanium dioxide powder and active alumina powder.
Further, the binder is silica sol or alumina sol.
Further, the additive for extrusion molding is one or more of bentonite, starch, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
Further, the additive for vacuum coating is one or more of hydroxyethyl cellulose, hydroxymethyl cellulose, isopropanol, nitric acid, acetic acid and polyethylene glycol.
Further, in the extruded protective agent block, the mass ratio of the protective agent substance to the binder to the additive is 10-50: 0 to 25:2 to 10.
Further, in the CO oxidation catalyst block, the mass ratio of the precursor of the CO oxidation catalytic active component to the binder to the additive is 0.1-10: 1 to 5:0 to 3.
Further, the extruded protective agent block is dried by hot air, the drying temperature is 80-110 ℃, and the drying time is 0.5-5 hours.
Further, the calcination temperature of the extruded protective agent block is 300-450 ℃ and the calcination time is 0.5-2 hours.
Further, the CO oxidation catalyst block is dried by hot air, the drying temperature is 80-110 ℃, and the drying time is 0.1-0.5 hour.
Further, the calcination temperature of the CO oxidation catalyst block is 300-500 ℃ and the calcination time is 1-5 hours.
By adopting the scheme, the invention has the following advantages compared with the prior art:
the protective agent of the invention has the function of removing SO in the flue gas 2 The function of capturing and adsorbing other harmful substances reduces the poisoning influence on the CO oxidation catalytic activity part by secondarily purifying the flue gas, thereby prolonging the service life of the catalyst. In addition, the protective agent and the CO oxidation catalytic active layer can be freely combined according to flue gas conditions and treatment requirements, and the use and design are convenient. When the service life of the protective agent is over, the protective agent can be directly replaced by a new protective agent to ensure the purification effect, the operation is simple, the cost is low, and the protective agent is practical to the greatest extentProtection of the catalytically active layer is now provided.
Drawings
FIG. 1 is a schematic illustration of the structure of a catalyst A formed by applying two different functional coatings to a honeycomb carrier according to example 1.
FIG. 2 is a schematic diagram of the structure of a catalyst B in example 2, which is composed of two blocks each having a protecting agent and a catalytic reaction function.
Fig. 3 is a graph of CO oxidation performance under actual flue gas conditions for catalyst a prepared in example 1, catalyst B prepared in example 2, and catalyst C without added protective agent.
Fig. 4 is a graph showing the analysis of the S element content on the surface of the CO oxidation catalyst layer after the catalyst A, B, C prepared in examples 1 and 2 was used.
Fig. 5 is a graph showing the analysis of the surface element content of the protective agent layer after use of the catalyst A, B prepared in examples 1 and 2.
Detailed Description
The technical scheme of the invention is specifically described below through specific embodiments and with reference to the accompanying drawings. The experimental methods used in the following examples are all conventional methods unless otherwise specified; materials, reagents and the like used, unless otherwise indicated, are all commercially available.
Titanium dioxide powder and titanium dioxide honeycomb carrier are provided by Jiangxi An Tian high new material Co., ltd, hydroxypropyl methylcellulose and bentonite are provided by Shandong Ruitai chemical Co., ltd, and the acidic nanometer aluminum sol is provided by Texas Crystal fire technology glass Co., ltd.
Example 1
Honeycomb titania with a pore number of 30 and a size of 60 x 120mm was selected as the support. 350g of manganese acetate was added to 1000g of deionized water, and a 0.5mol/L NaOH solution was added to a pH of 12. The resulting precipitate was collected by filtration and washed clean with deionized water. The precipitate was dried at 100 ℃ for 12 hours and then calcined at 450 ℃ in a muffle furnace for 3 hours to obtain a powdered manganese dioxide protectant material. Adding the prepared 300g of protective agent substance and 100g of acid aluminum sol into 1000g of deionized water, uniformly stirring, then placing into a grinder for grinding (the rotating speed is 500r/min, the grinding time is 1 h) until the D90 is 1.8-2.8 mu m, and adding 25g of 5.0wt% hydroxypropyl methyl cellulose aqueous solution into the solution after the grinding is finished to obtain the slurry for coating. The slurry is coated into the pore canal of the carrier by using a coating machine, the coating amount is 90g/L, the coating length occupies 1/4 of the length of the carrier from the front end to the carrier, the carrier is dried for 0.5 hour under 80 ℃ hot air, and then calcined for 3 hours under the 450 ℃ condition of a muffle furnace, so as to obtain a protective agent part for standby.
500ml of 0.01mol/L palladium acetate solution, 100g of titanium dioxide powder and 50g of acid aluminum sol are added into 500g of deionized water, the mixture is stirred uniformly and then is ground in a grinding machine (the rotating speed is 800r/min, the grinding time is 0.5 h) until D90 is 1.3-1.8 mu m, and 20g of polyethylene glycol is added into the solution after the grinding is finished to obtain CO oxidation catalytic active component slurry for coating. The slurry was coated on the above-mentioned carrier containing the protective agent portion using a coater to occupy the remaining blank portion (3/4 of the length of the carrier) on the carrier in an amount of 90g/L, and dried at 80 c under hot air for 0.5 hours, and then calcined at 450 c in a muffle furnace for 4 hours, to obtain a catalyst a formed by coating two different functional coatings on a honeycomb carrier. The schematic structure of the catalyst A is shown in FIG. 1.
The catalyst C with the single CO oxidation catalytic activity coating is obtained by only coating the CO oxidation catalytic activity component on the carrier (the preparation method is the same as the above), wherein the length of the coating occupies 3/4 of the carrier, and drying and calcining.
Example 2
150g of calcium hydroxide powder, 30g of hydroxypropyl methylcellulose, 30g of bentonite and 200g of deionized water are sequentially added into an electric mixer, and stirred (stirring speed is 30r/min, stirring time is 0.5 h) until the mixture is in a dough shape. The stirred material was placed in a vacuum extruder and a 30-cell honeycomb extrudate having a length of 40mm and a width and height of 60mm was extruded under a pressure of 20 MPa. The extrudate was dried at 80 ℃ hot air for 0.5 hours and then calcined at 400 ℃ in a muffle furnace for 2 hours to obtain a protective agent block.
Honeycomb titania with a pore number of 30 and a size of 60 x 80mm was selected as the carrier. The CO oxidation catalytic portion was prepared in the same formulation and method as in example 1, with the coating length occupying the monolith support, resulting in a monolith having CO oxidation catalytic function.
And putting the two parts of blocks together to obtain the catalyst B, wherein the structural schematic diagram of the catalyst B is shown in figure 2.
Example 3
The catalysts A, B and C prepared in examples 1 and 2 were evaluated for their performance in a fixed bed. After the fixed bed is introduced into the ultralow emission of the sintering plant, detecting O in the flue gas 2 Concentration 14% (volume percentage), CO concentration 4000-8000 ppm, H 2 O content 14% (volume percent), SO 2 Concentration of 5-12 ppm, CO 2 The concentration was 8% (volume percent), the flow rate of the flue gas was 1.5L/min, and the reaction temperature was 280 ℃. The length of the catalyst is 60 x 120mm, and the protecting agent part is used as the upper end of the catalyst and is contacted with the flue gas first.
The catalyst was tested in a fixed bed for 168 hours, the powder of the protective agent layer, CO oxidation catalyst layer was scraped off with a spatula, the S element in the powder was measured by inductively coupled plasma emission spectroscopy (ICP-OES), and the C element in the powder was measured by scanning electron microscopy and X-ray energy dispersive spectroscopy (SEM-EDS).
From the test results of fig. 3, the three catalysts can maintain the CO conversion of 98% or more at 24 hours from the start of the reaction. After 72 hours of reaction, the CO conversion of catalyst C without the protective agent was reduced to 82%, and the CO conversion of catalyst A, B with the protective agent was maintained at 95% or more. After 168 hours of reaction, the CO conversion of catalyst C without the protective agent was reduced to 52%, and the CO conversion of catalyst A, B with the protective agent was about 92%. Therefore, under the actual flue gas test condition, the service life of the catalyst can be obviously prolonged by adding the protective agent, and the catalyst can still maintain high CO conversion efficiency after 168 hours of reaction.
From the test results of FIG. 4, the content of S element deposited on the CO oxidation catalytic coating of the catalyst A, B is significantly lower than that of the catalyst C, indicating SO 2 Catalysis at A, BThe amount of deposition on the coating is small and the negative impact on the catalyst is small. From the test results of FIG. 5, the surface of the protective agent layer of catalyst A, B was deposited with higher amounts of S and C elements (degassing treatment was performed during the experiment to exclude CO) 2 The interference of (2) shows that the protective agent plays a good role in adsorbing SO in the flue gas 2 And tar and carbon particles. In addition, a certain amount of Pb is detected on the surface of the protective agent, which shows that the protective agent has good adsorption capacity on some heavy metal poisons in the flue gas, and the chemical poisoning of the downstream catalytic coating is effectively slowed down.
Claims (10)
1. A monolithic CO oxidation catalyst with a protectant, wherein the catalyst consists of a protectant portion and a CO oxidation catalytically active portion; the protective agent part and the catalytic active part are coatings at different parts of the surface of the same honeycomb carrier, or are two independent reaction blocks.
2. A method of preparing the catalyst of claim 1, comprising the steps of:
(1) When the catalyst consists of front and rear sections of coatings with different functions on the same honeycomb carrier, uniformly mixing a protective agent substance with a binder, grinding, adding an additive into the ground material to obtain a slurry for coating, coating the slurry on a part of the area of the honeycomb carrier, and drying and calcining to obtain a protective agent part;
after the preparation of the protective agent part is completed, uniformly mixing a precursor of the CO oxidation catalytic active component with a binder, grinding, adding an additive after the grinding is completed to obtain a slurry for coating, coating the slurry on the rest area of the honeycomb carrier, and drying and calcining to obtain the CO oxidation catalytic active part;
(2) When the catalyst is formed by combining two reaction blocks with a protective agent and a catalytic function respectively, uniformly mixing and stirring a protective agent substance, a binder and an additive, extruding the mixture into a honeycomb shape through an extruder, and drying and calcining the extrudate to obtain a honeycomb protective agent block;
mixing the precursor of the CO oxidation catalytic active component with the binder uniformly, grinding, adding the additive after finishing grinding to obtain slurry for coating, coating the slurry on the surface of a honeycomb carrier, drying and calcining to obtain a CO oxidation catalyst block, and combining the protective agent block and the catalyst block to obtain the integral CO oxidation catalyst with the protective agent.
3. The method according to claim 2, wherein the honeycomb carrier is honeycomb cordierite or honeycomb titania, and the number of holes of the honeycomb carrier or the honeycomb titania is 20 to 70.
4. The preparation method according to claim 2, wherein the protective agent substance is one or more of calcium hydroxide, sodium hydroxide, calcium oxide, manganese dioxide, cerium oxide, zinc oxide, magnesium oxide, and copper oxide;
the precursor of the CO oxidation catalytic active component is one or more of chloride, nitrate, sulfate and acetate of platinum, palladium, gold, copper, cerium, tin or iron, and is combined with one or two of titanium dioxide powder and active alumina powder.
5. The method according to claim 2, 3 or 4, wherein the binder in the mode (1) is a silica sol or an alumina sol;
the additive in the mode (1) is one or more of hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, isopropanol, nitric acid, acetic acid and polyethylene glycol;
the binder in the mode (2) is silica sol or aluminum sol;
the additive for extrusion molding in the mode (2) is one or more of bentonite, starch, hydroxyethyl cellulose and hydroxypropyl methyl cellulose;
the additive for vacuum coating in the mode (2) is one or more of hydroxyethyl cellulose, hydroxymethyl cellulose, isopropanol, nitric acid, acetic acid and polyethylene glycol.
6. The preparation method according to claim 2, 3 or 4, wherein in the preparation process of the protective agent part in the mode (1), the mass ratio of the protective agent substance to the binder to the additive is (10-20): 1-5: 0-2, wherein in the CO oxidation catalytic active layer coating process of the mode (1), the mass ratio of the precursor of the CO oxidation catalytic active component to the binder to the additive is 0.1-10: 1-5: 0-3;
in the mode (2), in the extruded protective agent block, the mass ratio of the protective agent substance to the binder to the additive is 10-50: 0-25: 2-10, wherein in the CO oxidation catalyst block, the mass ratio of the precursor of the CO oxidation catalytic active component to the binder to the additive is 0.1-10: 1-5: 0-3.
7. The production method according to claim 2, 3 or 4, wherein the protective agent part in the mode (1) is dried at 80 to 110 ℃ for 0.1 to 0.5 hour, calcined at 300 to 450 ℃ for 0.5 to 4 hours, and the CO oxidation catalyst active layer is dried at 80 to 110 ℃ for 0.1 to 0.5 hour, calcined at 300 to 500 ℃ for 1 to 5 hours;
the drying temperature of the extruded protective agent block in the mode (2) is 80-110 ℃, the drying time is 0.5-5 hours, the calcining temperature is 300-450 ℃, the calcining time is 0.5-2 hours, the drying temperature of the CO oxidation catalyst block is 80-110 ℃, the drying time is 0.1-0.5 hours, the calcining temperature is 300-500 ℃, and the calcining time is 1-5 hours.
8. The method according to claim 2, 3 or 4, wherein the grinding speed is 500 to 800r/min and the time is 1 to 3 hours in the preparation process of the protectant part of the mode (1);
in the preparation process of the CO oxidation catalytic active part, the grinding rotating speed is 800-1200 r/min, and the time is 0.5-2 h.
9. The production method according to claim 2, 3 or 4, wherein in the mode (1), the coating amount of the protective agent layer is 20 to 120g/L, the coating length occupies 1/4 to 1/2 of the carrier, the coating amount of the co oxidation catalyst active layer is 60 to 120g/L, and the coating length occupies 1/2 to 3/4 of the carrier;
in the mode (2), the coating amount of the CO oxidation catalytic active component is 60-120 g/L.
10. Use of the catalyst of claim 1 or the catalyst prepared according to the preparation method of any one of claims 2-9 for purifying carbon monoxide in sintering flue gas.
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