CN110975905A - Wear-resistant catalyst and preparation method thereof - Google Patents
Wear-resistant catalyst and preparation method thereof Download PDFInfo
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- CN110975905A CN110975905A CN201911153259.9A CN201911153259A CN110975905A CN 110975905 A CN110975905 A CN 110975905A CN 201911153259 A CN201911153259 A CN 201911153259A CN 110975905 A CN110975905 A CN 110975905A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004005 microsphere Substances 0.000 claims abstract description 63
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 60
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000001694 spray drying Methods 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000009718 spray deposition Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 12
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 12
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 12
- 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 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 2
- XGBLLQBZRQMYNV-UHFFFAOYSA-N 1-butyl-3-methyl-2H-imidazole nitric acid Chemical compound [N+](=O)(O)[O-].C(CCC)N1CN(C=C1)C XGBLLQBZRQMYNV-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- -1 organic acid salt Chemical class 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000013370 mesoporous silicon carbide Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 3
- PNEBHVWHKXQXDR-UHFFFAOYSA-N [O].[Mn].[Cu] Chemical compound [O].[Mn].[Cu] PNEBHVWHKXQXDR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003486 chemical etching Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 101
- 239000003546 flue gas Substances 0.000 description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 238000005485 electric heating Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 238000004846 x-ray emission Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000005751 Copper oxide Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 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 2
- 229910002089 NOx Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910000896 Manganin Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a wear-resistant catalyst and a preparation method thereof, wherein the catalyst takes mesoporous silicon carbide microspheres as a carrier and manganese-copper oxide as an active component, the preparation method comprises the steps of firstly, fully mixing pseudo-boehmite and nano silicon carbide powder, then, carrying out spray drying molding to prepare a mixed microsphere carrier, then, carrying out chemical etching treatment on the microspheres by using a treating agent under a hydrothermal condition to obtain mesoporous SiC microspheres, and finally, sequentially adding copper salt and manganese salt, and uniformly mixing to prepare the catalyst. The catalyst carrier is mesoporous silicon carbide microspheres, and the mesoporous structure with uniform pore diameter is beneficial to the reactants to reach active sites, so that the activity and the stability of the catalyst are improved.
Description
Technical Field
The invention belongs to the technical field of catalytic denitration, and particularly relates to an abrasion-resistant catalyst and a preparation method thereof.
Background
Utility power plants and other stationary fuel burning facilities, such as industrial boilers, garbage incinerators, and manufacturing plants, are important sources of combustion process air pollutants. Of particular concern are nitrogen oxides in the pollutants formed by these stationary combustion sources. Nitrogen oxides, also known as NOxA gas mainly comprising Nitric Oxide (NO) and nitrogen dioxide (N0)2Is NOxNormal components of (ii). These compounds play an important role in atmospheric reactions that cause harmful particulates, ground ozone (smog), acidified nitrate deposits (acid rain), ozone depletion, and greenhouse effect. Thus, NO from a stationary combustion sourcexIncreasingly stringent regulatory requirements have been experienced over the last three decades and emission standards are likely to tighten in the future.
The flue gas denitration technology has various technologies, the main technologies are Selective Non-Catalytic Reduction (SNCR) technology and Selective Catalytic Reduction (SCR) technology, and the SNCR method utilizes reducing agent ammonia or urea and NO in the absence of catalystxReaction to form N2And H2O, the reaction temperature is between 900 and 10000 ℃, and the denitration rate is 30-50%. For coal-fired power units, V is mainly adopted for mature technology and wide industrial application205-W03/Ti02The method is an SCR denitration technology of the catalyst, has high denitration efficiency, and can meet the most strict emission regulation and standard requirements at present. In view of economic and technical efficiencies, ammonia Selective Catalytic Reduction (SCR) is considered to remove NOxThe most useful commercial method of (1).
At present, the traditional vanadium tungsten titanium catalyst has higher denitration rate at 300-. For flue gas under low-temperature working conditions (<300 ℃), the denitration effect of the catalyst is limited. In addition, after long-range operation, catalyst particles are easy to agglomerate, the surface is easy to pollute, the catalytic activity is reduced, and the stability is poor.
For example, patent 201811080629.6 describes a low temperature SCR catalyst comprising a base catalyst and a second active component, the base catalyst being a vanadium tungsten titanium catalyst and the second active component being MnOxThe particle size of the vanadium-tungsten-titanium catalyst is 20-40 meshes, and the second active component is uniformly distributed on the surface of the vanadium-tungsten-titanium catalyst, so that the vanadium-tungsten-titanium catalyst has excellent denitration performance at the temperature of 100-300 ℃. Although this patent produces more active sites by greatly reducing the catalyst particle size and increasing the specific surface area, it is susceptible to SO in flue gas2Dust, a rapid decrease in activity, and a greater impact on catalyst life.
Patent 201710145515.4 discloses a cocatalyst for reducing the emission of FCC regeneration flue gas pollutants and its application. The catalyst promoter comprises a particle A and a microsphere particle B, wherein the microsphere A uses silicon-aluminum oxide as a carrier, the active component selects one or two oxides of families VIB and IB and the auxiliary agent selects an oxide of a rare earth element; the microsphere B consists of alumina, one or more oxides of metals in IIA group, IVB group and VIII group, and oxides of rare earth elements. The catalyst prepared by the patent is used as a cocatalyst to be mixed with an industrial balancing agent, so that the emission of nitrogen oxides in FCC regenerated flue gas is reduced. But the catalyst has small application range, lower catalyst strength and quicker pulverization in industrial use.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a wear-resistant catalyst and a preparation method thereof, so that the wear-resistant catalyst has excellent wear resistance, water resistance and sulfur resistance.
In order to solve the problems, the invention adopts the technical scheme that: a method of making an attrition resistant catalyst comprising the steps of:
A. preparing mesoporous SiC microspheres: firstly, dispersing SiC powder into an organic solvent to form a solution a, dissolving pseudo-boehmite into deionized water to obtain a solution b, and then adding the solution b into the solution bStirring for 20-60min to obtain uniform suspension, drying, shaping, and cooling to room temperature to obtain Al2O3@ SiC microspheres, washing, and then mixing the prepared Al2O3Adding @ SiC and a treating agent into deionized water for ultrasonic and magnetic stirring for 2-3h, then heating to 180 ℃ and 220 ℃, keeping for 1-3h, cooling to room temperature to obtain mesoporous SiC microspheres, centrifuging, washing and drying;
B. preparing catalyst slurry: adding deionized water into a stirring kettle, then sequentially adding metal salt, stirring to completely dissolve the metal salt, then sequentially adding mesoporous SiC microspheres and a binder, and uniformly stirring to prepare slurry;
C. and (3) forming of the catalyst: and D, drying and molding the slurry obtained in the step B, and then roasting at 550-650 ℃ for 7-9h to obtain the target catalyst.
In the invention, the silicon carbide powder is preferably nano silicon carbide.
In a preferred embodiment of the present invention, the preparation method of the mesoporous SiC microsphere in step a comprises: firstly dispersing nano SiC powder into ethylene glycol solution to form solution a, dissolving pseudo-boehmite into deionized water to obtain solution b, then adding the solution b into the solution a, continuously stirring for 30min to form uniform suspension, then performing spray drying forming in a spray drying forming device, and naturally cooling to room temperature to obtain Al2O3@ SiC microspheres washed three times with deionized water and ethanol, respectively, and then Al is added2O3Adding @ SiC and a fluorine-containing reagent into deionized water, performing ultrasonic and magnetic stirring for 2h, transferring the suspension to a hydrothermal kettle, heating to 200 ℃, keeping for 2h, cooling to room temperature to obtain mesoporous SiC microspheres, and performing centrifugation, washing and drying.
In the step A, the mass ratio of the silicon carbide to the alumina in the pseudo-boehmite is 60-98:2-40, preferably 70-80: 20-30;
in the step A, a spray drying forming device is adopted for drying and forming, the temperature in the furnace of the spray drying forming device is 300-350 ℃, the temperature at the outlet of the spray drying forming device is 200-250 ℃, and the pressure is 3-4 Mpa;
in the step C, a spray drying forming device is adopted for drying and forming, the temperature in the furnace of the spray drying forming device is 300-350 ℃, the temperature at the outlet of the spray drying forming device is 200-250 ℃, and the pressure is 3-4 MPa;
the organic solvent in the step A comprises one or more of glycol, acetone, butanol and ethyl acetate, preferably glycol;
the treating agent in the step A comprises a fluorine-containing agent and an auxiliary agent, wherein the fluorine-containing agent comprises HF or NH4One or two of F, preferably NH4F; the auxiliary agent is [ Bmin]Ionic salt solutions of the type, preferably one or more of 1-butyl-3-methylimidazole hydrogensulfate, 1-butyl-3-methylimidazole hydrochloride, or 1-butyl-3-methylimidazole nitrate, more preferably 1-butyl-3-methylimidazole hydrogensulfate;
the [ Bmin ] ionic salt solution can enhance the permeability of fluoride to the microsphere carrier, so that the fluoride ionic salt solution can more effectively remove alumina in the microsphere and is beneficial to forming a regular mesoporous structure. In the roasting process of the catalyst, the dispersion degree of active components Mn and Cu can be enhanced by the ionic liquid in the pore channel, and the activity of the catalyst is improved.
The mass ratio of the fluorine-containing reagent to the auxiliary agent in the treating agent in the step A is 60-90: 10-40, preferably 2-4: 1;
the molar ratio of the alumina contained in the pseudo-boehmite added in the step A and the fluorine-containing reagent in the treating agent is 1:6-12, and preferably 1: 8-10.
The metal salt added in the step B comprises copper salt and manganese salt, wherein the copper salt is one or more of copper chloride, nitrate, sulfate or organic acid salt, and is preferably copper nitrate; the manganese salt is one or more of chloride, nitrate and sulfate of manganese, preferably manganese nitrate;
the binder in step B of the invention is one or two of polyvinyl alcohol and hydroxypropyl methyl cellulose, preferably hydroxypropyl methyl cellulose.
The amount of the binder to be added may be selected according to the common general knowledge of those skilled in the art, and is not particularly limited in the present application, and may be, for example, 1 to 5% by mass based on the total mass of the raw materials
Preferably, in the copper salt and the manganese salt, the mass ratio of the copper element to the manganese element is 0.8-8:0.6-19
The average grain diameter of the mesoporous silicon carbide microsphere carrier prepared in the step A is 10-50 mu m, and the specific surface area is 50-500m2Per g, the pore diameter is 4-50 nm;
the invention also provides the catalyst prepared by the preparation method, which comprises 60-98% of SiC, 1-10% of CuO and 1-30% of MnO by taking the total mass of the catalyst as a reference2。
The bulk density of the catalyst is 1.0-1.2 g/mL;
the sieving composition of the catalyst is 0-20 μm <0.1 wt%, and the average particle size is 40-120 μm;
the catalyst had an attrition rate of < 1.0%.
The catalyst carrier is mesoporous silicon carbide microspheres, and the mesoporous structure with uniform pore diameter is beneficial to the reactants to reach active sites, so that the activity and the stability of the catalyst are improved. However, the surface of the inorganic silicon carrier has no active group, so that the manganese copper oxide is required to be introduced as an active component. The mesoporous SiC microspheres are used for optimizing the loading amounts and loading modes of active components Cu and Mn, and the problems of high pulverization speed and poor water and sulfur resistance of the traditional microsphere catalyst when the air speed of the smoke containing the nitrate is greatly changed are solved.
In the catalyst, the carrier takes mesoporous silicon carbide microspheres as the carrier, and manganin oxide as an active component.
In this application the pressures are gauge pressures.
The invention has the following beneficial effects:
1. the invention uses fluorine-containing agent (containing auxiliary agent) to Al2O3Etching the @ SiC microsphere carrier to remove the alumina in the microsphere carrier. [ Bmin]The ionic salt solution can enhance the permeability of fluoride to the microsphere carrier, so that the alumina in the microsphere can be more effectively removed, and the formation of a regular mesoporous structure is facilitated. In the roasting process of the catalyst, the dispersion degree of active components Mn and Cu can be enhanced by the ionic liquid in the pore channel, and the activity of the catalyst is improved.
2. The method for preparing the carrier improves the specific surface area in the carrier, increases the loading capacity of the active components of the catalyst in unit mass, and is beneficial to the reactants to reach the active sites, thereby improving the activity and stability of the catalyst.
3. The microspherical catalyst of the invention takes SiC as a carrier, enhances the wear resistance, sulfur resistance and water resistance of the catalyst, and CuO and MnO2As active component, wherein MnO2The catalyst has strong reducibility, and the CuO enhances the dispersion degree of Mn, so that the temperature window of the catalyst can be widened. Attrition rate of the catalyst of the invention<1 percent, can keep higher reaction activity in flue gas containing water and sulfur.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The invention adopts a quartz tube fixed fluidized bed reactor (reactor for short) as a reaction device, and is provided with an electric wire heating device and a flue gas generating device. The composition of the flue gas is 600ppm NO and 600ppm NH3、3％O2、N2For the balance gas, the gas volume space velocity (the amount of gas treated per unit volume of catalyst per unit time) was 6000h-1The reaction temperature interval of the fluidized bed reactor is 180-340 ℃, a testo350-XL type flue gas analyzer is adopted to measure the concentration of NO of the gas at the inlet and the outlet of the fixed reactor on line, and a gas mass flow meter is adopted to control the flow of the flue gas.
The method for testing the wear rate of the catalyst is to use a catalyst wear index tester (meeting the ASTM D5577-2000 standard) to determine, set the air speed of a nozzle at 240m/s, use compressed air as an air source and 100% relative humidity, sieve the catalyst with the particle size of 20-200 μm and continuously test for 24h, and obtain the wear rate as the mass loss rate.
Copper nitrate (purity >99.99 wt%) used in the preparation process of the microsphere SCR catalyst of the invention, Shanghai Allantin Biotechnology Co., Ltd; manganese nitrate solution (AR, content 50 wt%), chemical judgments, inc; ammonium fluoride (AR, 98% content), Shanghai Allantin Biotech Co., Ltd; 1-butyl-3-methylimidazolium hydrogen sulfate (AR, content 95%), Tianjin Kemi Euro Chemicals Co., Ltd; pseudoboehmite (purity >98.5 wt%), Shandong aluminum industries, Inc.; silicon carbide (purity >99.5 wt%), shanghai alatin biochemistry science and technology, ltd; hydroxypropyl methylcellulose (AR), available from Shigaku chemical Co., Ltd.
Example 1
(1) Firstly, 75.38g of nano SiC powder is dispersed into 500mL of glycol solution to form a solution a, and 29.86g of pseudo-boehmite is dissolved into 100mL of deionized water to obtain a solution b. And then adding the solution b into the solution a, continuously stirring for 30min to form uniform suspension, and spray-drying and forming in a spray-drying forming device at the temperature of 350 ℃ in a spray-drying furnace, the outlet temperature of 250 ℃ and the outlet pressure of 4 MPa. Naturally cooling to room temperature to obtain Al2O3@ SiC microspheres were washed three times with deionized water and ethanol, respectively. Then the prepared Al is added2O3@ SiC microsphere, 99.47g ammonium fluoride, 33.16g [ Bmim ]][HSO4]Mixing, adding into deionized water, performing ultrasonic treatment, magnetically stirring for 2h, transferring the suspension into a hydrothermal kettle, heating to 200 deg.C, and maintaining for 2 h. When the reaction kettle is naturally cooled to room temperature, mesoporous SiC microspheres are obtained, and centrifugation, washing and drying are carried out;
(2) 82.30g of Mn (NO)3)2Solution and 15.19g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. And (3) sequentially adding the microsphere carrier prepared in the step (1) and 6g of hydroxypropyl methyl cellulose, and continuously stirring for 8 hours to obtain slurry.
(3) Spray-drying and forming the slurry obtained in the step (2) in a spray-drying and forming device, setting the temperature in the furnace to be 300 ℃, the outlet temperature to be 220 ℃ and the pressure to be 4MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst A.
The average grain diameter of the mesoporous SiC carrier is 45 mu m, and the pore diameter is 48 nm; the bulk density of microspherical SCR catalyst A was 1.145g/mL and the attrition index was 0.816%. X-ray fluorescence Spectroscopy (XRF) analysis the composition of microspheroidal catalyst A contained 75 wt% silicon carbide, 20 wt% manganese oxide, 5 wt% copper oxide.
(4) Adding microsphere SCR catalysts A and N into a fluidized bed reactor of a reaction device2The catalyst is fluidized by passing through the catalyst bed layer from bottom to top of the reactor, and the catalyst is heated to 450 ℃ by starting the electric heating device. Then stopping introducing N2The simulated flue gas (from 600ppm of NH) is introduced from the bottom to the top of the reactor3600ppm NO, 50ppm SO250ppm of H2O, 3 vt% of O2And N2Mixed gas of the components) and controlling the volume space velocity of the flue gas to be 6000h-1. The volume airspeed is the ratio of the simulated flue gas volume flow to the volume of the microsphere SCR catalyst A in the reactor, and the flue gas removal is carried out under normal pressure. The experimental time lasts for 2h, the NO discharge amount is measured every 30min, the average value is 60ppm, and the NO removal rate of the microsphere SCR catalyst A under the experimental conditions is 90.0%.
Examples 1 to 2
NO removal experiments: the catalyst A is heated to350 ℃ by an electric heating device, the experiment time lasts for 2h, the discharge amount of NO is measured every 30min, the average value is 93ppm, and the NO removal rate of the microsphere SCR catalyst A at the reaction temperature of 180 ℃ is 84.5%.
Examples 1 to3
NO removal experiments: the catalyst A is heated to 400 ℃ by an electric heating device, the experiment time lasts for 2h, the discharge amount of NO is measured every 30min, the average value is 76ppm, and the NO removal rate of the microsphere SCR catalyst A at the reaction temperature of 180 ℃ is 87.3%.
Examples 1 to 4
NO removal experiments: the electric heating device heats the catalyst A to 550 ℃, the experiment time lasts for 2h, the discharge amount of NO is measured every 30min, the average value is 63ppm, and the NO removal rate of the microsphere SCR catalyst A at the reaction temperature of 220 ℃ is 89.5%.
Example 2
(1) Firstly, 60.30g of nano SiC powder is dispersed into 500mL of glycol solution to form a solution a, and 47.77g of pseudo-boehmite is dissolved into 100mL of deionized water to obtain a solution b. Subsequently, the process of the present invention,adding the solution b into the solution a, continuously stirring for 30min to form uniform suspension, and spray-drying and forming in a spray-drying forming device at the temperature of 320 ℃, the outlet temperature of 220 ℃ and the outlet pressure of 3.5Mpa in a spray-drying furnace. Naturally cooling to room temperature to obtain Al2O3@ SiC microspheres were washed three times with deionized water and ethanol, respectively. Then the prepared Al is added2O3@ SiC microsphere, 178g ammonium fluoride, 122.2g [ Bmim ]][HSO4]The solution is mixed and added into deionized water for ultrasonic and magnetic stirring for 2 hours, and then the suspension is transferred to a hydrothermal kettle and heated to 200 ℃ for 2 hours. When the reaction kettle is naturally cooled to room temperature, mesoporous SiC microspheres are obtained, and centrifugation, washing and drying are carried out;
(2) 123.45g of Mn (NO)3)2Solution and 30.38g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. And (3) sequentially adding the microsphere carrier prepared in the step (1) and 6g of hydroxypropyl methyl cellulose, and continuously stirring for 8 hours to obtain slurry.
(3) Spray-drying and forming the slurry obtained in the step (2) in a spray-drying and forming device, setting the temperature in the furnace to be 300 ℃, the outlet temperature to be 220 ℃ and the pressure to be 4MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst B.
The average grain diameter of the mesoporous SiC carrier is 38 mu m, and the pore diameter is 32 nm; the bulk density of microspherical SCR catalyst B was 1.135g/mL and the attrition index was 0.747%. XRF analysis the composition of microspherical catalyst B contained 60 wt% silicon carbide, 30 wt% manganese oxide, 10 wt% copper oxide.
(4) Adding microspherical SCR catalysts A and N with the same mass as that of the microspherical SCR catalyst A and N in example 1 into a fluidized bed reactor of a reaction device2The catalyst is fluidized by passing through the catalyst bed layer from bottom to top of the reactor, and the catalyst is heated to 450 ℃ by starting the electric heating device. Then stopping introducing N2The simulated flue gas is introduced from the bottom of the reactor from bottom to top, and the volume airspeed of the flue gas is controlled to be 6000h-1. Using the same test conditions as in example 1, the average value of the outlet NO was determined to be 98ppmThe removal rate of the microsphere SCR catalyst B to NO under the experimental conditions is 83.7%.
Example 3
(1) Firstly, 98.49g of nano SiC powder is dispersed into 500mL of glycol solution to form a solution a, and 2.39g of pseudo-boehmite is dissolved into 100mL of deionized water to obtain a solution b. And then adding the solution b into the solution a, continuously stirring for 30min to form uniform suspension, and spray-drying and forming in a spray-drying forming device at the temperature of 350 ℃ in a spray-drying furnace, the outlet temperature of 250 ℃ and the outlet pressure of 4 MPa. Naturally cooling to room temperature to obtain Al2O3@ SiC microspheres were washed three times with deionized water and ethanol, respectively. Then the prepared Al is added2O3@ SiC microsphere and 4.44g ammonium fluoride, 0.51g [ Bmim ]][HSO4]The solution is mixed and added into deionized water for ultrasonic and magnetic stirring for 2 hours, and then the suspension is transferred to a hydrothermal kettle and heated to 200 ℃ for 2 hours. When the reaction kettle is naturally cooled to room temperature, mesoporous SiC microspheres are obtained, and centrifugation, washing and drying are carried out;
(2) 4.11g of Mn (NO)3)2Solution and 3.04g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. And (3) sequentially adding the microsphere carrier prepared in the step (1) and 6g of hydroxypropyl methyl cellulose, and continuously stirring for 8 hours to obtain slurry.
(3) Spray-drying and forming the slurry obtained in the step (2) in a spray-drying and forming device, setting the temperature in the furnace to be 300 ℃, the outlet temperature to be 220 ℃ and the pressure to be 4MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst C.
The average grain diameter of the mesoporous SiC carrier is 39 mu m, and the pore diameter is 29 nm; the bulk density of microspherical SCR catalyst C was 1.086g/mL and the attrition index was 0.625%. XRF analysis the composition of microspherical catalyst C contained 98 wt% silicon carbide, 1 wt% manganese oxide, 1 wt% copper oxide.
(4) Adding microspherical SCR catalysts A and N with the same mass as that of the microspherical SCR catalyst A and N in example 1 into a fluidized bed reactor of a reaction device2From the bottom of the reactor to the topAnd (3) fluidizing the catalyst in the catalyst bed layer, and starting an electric heating device to heat the catalyst to 450 ℃. Then stopping introducing N2The simulated flue gas is introduced from the bottom of the reactor from bottom to top, and the volume airspeed of the flue gas is controlled to be 6000h-1. Using the same test conditions as in example 1, the average value of the outlet NO was determined to be 566ppm, and the removal rate of NO by microspherical SCR catalyst C under the above experimental conditions was 5.7%.
Example 4
(1) Firstly, 69.35g of nano SiC powder is dispersed into 500mL of glycol solution to form a solution a, and 37.03g of pseudo-boehmite is dissolved into 100mL of deionized water to obtain a solution b. And then adding the solution b into the solution a, continuously stirring for 30min to form uniform suspension, and spray-drying and forming in a spray-drying forming device at the temperature of 300 ℃ in a spray-drying furnace, the outlet temperature of 200 ℃ and the outlet pressure of 3 Mpa. Naturally cooling to room temperature to obtain Al2O3@ SiC microspheres were washed three times with deionized water and ethanol, respectively. Then the prepared Al is added2O3@ SiC microsphere, 136.6g ammonium fluoride, 82.23g [ Bmim ]][HSO4]The solution is mixed and added into deionized water for ultrasonic and magnetic stirring for 2 hours, and then the suspension is transferred to a hydrothermal kettle and heated to 200 ℃ for 2 hours. When the reaction kettle is naturally cooled to room temperature, mesoporous SiC microspheres are obtained, and centrifugation, washing and drying are carried out;
(2) 123.45g of Mn (NO)3)2Solution and 3.04g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. And (3) sequentially adding the microsphere carrier prepared in the step (1) and 6g of hydroxypropyl methyl cellulose, and continuously stirring for 8 hours to obtain slurry.
(3) Spray-drying and forming the slurry obtained in the step (2) in a spray-drying and forming device, setting the temperature in the furnace to be 300 ℃, the outlet temperature to be 220 ℃ and the pressure to be 4MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst D.
The average grain diameter of the mesoporous SiC carrier is 42 mu m, and the pore diameter is 43 nm; the bulk density of microspherical SCR catalyst D was 1.135g/mL and the attrition index was 0.853%. XRF analysis the composition of microspherical catalyst D contained 69 wt% silicon carbide, 30 wt% manganese oxide, 1 wt% copper oxide.
(4) Adding microspherical SCR catalysts A and N with the same mass as that of the microspherical SCR catalyst A and N in example 1 into a fluidized bed reactor of a reaction device2The catalyst is fluidized by passing through the catalyst bed layer from bottom to top of the reactor, and the catalyst is heated to 450 ℃ by starting the electric heating device. Then stopping introducing N2The simulated flue gas is introduced from the bottom of the reactor from bottom to top, and the volume airspeed of the flue gas is controlled to be 6000h-1. Using the same test conditions as in example 1, the average value of outlet NO was determined to be 123ppm and the removal rate of NO by microspherical SCR catalyst C under the above experimental conditions was 79.5%.
Example 5
(1) Firstly, 89.45g of nano SiC powder is dispersed into 500mL of glycol solution to form a solution a, and 13.14g of pseudo-boehmite is dissolved into 100mL of deionized water to obtain a solution b. And then adding the solution b into the solution a, continuously stirring for 30min to form uniform suspension, and spray-drying and forming in a spray-drying forming device at the temperature of 300 ℃ in a spray-drying furnace, the outlet temperature of 200 ℃ and the outlet pressure of 3 Mpa. Naturally cooling to room temperature to obtain Al2O3@ SiC microspheres were washed three times with deionized water and ethanol, respectively. Then the prepared Al is added2O3@ SiC microsphere and 24.5g ammonium fluoride, 7.29g [ Bmim ]][HSO4]The solution is mixed and added into deionized water for ultrasonic and magnetic stirring for 2 hours, and then the suspension is transferred to a hydrothermal kettle and heated to 200 ℃ for 2 hours. When the reaction kettle is naturally cooled to room temperature, mesoporous SiC microspheres are obtained, and centrifugation, washing and drying are carried out;
(2) 4.11g of Mn (NO)3)2Solution and 30.38g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. And (3) sequentially adding the microsphere carrier prepared in the step (1) and 6g of hydroxypropyl methyl cellulose, and continuously stirring for 8 hours to obtain slurry.
(3) Spray-drying and forming the slurry obtained in the step (2) in a spray-drying and forming device, setting the temperature in the furnace to be 300 ℃, the outlet temperature to be 220 ℃ and the pressure to be 4MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst E.
The average grain diameter of the mesoporous SiC carrier is 32 mu m, and the pore diameter is 25 nm; the bulk density of microspherical SCR catalyst E was 1.073g/mL and the attrition index was 0.738%. XRF analysis the composition of microspherical catalyst E contained 89 wt% silicon carbide, 1 wt% manganese oxide, 10 wt% copper oxide.
(4) Adding microspherical SCR catalysts A and N with the same mass as that of the microspherical SCR catalyst A and N in example 1 into a fluidized bed reactor of a reaction device2The catalyst is fluidized by passing through the catalyst bed layer from bottom to top of the reactor, and the catalyst is heated to 450 ℃ by starting the electric heating device. Then stopping introducing N2The simulated flue gas is introduced from the bottom of the reactor from bottom to top, and the volume airspeed of the flue gas is controlled to be 6000h-1. Using the same test conditions as in example 1, the mean value of the outlet NO was determined to be 347ppm and the removal rate of NO by microspherical SCR catalyst E under the above experimental conditions was 42.2%.
Comparative example 1
(1) 82.30g of Mn (NO)3)2Solution and 15.19g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. Then, 75.38g of nano silicon carbide powder and 6g of hydroxypropyl methyl cellulose are sequentially added, and stirring is continued for 8 hours to obtain slurry.
(2) Spray-drying and forming the slurry obtained in the step (1) in a spray-drying and forming device, setting the temperature in a furnace to be 300 ℃, the outlet temperature to be 220 ℃ and the pressure to be 4MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst F.
The bulk density of microspherical SCR catalyst F was 1.113g/mL and the attrition index was 0.983%. X-ray fluorescence Spectroscopy (XRF) analysis the composition of microspherical catalyst F contained 75 wt% silicon carbide, 20 wt% manganese oxide, 5 wt% copper oxide.
(3) Adding microsphere SCR catalysts F and N into a fluidized bed reactor of a reaction device2The catalyst is fluidized by passing through the catalyst bed layer from bottom to top of the reactor, and the catalyst is heated to 450 ℃ by starting the electric heating device. Then stopping introducing N2The simulated flue gas (from 600ppm of NH) is introduced from the bottom to the top of the reactor3600ppm NO, 50ppm SO250ppm of H2O, 3 vt% of O2And N2Mixed gas of the components) and controlling the volume space velocity of the flue gas to be 6000h-1. The volume airspeed is the ratio of the simulated flue gas volume flow to the volume of the microsphere SCR catalyst A in the reactor, and the flue gas removal is carried out under normal pressure. The experiment lasts for 2h, the NO discharge amount is measured every 30min, the average value is 189ppm, and the NO removal rate of the microsphere SCR catalyst A under the experiment conditions is 68.5%.
Comparative example 2
(1) 123.45g of Mn (NO)3)2Solution and 30.38g of Cu (NO)3)2·3H2Adding O into 1000g of deionized water at 65 ℃, stirring at the speed of 300r/min for 6 hours to completely dissolve the O, and continuing stirring. Then 60.30g of nano silicon carbide powder and 6g of hydroxypropyl methyl cellulose are added in sequence, and stirring is continued for 8 hours to obtain slurry.
(2) Spray-drying and forming the slurry obtained in the step (1) in a spray-drying and forming device, setting the temperature in a furnace to be 300 ℃, the outlet temperature to be 200 ℃ and the pressure to be 3MPa to obtain particles; the particles are dried for 3h at 150 ℃ and calcined for 8h at 600 ℃ to obtain the target catalyst G.
The bulk density of microspherical SCR catalyst G was 1.099G/mL and the attrition index was 1.026%. X-ray fluorescence Spectroscopy (XRF) analysis the composition of microspherical catalyst G contained 60 wt% silicon carbide, 30 wt% manganese oxide, 10 wt% copper oxide.
(3) Adding microsphere SCR catalysts G and N into a fluidized bed reactor of a reaction device2The catalyst is fluidized by passing through the catalyst bed layer from bottom to top of the reactor, and the catalyst is heated to 450 ℃ by starting the electric heating device. Then stopping introducing N2The simulated flue gas (from 600ppm of NH) is introduced from the bottom to the top of the reactor3600ppm NO, 50ppm SO2、50ppH of m2O, 3 vt% of O2And N2Mixed gas of the components) and controlling the volume space velocity of the flue gas to be 6000h-1. The volume airspeed is the ratio of the simulated flue gas volume flow to the volume of the microsphere SCR catalyst A in the reactor, and the flue gas removal is carried out under normal pressure. The experiment lasts for 2h, the NO discharge amount is measured every 30min, the average value is 253ppm, and the NO removal rate of the microspherical SCR catalyst A under the experiment conditions is 57.8%.
Claims (10)
1. A method of making an attrition resistant catalyst comprising the steps of:
A. preparing mesoporous SiC microspheres: firstly, dispersing SiC powder into an organic solvent to form a solution a, dissolving pseudo-boehmite into deionized water to obtain a solution b, then adding the solution b into the solution a, continuously stirring for 20-60min to form a uniform suspension, drying and forming, and cooling to room temperature to obtain Al2O3@ SiC microspheres, washed, then Al2O3Adding @ SiC and a treating agent into deionized water for ultrasonic and magnetic stirring for 2-3h, then heating to 180 ℃ and 220 ℃, keeping for 1-3h, cooling to room temperature to obtain mesoporous SiC microspheres, centrifuging, washing and drying;
B. preparing catalyst slurry: adding deionized water into a stirring kettle, then sequentially adding metal salt, stirring to completely dissolve the metal salt, then sequentially adding mesoporous SiC microspheres and a binder, and uniformly stirring to prepare slurry;
C. and (3) forming of the catalyst: and D, drying and molding the slurry obtained in the step B, and then roasting at 550-650 ℃ for 7-9h to obtain the target catalyst.
2. The method according to claim 1, wherein in step A, the mass ratio of alumina to silicon carbide contained in the silicon carbide and pseudo-boehmite is 60-98:2-40, preferably 70-80: 20-30.
3. The method as claimed in claim 1 or 2, wherein the step A is performed by a spray drying and forming device, wherein the temperature inside the furnace of the spray drying and forming device is 300-350 ℃, the temperature at the outlet of the spray drying and forming device is 200-250 ℃, and the pressure of the spray drying and forming device is 3-4 Mpa;
in the step C, a spray drying forming device is adopted for drying and forming, the temperature in the furnace of the spray drying forming device is 300-350 ℃, the temperature at the outlet of the spray drying forming device is 200-250 ℃, and the pressure is 3-4 MPa.
4. The method according to claim 1 or 2, wherein the organic solvent in step a comprises one or more of ethylene glycol, acetone, butanol, ethyl acetate, preferably ethylene glycol.
5. The method according to claim 1 or 2, wherein the treating agent in the step A comprises a fluorine-containing agent containing HF or NH and a co-agent4One or two of F, preferably NH4F; the auxiliary agent is [ Bmin]Ionic salt solutions of the type, preferably one or more of 1-butyl-3-methylimidazole hydrogensulfate, 1-butyl-3-methylimidazole hydrochloride, or 1-butyl-3-methylimidazole nitrate, more preferably 1-butyl-3-methylimidazole hydrogensulfate;
preferably, the mass ratio of the fluorine-containing agent to the auxiliary agent in the treating agent in the step A is 60-90: 10-40, preferably 2-4: 1.
6. The method according to claim 1 or 2, wherein in the step a, the molar ratio of the alumina contained in the pseudoboehmite to the fluorine-containing agent contained in the treating agent is 1:6 to 12, preferably 1:8 to 10.
7. The preparation method according to claim 1 or 2, wherein the metal salt added in step B comprises copper salt and manganese salt, the copper salt is one or more of chloride, nitrate, sulfate or organic acid salt of copper, preferably copper nitrate; the manganese salt is one or more of chloride, nitrate and sulfate of manganese, and preferably manganese nitrate.
8. The method according to claim 1 or 2, wherein the binder in step B is one or two of polyvinyl alcohol and hydroxypropyl methylcellulose, preferably hydroxypropyl methylcellulose.
9. The production method according to claim 1 or 2, wherein the mass ratio of the copper element to the manganese element in the copper salt and the manganese salt is 0.8 to 8:0.6 to 19.
10. A method of preparing a catalyst according to any one of claims 1 to 9, wherein the catalyst prepared by the method comprises, based on the total mass of the catalyst, 60 to 98% of SiC, 1 to 10% of CuO, and 1 to 30% of MnO2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911153259.9A CN110975905B (en) | 2019-11-22 | 2019-11-22 | Wear-resistant catalyst and preparation method thereof |
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| CN113786852A (en) * | 2021-09-29 | 2021-12-14 | 上海电力大学 | Low-temperature SCR denitration catalyst with SiC as carrier and its preparation method and application |
| CN114289046A (en) * | 2021-12-14 | 2022-04-08 | 上海电力大学 | Denitration catalyst with Sm as active ingredient, and preparation and application thereof |
| CN116393177A (en) * | 2021-12-28 | 2023-07-07 | 万华化学集团股份有限公司 | Catalyst for catalytic ozone oxidation of NOx and its preparation method and application |
| CN116510510A (en) * | 2023-06-11 | 2023-08-01 | 连云港中星能源有限公司 | Efficient energy-saving denitration process based on electric heating assistance |
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