CN113426458B - 一种用于含卤素挥发性有机物催化燃烧的催化剂及其用途 - Google Patents
一种用于含卤素挥发性有机物催化燃烧的催化剂及其用途 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 33
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 28
- 150000002367 halogens Chemical class 0.000 title claims abstract description 28
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 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 abstract 2
- 239000007789 gas Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010815 organic waste Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940062057 nitrogen 80 % Drugs 0.000 description 3
- 229940063746 oxygen 20 % Drugs 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940073584 methylene chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2025—Chlorine
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- B01D2257/204—Inorganic halogen compounds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
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- 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
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Abstract
本发明涉及一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，所述催化剂包括整体式或颗粒状载体以及负载在载体上的高粘度涂层、助剂和活性组分涂层，所述高粘度涂层为铝溶胶涂敷于无机氧化物载体后焙烧所得，所述活性组分采用氧化还原法沉淀于高粘度涂层表面，所述活性组分包括过渡金属和贵金属，过渡金属为铁和锰，贵金属为钌。所述氧化还原法包括如下步骤：(a)前驱体水溶液调制；(b)氧化还原法沉淀涂层；(c)加入活性组分三氯化钌；(d)过氧化氢氧化还原沉淀活性组分。所述催化剂具有良好的稳定性、再生性和高耐湿性，对含卤素挥发性有机物的转化效率高，同时催化剂制备成本低廉、活性涂层与整体式或颗粒状无机氧化物载体结合牢固。
Description
技术领域
本发明属于废气处理领域，涉及一种用于含卤素挥发性有机物催化燃烧的催化剂及其用途。
背景技术
挥发性有机化合物（VOCs）作为主要的空气污染物之一，造成了许多环境问题，如地面臭氧、光化学烟雾、PM2.5、有毒气体排放和对人体健康的不良影响。VOCs在环境中具有一定的积累性且稳定性极强。其中，含卤素（Cl、Br等）挥发性有机物有更强的致癌、致畸、致突变的“三致”作用，其引发的环境问题已得到全社会的密切关注。目前我国工业源VOCs中含有大量的含卤素挥发性有机物，其排放量占比将持续上升，因此，对于含卤素挥发性有机物的排放和控制研究一直是科研工作者关注的热点。现有技术中对于含卤素挥发性有机物废气进行净化的方式有多种，低温催化燃烧作为一种节能有效的燃烧方式，越来越受到人们的重视，其操作成本低、反应温度低、催化效率高，能很好地满足环保要求，使其成为处理含卤素挥发性有机物废气的主流技术和发展方向。
VOCs催化剂分为贵金属催化剂、非贵金属催化剂，贵金属催化剂与非贵金属催化剂相比，这类催化剂具有起燃温度低、燃烧完全、副产物少等优点，但是这类催化剂价格昂贵，反应过程中易受到Cl、Br离子或HCl/HBr毒化而失活，而铁、锰作为地壳中储量较大的过渡金属元素，又具有较多可变价态，适合于多种催化反应类型，因此在铁锰组分中加入适量的贵金属制得的催化剂具有较大研发价值，这类催化剂可降低成本、催化温度，也能提高活性、抗中毒性以及增加催化剂使用寿命。
例如文献(Gang Wang, Yu Wang, Linbo Qin, Bo Zhao, Limin Guo and JunHan, Catalysis Science & Technology 2020, 10 (21), 7203-7216)采用无模板草酸盐热解法制备了铁锰双金属氧化物样品，然后采用湿法浸渍将钌负载在铁锰样品上，最后烘干焙烧得到表面负载钌/铁锰活性组分催化剂，该催化剂在Fe-Mn氧化物的介孔中能有效地负载Ru纳米粒子，改善了金属粒子与载体之间的相互作用，从而确保了材料对氯苯的催化效率和稳定性的提高，使氯苯低温高效催化转化。又例如中国专利CN109833864A公开了一种含卤素VOCs催化燃烧催化剂及其制备方法，其催化剂为四元金属复合氧化物，其结构形式为CexZryM1-x-yO2，M为Fe、Co、Cu、Mn、Ni、Zn或Mg；x为0.2~0.8，y为0.8~0.2。该催化剂通过将金属前驱体盐按照一定比例均相沉淀制得，该发明的催化剂具有高的含卤素VOCs催化燃烧活性和稳定性，但是其制备工艺复杂、催化温度高、能耗大，对卤素挥发性有机物的催化稳定性一般。
本发明提供了一种钌/铁锰催化剂制备方法，该催化剂对卤素挥发性有机物转化率高、制备简单、节能环保、负载牢固、稳定性高、耐湿性强、使用寿命长，便于广泛应用。
发明内容
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的目的是在于提出一种对卤素挥发性有机物转化率高、制备简单、节能环保、负载牢固、稳定性高、耐湿性强、使用寿命长的钌/铁锰催化剂制备方法及其应用。
本发明的解决方案如下：
步骤1：将无机氧化物载体放入稀酸溶液中，煮沸2h，然后用去离子水反复冲洗至中性，80-110℃下干燥10-12h，然后在马弗炉里500℃焙烧1-5h，得到表面活化的载体；
优选地，所述无机氧化物载体可为沸石、海泡石、多孔炭材料、球状氧化铝、球状二氧化硅、整体式蜂窝陶瓷的一种或者至少两种的复合物。
优选地，所述无机氧化物载体的比表面积为5~500m2/g。
优选地，所述无机氧化物载体的粒径为2~200微米。
步骤2：取一定量去离子水，加入铝源，胶溶剂，分散剂，并在室温20-30℃搅拌10-30min，形成铝溶胶涂层浆液；将步骤1处理后的载体置于制备好的铝溶胶涂层浆液，反复抽提5-10min，陈化1h，80~110℃下干燥10-12h，然后在马弗炉里500℃焙烧2-4h，得到高粘度涂层；
在步骤2中，铝源为提供铝元素的物质，如拟薄水铝石、偏铝酸钠、无定型氢氧化铝粉末、异丙醇铝；胶溶剂为稀硝酸或草酸的任意一种；分散剂为聚乙二醇、乙二醇、羧甲基纤维素中的任意一种。
本发明催化剂的制备方案如下：
步骤3：将一定比例含有二价铁的水溶性铁盐和含有二价锰的水溶性锰盐混合均匀形成前驱体水溶液。将上述混合溶液逐滴加入一定浓度的高锰酸钾或高锰酸钠的水溶液中混合搅拌反应，反应物之间发生氧化还原反应在高粘度涂层表面生成褐色沉淀物涂层。
步骤4：在上述溶液中继续加入一定量的钌的前驱体溶液并搅拌混合均匀。随后将一定浓度的过氧化氢溶液逐滴加入上述溶液。三氯化钌与铁锰双金属氧化物涂层发生氧化还原沉淀反应，形成钌/铁锰复合氧化物涂层。
步骤3和4涉及到的氧化还原反应的化学反应方程式如下：
步骤5：将上述整体式或颗粒状催化剂取出，进行抽滤、洗涤，去除残留溶剂并干燥。
优选地，所述铁和锰的摩尔比为0.1~0.9，以催化剂的重量为100%计，过渡金属按金属元素重量计，所述过渡金属的重量百分比为0.1~20%。
优选地，所述钌与过渡金属的摩尔比为0.01~0.2，以催化剂的重量为100%计，过渡金属按金属元素重量计，贵金属按金属元素重量计，所述贵金属钌的重量百分比为0.01~5%。
步骤6：取一定量的助剂，对上述整体式或颗粒状催化剂进行浸渍处理，浸渍一定时间后，烘干，得到所需催化剂。
优选地，所述助剂组分是碱金属、无机酸或稀土元素氧化物的任意一种或至少两种的组合。
优选地，所述碱金属为钠、钾的氧化物。
优选地，所述无机酸为硫酸或磷酸。
优选的，所述稀土元素氧化物为氧化铈或氧化镧。
所述助剂组分以催化剂的重量为100%计，其重量百分比为0.2~20%。
步骤7：将所得催化剂用于含有卤素挥发性有机物的催化燃烧的方法包括如下步骤：
1）将整体式或颗粒状催化剂组装到催化燃烧设备中。
2）混合有含卤素挥发性有机物的有机废气通过上述设备。
3）在换热器和电热管的作用下加热到200~400℃，预热后的有机废气与催化燃烧组件接触并发生催化燃烧反应。
4）尾气中的氯化氢和氯气通过含有碱性溶液的喷淋塔进行吸收，最终排放出无害的二氧化碳和水，从而实现对含卤素挥发性有机物的净化。
实施例
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
实施例1：
一种用于催化燃烧氯苯的催化剂，该催化剂由无机氧化物载体以及负载在载体上的高粘度涂层、助剂和活性组分涂层，所述高粘度涂层为铝溶胶涂敷于无机氧化物载体后焙烧所得，所述多孔无机氧化物载体为球状氧化铝，其比表面积为200m2/g，粒径为180微米，助剂组分是钠、钾的氧化物，助剂重量占催化剂重量的10%，活性组分中：铁与锰的摩尔比为0.5，钌与过渡金属的质量比为15%，钌的重量百分比为2%。
实施例2
其余与实施例1相同，除比表面积为380m2/ g。
实施例3
其余与实施例1相同，除比表面积为500m2/g。
实施例4
其余与实施例1相同，除比表面积为80m2/ g。
分别取2g实施例1~4催化剂，放置于管式固定床反应器中进行实验，实验条件如下：氧气20%，氮气80%，氯苯气体用氯苯气体发生器产生，由氮气吹入反应体系，控制氯苯浓度为500ppm，相对湿度50%，反应空速(GHSV)为15000 h-1，在反应500小时内，实施例1~4催化剂活性组分未有明显脱落，其活性组分负载牢固。氯苯转化率结果如表1所示，二氧化碳的选择性如表2所示。
表1
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | |
| 200℃ | 59.3% | 62.5% | 65.5% | 56.8% |
| 250℃ | 78.7% | 82.3% | 84.5% | 80.1% |
| 300℃ | 89.9% | 92.1% | 91.6% | 90.8% |
| 350℃ | 92.1% | 96.5% | 95.3% | 94.3% |
| 400℃ | 96.4% | 99.4% | 98.2% | 96.1% |
表2
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | |
| 200℃ | 88.6% | 87.9% | 85.5% | 82.8% |
| 250℃ | 90.2% | 90.2% | 94.5% | 80.1% |
| 300℃ | 95.0% | 96.4% | 96.4% | 90.8% |
| 350℃ | 97.1% | 99% | 98.6% | 94.3% |
| 400℃ | 98.9% | 100% | 99.2% | 95.8% |
实施例5
一种用于催化燃烧二氯甲烷的催化剂，对比实施例1，除了氧化铝的粒径为50微米，其余条件与实施例1相同。
实施例6
除了氧化铝粒径为100微米，其余条件与实施例5相同。
实施例7
除了氧化铝粒径为150微米，其余条件与实施例5相同。
实施例8
除了氧化铝粒径为200微米，其余条件与实施例5相同。
分别取2g实施例5~8催化剂，放置于管式固定床反应器中进行实验，实验条件如下：氧气20%，氮气80%，二氯甲烷气体用二氯甲烷气体发生器产生，由氮气吹入反应体系，控制二氯甲烷浓度为500ppm，相对湿度50%，反应空速(GHSV)为15000h-1，在反应500小时内，实施例5~8催化剂活性组分未有明显脱落，其活性组分负载牢固。二氯甲烷的转化率如表3所示。
表3
| 实施例5 | 实施例6 | 实施例7 | 实施例8 | |
| 200℃ | 59.3% | 62.5% | 65.5% | 56.8% |
| 250℃ | 78.7% | 82.3% | 84.5% | 80.1% |
| 300℃ | 89.9% | 92.1% | 91.6% | 90.8% |
| 350℃ | 92.1% | 96.5% | 95.3% | 94.3% |
| 400℃ | 96.4% | 99.4% | 98.2% | 96.1% |
分别取2g实施例5~8催化剂，放置于管式固定床反应器中进行实验，实验条件如下：氧气20%，氮气80%，二氯甲烷气体用二氯甲烷气体发生器产生，由氮气吹入反应体系,控制氯苯浓度为500ppm，相对湿度50-90%，反应空速(GHSV)为15000h-1，反应温度控制在400℃，在反应500小时内，实施例5~8催化剂活性组分未有明显脱落，其活性组分负载牢固。反应活性评价如表4所示。
表4
申请人声明,本发明通过上述实施例来说明本发明所述催化剂的详细组成，但本发明并不局限于上述详细组成，即不意味着本发明必须依赖上述详细组成才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均在本发明的保护范围和公开范围之内。
Claims (6)
1.一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，其特征在于：
首先将整体式或颗粒状催化剂组装到催化燃烧设备中，混合有含卤素挥发性有机物的有机废气通过上述设备，并在换热器和电热管的作用下加热到200~400℃，预热后的有机废气与催化燃烧组件接触并发生催化燃烧反应，生成二氧化碳、水、氯化氢和氯气，尾气通过含有碱性溶液的喷淋塔对氯化氢和氯气进行吸收，最终排放出无害的二氧化碳和水，从而实现对含卤素挥发性有机物的净化；
所述的整体式或颗粒状催化剂特征如下：
催化剂包括整体式或颗粒状无机氧化物载体以及负载在载体上的高粘度涂层、助剂和活性组分涂层，所述高粘度涂层为铝溶胶涂敷于无机氧化物载体后焙烧所得，所述活性组分采用氧化还原法沉淀于高粘度涂层表面，所述活性组分包括过渡金属和贵金属，过渡金属为铁和锰，贵金属为钌；
所述铁和锰的摩尔比为0.1~0.9，以催化剂的重量为100%计，过渡金属按金属元素重量计，所述过渡金属的重量百分比为0.1~20%；
所述钌与过渡金属的摩尔比为0.01~0.2，以催化剂的重量为100%计，过渡金属按金属元素重量计，以贵金属按金属元素重量计，所述贵金属的重量百分比为0.01~5%；
所述催化剂的制备过程如下：
(a)将含有二价铁的水溶性铁盐和含有二价锰的水溶性锰盐混合均匀形成前驱体水溶液；(b)将上述混合溶液逐滴加入一定浓度的高锰酸钾或高锰酸钠的水溶液中混合搅拌反应，反应物之间发生氧化还原反应在高粘度涂层表面生成褐色沉淀物涂层；(c)在上述溶液中继续加入钌的前驱体溶液并搅拌混合均匀；(d)将一定浓度的过氧化氢溶液逐滴加入上述溶液，钌的前驱体与铁锰双金属氧化物涂层发生氧化还原沉淀反应，形成钌/铁锰复合氧化物涂层；(e)将上述整体式或颗粒状催化剂取出，进行抽滤、洗涤，去除残留溶剂并干燥后获得所需催化剂。
2.根据权利要求1所述的一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，其特征在于：所述无机氧化物载体可为沸石、海泡石、多孔炭材料、球状氧化铝、球状二氧化硅、整体式蜂窝陶瓷的一种或者至少两种的复合物。
3.根据权利要求1所述的一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，其特征在于：所述无机氧化物载体的比表面积为5~500m2/g。
4.根据权利要求1所述的一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，其特征在于：所述无机氧化物载体的粒径为2-200微米。
5.根据权利要求1所述的一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，其特征在于：所述助剂组分是碱金属、无机酸或稀土元素氧化物的任意一种或至少两种的组合，所述碱金属为钠、钾的氧化物，所述无机酸为硫酸或磷酸，所述稀土元素氧化物为氧化铈或氧化镧。
6.根据权利要求5所述的一种催化剂用于含有卤素挥发性有机物催化燃烧的方法，其特征在于：所述助剂组分是通过浸渍法制备而成，以催化剂的重量为100%计，其重量百分比为0.2~20%。
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