CN109967129B - Composite catalyst capable of removing odor and recycling sulfur-containing compounds as resources and preparation method and application thereof - Google Patents
Composite catalyst capable of removing odor and recycling sulfur-containing compounds as resources and preparation method and application thereof Download PDFInfo
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- CN109967129B CN109967129B CN201711459693.0A CN201711459693A CN109967129B CN 109967129 B CN109967129 B CN 109967129B CN 201711459693 A CN201711459693 A CN 201711459693A CN 109967129 B CN109967129 B CN 109967129B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 30
- 239000011593 sulfur Substances 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 34
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 29
- 238000002791 soaking Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004966 Carbon aerogel Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000000571 coke Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 235000019645 odor Nutrition 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 208000010476 Respiratory Paralysis Diseases 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01D53/8603—Removing sulfur compounds
-
- 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
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a composite catalyst for removing malodor and recycling sulfur-containing compounds, which comprises the following components in percentage by weight: 50-90% of a carrier, 5-30% of a metal oxide and 5-30% of a reducing agent. The invention further provides a preparation method and application of the composite catalyst for removing the odor and recycling the sulfur-containing compounds. The composite catalyst for removing the odor and recycling the sulfur-containing compound as resources, and the preparation method and the application thereof provided by the invention have the advantages of economy, energy conservation, environmental friendliness, high purification efficiency, reusability, capability of being used under complex working conditions with a wider reaction temperature range and severe or frequent fluctuation of the concentration of the odor gas, extremely suitability for the field of purification of fixed-source odor gas containing organic sulfur, such as methyl mercaptan, methyl sulfide, dimethyl disulfide, carbon disulfide and the like, and wide actual industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental pollution treatment, relates to a composite catalyst for removing malodor and recycling sulfur-containing compounds, a preparation method and an application thereof, and particularly relates to a thiourea-supported composite denitration catalyst for removing malodor and recycling sulfur-containing compounds, a preparation method and an application thereof.
Background
The stink acts on the smell of people and causes harm to people, and is one of seven typical public hazards in the world. In the emission standard of malodorous pollutants (GB14554-1993) in China, 5 of the eight malodorous pollutants which are limited and controlled to be emitted are sulfur-containing substances, wherein organic sulfur compounds account for more than 4. The organic sulfur malodorous gas mainly comprises thiol, thioether, carbonyl sulfide, carbon disulfide and the like, generally has strong pungent odor and strong toxicity, and is an important malodorous pollutant. The organic sulfur malodorous gas has wide sources, and mainly comes from human sources, such as petrochemical industry, pesticide production, medicine and pharmacy, rubber processing, paper making and pulping, paint production, sewage treatment, food processing and the like. The organic sulfur malodorous substances can cause different degrees of damage to the respiratory system, the digestive system, the cardiovascular system, the endocrine system and the nervous system of a human body, and even can cause respiratory paralysis and death. In addition, organic sulfur malodorous substances can participate in a series of complex oxidation reactions and photochemical reactions in the atmospheric environment, which can cause climatic problems such as ozone layer depletion, acid rain, photochemical smog, parasol effect and the like, thereby influencing the global ecological environment.
Common methods for treating the organic sulfur malodorous gas include an adsorption method, a thermal combustion method, a biological filter method, a spray oxidation method, a photocatalytic oxidation method, a plasma method, a catalytic decomposition method and the like. Reference 1(V.G. Devalprolli et al, Applied Catalysis A-General, 2008, Vol.348, pp.86-93) reports a method of forming CuO-MoO3Loaded on gamma-Al2O3The catalyst is prepared by using ozone as an oxidant, and methyl sulfide can be catalytically oxidized into carbon dioxide and sulfur dioxide at the reaction temperature of 100-200 ℃. Document 2(c.l. hwang et al, Applied Catalysis a-General, 2011, 393, p. 251-256) reports that an ion-exchanged zeolite molecular sieve Ag-Mn/ZSM-5 as a catalyst, ozone as an oxidant, can catalytically oxidize methyl sulfide to sulfur dioxide at a temperature ranging from room temperature to 130 ℃, and can finally convert the sulfur dioxide to sulfuric acid in the presence of water, thereby recovering sulfur-containing compounds.
At present, the catalyst still has the problems of low catalytic efficiency, low selectivity and easy inactivation of active components, and the ozone serving as an oxidant has poor stability, high price, strong corrosion capability on equipment pipelines and certain toxicity. Therefore, an efficient catalyst system which takes cheap oxygen as an oxidant is developed, and the high-efficiency recovery of the sulfur-containing compounds can be realized, so that the method has very important environmental protection significance and economic value.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention aims to provide a composite catalyst which is economical, energy-saving, green and environment-friendly, has high low-temperature activity and a wide reaction temperature range, can remove malodors, and can recycle sulfur-containing compounds, and a preparation method and an application method thereof.
In order to achieve the above and other related objects, a first aspect of the present invention provides a composite catalyst for removing offensive odors and recycling sulfur-containing compounds, comprising the following components by weight:
50 to 90 percent of carrier,
5 to 30% of a metal oxide,
5-30% of a reducing agent.
Preferably, the composite catalyst for removing the malodor and recycling the sulfur-containing compounds comprises the following components in percentage by weight:
60 to 90 percent of carrier,
5 to 25% of a metal oxide,
5-25% of a reducing agent.
Preferably, the carrier is selected from one of activated carbon, activated carbon fiber, carbon aerogel, activated coke, activated semi-coke, natural zeolite or synthetic molecular sieve.
More preferably, the synthetic molecular sieve is selected from one of an SBA-15 molecular sieve, an MCM-41 molecular sieve or a ZSM-5 molecular sieve.
Preferably, the metal oxide is an AB type binary metal oxide, wherein A is an oxide of Mn and B is selected from one of oxides of La, Cu, Mg or Zr.
More preferably, in the AB type binary metal oxide, the molar ratio of the sum of the molar amounts of the metal elements in a and the metal elements in B to the molar amount of the metal elements in a is 1: 0.2 to 0.8.
More preferably, the AB type binary metal oxide is obtained by oxidizing an inorganic salt precursor corresponding to a metal element in AB.
Further preferably, the metal element inorganic salt precursor corresponding to the metal oxide a is a manganese salt.
Still more preferably, the manganese salt is selected from one of manganese acetate, manganese nitrate, manganese chloride or manganese sulfate.
Further preferably, the metal element inorganic salt precursor corresponding to the metal oxide B is selected from one of lanthanum salt, copper salt, magnesium salt or zirconium salt.
Still more preferably, the lanthanum salt is selected from one of lanthanum acetate, lanthanum nitrate or lanthanum sulfate.
Still more preferably, the copper salt is selected from one of copper chloride, copper nitrate or copper sulfate.
Still more preferably, the magnesium salt is selected from one of magnesium chloride or magnesium nitrate.
Still more preferably, the zirconium salt is selected from one of zirconium nitrate, zirconium sulfate, zirconium chloride or zirconium acetate.
Preferably, the reducing agent is selected from one of thiourea or thiosemicarbazide or a mixture of thiourea and the mixture in any proportion.
The second aspect of the invention provides a preparation method of a composite catalyst for removing malodor and recycling sulfur-containing compounds, which comprises the following steps:
1) dissolving inorganic salt corresponding to the metal element in the step A and inorganic salt corresponding to the metal element in the step B in water to obtain metal inorganic salt precursor solution;
2) dissolving a reducing agent in water to obtain a reducing agent solution;
3) soaking the carrier in the metal inorganic salt precursor solution obtained in the step 1) by adopting an isometric soaking method, uniformly stirring, and drying to obtain a solid sample;
4) heating and calcining the solid sample obtained in the step 3), and then cooling to obtain a calcined solid sample;
5) and soaking the calcined solid sample obtained in the step 4) in the reducing agent solution obtained in the step 2) by adopting an isometric soaking method, uniformly stirring, and drying to obtain the required composite catalyst.
Preferably, in the step 1), the ratio of the mass g of the inorganic salt corresponding to the metal element added in the step A to the volume mL of the water added in the step B is 2-20: 2-20: 100.
preferably, in step 1), the molar ratio of the sum of the molar amounts of the metal elements in a and the metal elements in B to the molar amount of the metal elements in a in the inorganic salt corresponding to the metal elements in B is 1: 0.2 to 0.8.
Preferably, in the step 1), the total concentration of the binary metal in the metal inorganic salt precursor solution is 0.5-3 mol/L.
Preferably, in the step 2), the concentration of the reducing agent solution is 0.6-3.23 mol/L.
Preferably, in the step 2), the dissolving temperature of the reducing agent is 25-80 ℃.
Preferably, in the step 3), the ratio of the added mass g of the carrier to the added volume mL of the metal inorganic salt precursor solution is 1: 3-20.
Preferably, in step 3), the impregnation conditions are: the dipping temperature is as follows: room temperature; dipping time: 6-24 h.
Preferably, in step 3), the drying conditions are as follows: drying temperature: 60-110 ℃; drying time: 12-48 h.
Preferably, in step 4), the calcination conditions are: a calcining device: a tube furnace; protective gas: nitrogen gas; calcination temperature rise rate: 1-5 ℃/min; calcination temperature: 350-800 ℃; calcining time: 2-6 h.
Preferably, in step 4), the cooling conditions are as follows: cooling temperature: room temperature; protective gas: nitrogen gas; a cooling mode: and (5) naturally cooling.
Preferably, in the step 5), the soaking time is 6-24 h.
Preferably, in the step 5), the temperature of the impregnation is 25-80 ℃.
Preferably, in step 5), the drying conditions are as follows: and (3) drying mode: vacuum drying; drying temperature: 60-120 ℃; drying time: 12-48 h.
Preferably, in step 3) or 5), the equal-volume impregnation method means that the volume of the impregnation liquid is equal to the void volume of the carrier, so that the carrier can be just completely immersed in the impregnation liquid.
The room temperature is 20-30 ℃.
The third aspect of the invention provides the application of the composite catalyst in removing the odor and recycling the sulfur-containing compounds.
Preferably, the sulfur-containing compound is selected from one or more of methyl mercaptan, methyl sulfide, dimethyl disulfide or carbon disulfide.
Preferably, the composite catalyst is filled in a fixed bed reactor, and malodorous gas containing sulfur is introduced.
More preferably, the reaction temperature is 0-160 ℃. A
More preferably, the malodorous gas may be operated at a pressure of 0.1 to 10 MPa.
More preferably, the space velocity of the malodorous gas is 500-100000 h-1。
More preferably, the malodorous gas contains sulfur compounds with concentration of 5-5000 ppm and O2The concentration is 1-21 vol%. The composite catalyst can be used under the working conditions that the concentration of the malodorous gas fluctuates violently and frequently, and particularly can stably run under the actual working conditions of the malodorous gas.
As described above, the composite catalyst for removing malodors and recycling sulfur-containing compounds, and the preparation method and the application thereof provided by the invention adopt the binary metal oxide with higher low-temperature catalytic activity as an active component, cheap and nontoxic oxygen as an oxidant, and adopt the solid sulfur-containing compound with higher low-temperature activity and wider reaction temperature range as a reducing component, so that methyl mercaptan, methyl sulfide, dimethyl disulfide, carbon disulfide and the like in malodorous gases can be converted into elemental sulfur with higher economic value to realize recycling. The supported denitration catalyst taking the solid sulfur-containing compound as the reducing agent has the advantages of economy, energy conservation, environmental friendliness, high purification efficiency, reusability, wide reaction temperature range and severe or frequent fluctuation of the concentration of malodorous gases, is extremely suitable for the field of purification of malodorous gases containing fixed sources such as methyl mercaptan, methyl sulfide, dimethyl disulfide, carbon disulfide and the like, and has wide actual industrial application prospect.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Manganese acetate and lanthanum nitrate are dissolved in water to prepare a metal inorganic salt precursor solution, wherein the molar ratio Mn/(Mn + La) is 0.2, and the total concentration of binary metals is 0.5 mol/L. Dissolving thiourea in water to prepare a reducing agent solution, wherein the concentration of the reducing agent solution is 0.6 mol/L. Weighing 0.5g of carbon aerogel with the particle size of 0.2-2.0 mm as a carrier, soaking the carbon aerogel in a metal inorganic salt precursor solution at room temperature for 6 hours by an isometric immersion method, uniformly stirring, drying at 80 ℃ for 48 hours in an oven, then placing a dried sample in a tubular furnace, introducing nitrogen as a protective gas, and heating to 350 ℃ at the speed of 1 ℃/min to calcine for 6 hours. Then continuing to cool to room temperature under the protection of nitrogen. And finally, soaking the sample in 0.6mol/L thiourea solution (25 ℃) for 6 hours by adopting an isometric soaking method, uniformly stirring, and then placing the sample in a drying oven to dry for 24 hours at 80 ℃ to obtain the composite denitration catalyst carrying thiourea and the Mn-La binary metal oxide. The composite catalyst comprises the following components in percentage by weight: 90% of carbon aerogel, 5% of Mn-La binary metal oxide and 5% of thiourea.
The prepared composite catalyst is filled in a fixed bed reactor, the temperature is raised to 0 ℃ for ventilation, and the simulated malodorous gas comprises the following components: 5ppm methyl mercaptan, 1 vol% O2，N2Is used as balance gas, is operated under the pressure of 0.1MPa and has the space velocity of 500h-1. The test results are as follows: the steady-state conversion of methyl mercaptan was 90%, the duration was 553h and the breakthrough sulfur capacity was 0.05g methyl mercaptan/g.
Example 2
Manganese nitrate and copper sulfate are dissolved in water to prepare a metal inorganic salt precursor solution, wherein the molar ratio Mn/(Mn + Cu) is 0.8, and the total concentration of binary metals is 3 mol/L. Dissolving thiosemicarbazide in water to prepare a reducing agent solution, wherein the concentration of the reducing agent solution is 3.23 mol/L. Weighing 0.5g of activated carbon fiber as a carrier, soaking the activated carbon fiber in a metal inorganic salt precursor solution at room temperature for 10 hours by an isometric soaking method, uniformly stirring, then placing in an oven to dry at 100 ℃ for 20 hours, then placing a dried sample in a tubular furnace, introducing nitrogen as a protective gas, heating to 500 ℃ at the speed of 2 ℃/min, and calcining for 5 hours. Then continuing to cool to room temperature under the protection of nitrogen. And finally, soaking the sample in 3.23mol/L thiosemicarbazide solution (60 ℃) for 12 hours by adopting an isometric soaking method, uniformly stirring, and then placing the mixture in a drying oven to dry the mixture for 30 hours at 100 ℃ to obtain the composite denitration catalyst carrying thiosemicarbazide and the Mn-Cu binary metal oxide. The composite catalyst comprises the following components in percentage by weight: 40% of activated carbon fiber, 30% of Mn-Cu binary metal oxide and 30% of thiosemicarbazide.
The prepared composite catalyst is filled in a fixed bed reactor, the temperature is raised to 160 ℃ for ventilation, and the simulated malodorous gas comprises the following components: 5000ppm of dimethylsulfide, 21 vol% O2，N2For balancing gas, the operation is carried out under the pressure of 10MPa, and the space velocity is 100000h-1. The test results are as follows: the steady-state conversion of dimethylsulfide was 95%, the duration was 70h and the breakthrough sulfur capacity was 0.35g dimethylsulfide/g.
Example 3
Manganese sulfate and magnesium chloride are dissolved in water to prepare a metal inorganic salt precursor solution, wherein the molar ratio Mn/(Mn + Mg) is 0.7, and the total concentration of binary metals is 1.54 mol/L. Dissolving thiosemicarbazide in water to prepare a reducing agent solution, wherein the concentration of the reducing agent solution is 0.86 mol/L. Weighing 0.5g of active coke with the particle size of 0.2-2.0 mm as a carrier, soaking the active coke in a metal inorganic salt precursor solution at room temperature for 24 hours by an isometric soaking method, uniformly stirring, drying at 110 ℃ for 36 hours in an oven, then placing a dried sample in a tubular furnace, introducing nitrogen as protective gas, and heating to 700 ℃ at the speed of 5 ℃/min to calcine for 3 hours. Then continuing to cool to room temperature under the protection of nitrogen. And finally, soaking the sample in 0.86mol/L thiosemicarbazide solution (80 ℃) for 6 hours by adopting an isometric soaking method, uniformly stirring, and then placing the mixture in a drying oven to dry for 26 hours at 110 ℃ to obtain the composite denitration catalyst carrying thiosemicarbazide and the Mn-Mg binary metal oxide. The composite catalyst comprises the following components in percentage by weight: 77% of active coke, 15% of Mn-Cr binary metal oxide and 8% of thiosemicarbazide.
The prepared composite catalyst is filled in a fixed bed reactor, the temperature is raised to 100 ℃ for ventilation, and the simulated malodorous gas comprises the following components: 1000ppm Dimethyldithio, 4 vol% O2，N2For balancing gas, the operation is carried out under the pressure of 1MPa, and the space velocity is 12000h-1. The test results are as follows: the steady-state conversion of methyl mercaptan was 98%, the duration was 67h, and the breakthrough sulfur capacity was 0.13g of dimethyldisulfide/g.
Example 4
Manganese acetate and zirconium sulfate are dissolved in water to prepare a metal inorganic salt precursor solution, wherein the molar ratio Mn/(Mn + Zr) is 0.8, and the total concentration of binary metals is 2.13 mol/L. Dissolving thiourea in water to prepare a reducing agent solution, wherein the concentration of the reducing agent solution is 1.05 mol/L. Weighing 1.0g of powdered SBA-15 molecular sieve as a carrier, soaking the SBA-15 molecular sieve in a metal inorganic salt precursor solution at room temperature for 6 hours by adopting an isometric impregnation method, uniformly stirring, then placing the obtained product in an oven to dry at 90 ℃ for 48 hours, then placing a dried sample in a tube furnace, introducing nitrogen as a protective gas, and heating to 400 ℃ at the speed of 1 ℃/min to calcine for 6 hours. Then continuing to cool to room temperature under the protection of nitrogen. And finally, soaking the sample in 1.05mol/L thiourea solution (25 ℃) for 6 hours by adopting an isometric soaking method, uniformly stirring, and then placing the sample in a drying oven to dry for 24 hours at 60 ℃ to obtain the composite denitration catalyst carrying thiourea and the Mn-Zr binary metal oxide. The composite catalyst comprises the following components in percentage by weight: 70% of SBA-15 molecular sieve, 20% of Mn-Zr binary metal oxide and 10% of thiourea.
The prepared composite catalyst is filled in a fixed bed reactor, the temperature is raised to 60 ℃ for ventilation, and the simulated malodorous gas comprises the following components: 300ppm carbon disulfide, 21 vol% O2，N2Is balance gas, 5MPa and the space velocity is 8000h-1. The test results are as follows: the steady state conversion of carbon disulphide was 83%, the duration was 169h, and the breakthrough sulphur capacity was 0.14g carbon disulphide/g.
Example 5
Manganese acetate and lanthanum sulfate are dissolved in water to prepare a metal inorganic salt precursor solution, wherein the molar ratio Mn/(Mn + La) is 0.4, and the total concentration of binary metals is 2.7 mol/L. Dissolving thiosemicarbazide in water to prepare a reducing agent solution, wherein the concentration of the reducing agent solution is 1.83 mol/L. Weighing 1.0g of powdered ZSM-5 molecular sieve as a carrier, soaking the ZSM-5 molecular sieve in a metal inorganic salt precursor solution at room temperature for 10 hours by an isometric impregnation method, uniformly stirring, then placing in a drying oven to dry at 110 ℃ for 20 hours, then placing a dried sample in a tube furnace, introducing nitrogen as a protective gas, and heating to 450 ℃ at a speed of 2 ℃/min to calcine for 5 hours. Then continuing to cool to room temperature under the protection of nitrogen. And finally, soaking the sample in 0.97mol/L thiosemicarbazide solution (70 ℃) for 6 hours by adopting an isometric soaking method, uniformly stirring, and then placing the mixture in a drying oven to dry the mixture for 30 hours at 85 ℃ to obtain the composite denitration catalyst carrying thiosemicarbazide and the Mn-La binary metal oxide. The composite catalyst comprises the following components in percentage by weight: 55% of ZSM-5 molecular sieve, 25% of Mn-Ce binary metal oxide and 20% of amino thiourea.
The prepared composite catalyst is filled in a fixed bed reactor, the temperature is raised to 150 ℃ for ventilation, and the simulated malodorous gas comprises the following components: 100ppm of dimethylsulfide, 15 vol% O2，N2Is used as balance gas, is operated at 0.5MPa, and has space velocity of 50000h-1. The test results are as follows: the steady-state conversion of dimethylsulfide was 88%, the duration was 312h and the breakthrough sulfur capacity was 0.26g dimethylsulfide/g.
Example 6
Manganese acetate and zirconium nitrate are dissolved in water to prepare a metal inorganic salt precursor solution, wherein the molar ratio Mn/(Mn + Zr) is 0.2, and the total concentration of binary metals is 2.54 mol/L. Dissolving thiourea in water at 25 ℃ to prepare a reducing agent solution, wherein the concentration of the reducing agent solution is 2.13 mol/L. Weighing 1.0g of carbon aerogel as a carrier, soaking the carbon aerogel in a metal inorganic salt precursor solution at room temperature for 6 hours by an isometric immersion method, uniformly stirring, placing in a drying oven for drying at 80 ℃ for 48 hours, then placing a dried sample in a tubular furnace, introducing nitrogen as a protective gas, heating to 350 ℃ at the speed of 1 ℃/min, and calcining for 6 hours. Then continuing to cool to room temperature under the protection of nitrogen. And finally, soaking the sample in 2.13mol/L thiourea solution (25 ℃) for 6 hours by adopting an isometric soaking method, uniformly stirring, and then placing the sample in a drying oven to dry for 48 hours at 80 ℃ to obtain the composite denitration catalyst carrying thiourea and the Mn-Zr binary metal oxide. The composite catalyst comprises the following components in percentage by weight: 50% of carbon aerogel, 25% of Mn-Zr binary metal oxide and 25% of thiourea.
Filling the prepared composite catalyst into a fixed bed reactor, controlling the reaction temperature to be 25 ℃ for ventilation, introducing malodorous gas with the pressure of 0.1MPa, and reacting sulfur-containing compounds in flue gas with thiourea loaded on the composite catalyst to generate a simple substance S, N2、CO2And H2O, has the characteristics of economy, energy conservation, no secondary pollution, high purification efficiency and the like.
In conclusion, the composite catalyst for removing the odor and recycling the sulfur-containing compounds as resources, and the preparation method and the application thereof provided by the invention have the advantages of economy, energy conservation, environmental friendliness, high purification efficiency, reusability, capability of being used under complex working conditions with a wider reaction temperature range and severe or frequent fluctuation of the concentration of the odor gas, and great suitability for fixed-source methyl mercaptan, methyl sulfide and H2S and other malodorous gases, and has wide practical industrial application prospect. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (3)
1. The application of the composite catalyst in removing the odor and recycling the sulfur-containing compounds;
the composite catalyst comprises the following components in percentage by weight:
50 to 90 percent of carrier,
5 to 30% of a metal oxide,
5-30% of a reducing agent;
the carrier is selected from one of active carbon, active carbon fiber, carbon aerogel, active coke, active semicoke, natural zeolite or synthetic molecular sieve; the reducing agent is selected from one of thiourea or thiosemicarbazide or a mixture of the thiourea and the thiosemicarbazide in any proportion;
the metal oxide is AB type binary metal oxide, wherein A is Mn oxide, and B is selected from one of La, Cu, Mg or Zr oxide; in the AB type binary metal oxide, the molar ratio of the sum of the molar amounts of the metal elements in A and the metal elements in B to the molar amount of the metal elements in A is 1: 0.2 to 0.8;
the preparation method of the composite catalyst comprises the following steps:
1) dissolving inorganic salt corresponding to the metal element in the step A and inorganic salt corresponding to the metal element in the step B in water to obtain metal inorganic salt precursor solution;
2) dissolving a reducing agent in water to obtain a reducing agent solution;
3) soaking the carrier in the metal inorganic salt precursor solution obtained in the step 1) by adopting an isometric soaking method, uniformly stirring, and drying to obtain a solid sample;
4) heating and calcining the solid sample obtained in the step 3), and then cooling to obtain a calcined solid sample;
5) soaking the calcined solid sample obtained in the step 4) in the reducing agent solution obtained in the step 2) by adopting an isometric soaking method, uniformly stirring, and drying to obtain the required composite catalyst;
the preparation method comprises any one or more of the following conditions:
A1) in the step 1), the ratio of the mass g of the inorganic salt corresponding to the metal element in the step A to the volume mL of the inorganic salt corresponding to the metal element in the step B to the volume mL of the water is 2-20: 2-20: 100, respectively;
A2) in the step 1), the total concentration of binary metals in the metal inorganic salt precursor solution is 0.5-3 mol/L;
A3) in the step 2), the concentration of the reducing agent solution is 0.6-3.23 mol/L;
A4) in the step 3), the ratio of the mass g of the carrier to the volume mL of the metal inorganic salt precursor solution is 1: 3-20 parts of;
A5) in the step 3), the impregnation conditions are as follows: the dipping temperature is as follows: room temperature; dipping time: 6-24 h;
A6) in the step 3), the drying conditions are as follows: drying temperature: 60-110 ℃; drying time: 12-48 h;
A7) in the step 4), the calcining conditions are as follows: a calcining device: a tube furnace; protective gas: nitrogen gas; calcination temperature rise rate: 1-5 ℃/min; calcination temperature: 350-800 ℃; calcining time: 2-6 h;
A8) in the step 5), the dipping time is 6-24 h, and the dipping temperature is 25-80 ℃;
A9) in the step 5), the drying conditions are as follows: and (3) drying mode: vacuum drying; drying temperature: 60-120 ℃; drying time: 12-48 h;
the sulfur-containing compound is one or more of methyl mercaptan, methyl sulfide, dimethyl disulfide or carbon disulfide.
2. The use according to claim 1, characterized in that the composite catalyst is filled in a fixed bed reactor, and malodorous gas containing sulfur is introduced.
3. Use according to claim 2, characterized in that it comprises any one or more of the following conditions:
B1) the reaction temperature is 0-160 ℃;
B2) the malodorous gas can be operated under a certain pressure, and the pressure is 0.1-10 MPa;
B3) the space velocity of the malodorous gas is 500-100000 h-1；
B4) In the malodorous gas, the concentration of sulfur-containing compounds is 5-5000 ppm, and O is2The concentration is 1-21 vol%.
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