CN113877623B - Preparation method and application of catalyst for purifying tail gas of submerged arc furnace - Google Patents
Preparation method and application of catalyst for purifying tail gas of submerged arc furnace Download PDFInfo
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- CN113877623B CN113877623B CN202111070615.8A CN202111070615A CN113877623B CN 113877623 B CN113877623 B CN 113877623B CN 202111070615 A CN202111070615 A CN 202111070615A CN 113877623 B CN113877623 B CN 113877623B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 65
- 239000002253 acid Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 10
- 238000010025 steaming Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011258 core-shell material Substances 0.000 abstract description 11
- 238000003723 Smelting Methods 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 10
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 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 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008021 deposition 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
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
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- 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
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01D53/8634—Ammonia
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- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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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)
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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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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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
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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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
- B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
- B01D2257/553—Compounds comprising hydrogen, e.g. silanes
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
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- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a catalyst for purifying tail gas of an ore smelting furnace, which belongs to the technical field of catalysts, and the invention takes a TS-1 molecular sieve as a carrier to load metal oxide as a core and takes mesoporous SBA-15 as a shell to prepare a core-shell catalyst by self-assembly; the core-shell molecular sieve has the characteristics of high activity, good removal effect, simple preparation method, easy operation, low cost and the like.
Description
Technical Field
The invention relates to a preparation method of a catalyst for purifying tail gas of an ore smelting furnace, and belongs to the technical field of catalyst preparation.
Background
In recent years, the ore smelting industry such as nonferrous metallurgy, phosphorus chemical industry, coal chemical industry and the like brings convenience to technological development, and simultaneously, the ore smelting industry also brings burden to the environment, particularly, a large amount of generated tail gas can become one of atmospheric pollution sources due to the factors such as unreasonable energy utilization and recovery in partial production, and the tail gas has the characteristics of deposition, variability and the like, and can continuously migrate and transform in the environment, thereby not only negatively affecting the health of a human body, but also causing serious threat to the ecological environment. The submerged arc smelting production process belongs to a smelting production process with high energy consumption and high pollution, and a large amount of CO-rich gas is generated in the process of producing industrial products by using a submerged arc smelting technology, wherein the content of the CO-rich gas is about 80% -85%, and the main gas of submerged arc tail gas is as follows in percentage by volume or content: h 2 （7%），CO 2 （2.4%），O 2 （0.5%），N 2 （7%），AsH 3 （210 mg·m -3 ），H 2 S（800 mg·m -3 ），PH 3 （275mg·m -3 ），HCN（500mg·m -3 ），COS（550 mg·m -3 ），CS 2 （350 mg·m -3 ），Hg 0 （12～18 mg·m -3 ) Etc. Wherein, HCN generates NH through catalytic hydrolysis 3 COS and CS 2 H is generated through catalytic hydrolysis reaction 2 S, S. Therefore, the study is to adopt a catalyst to simultaneously remove PH in the tail gas of the submerged arc furnace 3 、H 2 S、AsH 3 、NH 3 . Current PH 3 、H 2 The S removing method comprises absorption method, liquid phase catalytic oxidation method, wet oxidation method, adsorption-oxidation method, catalytic decomposition method, etc., and AsH 3 The removal technology of (2) comprises a solution absorption method, an adsorption method, a catalytic decomposition method, a catalytic oxidation method and the like. NH (NH) 3 The purification technology of (2) comprises an absorption method, an adsorption method, a high-temperature combustion method, a catalytic oxidation method, a catalytic decomposition method and the like. The catalytic oxidation method has wide application, small secondary pollution and ideal removal effect, so the catalytic oxidation method is selected for gas removal in the research.
CN104888692a discloses the invention named "a preparation method of adsorbent for simultaneously removing hydrogen sulfide, phosphine and arsine", and the material prepared by the invention has good purifying effect on phosphine and arsine, but the adsorbent used has the disadvantage of easy penetration.
CN104888845a discloses the invention named "a platinum/cerium aluminum-molecular sieve catalyst for catalytic oxidation of ammonia gas and preparation method thereof", the catalytic active center of the catalyst layer of the invention is composed of noble metal platinum, cerium-aluminum composite oxide and rubidium modified molecular sieve, the cost of using noble metal platinum is high, and the industrial cost is increased; meanwhile, the ammonia conversion rate is very low when the reaction temperature of the catalyst is about 200 ℃.
At present, PH in tail gas of submerged arc furnace is removed by simultaneous catalytic oxidation 3 、H 2 S、AsH 3 、NH 3 No report was seen on the preparation of the catalystA lane.
Disclosure of Invention
Aiming at the problem of impurity removal in the tail gas of the submerged arc furnace in the prior art, the invention provides a preparation method of a catalyst for purifying the tail gas of the submerged arc furnace, which comprises the following specific steps:
(1) Adding a TS-1 molecular sieve into a metal salt solution, mixing and stirring for 2-5 hours, performing rotary evaporation, drying and roasting to obtain a metal oxide/TS-1 molecular sieve catalyst;
the metal salt is metal I salt and metal II salt, wherein the metal I salt is one of copper salt, ferric salt and nickel salt, the metal II salt is one of cerium salt, zirconium salt and lanthanum salt, and the metal I accounts for 10-40% of the mass of the TS-1 molecular sieve; the metal II accounts for 0.5 to 5 percent of the mass of the TS-1 molecular sieve; spin steaming is to treat at 40-80 deg.c for 0.5-1.5 hr and roasting at 350-600 deg.c for 3-6 hr;
(2) Adding a silicon source into a dilute acid solution, stirring at room temperature, standing and aging;
the silicon source is one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate, the dilute acid is one of hydrochloric acid, sulfuric acid and phosphoric acid, the concentration of the dilute acid solution is 0.2-1 mol/L, the mass volume ratio g of the silicon source and the dilute acid solution is (0.5-5): 1, the stirring time of the silicon source in the dilute acid solution is 3-12 h, and the silicon source is kept stand and aged for 4-36 h;
(3) Dissolving a template agent in a dilute acid solution, adding the metal oxide/TS-1 molecular sieve catalyst in the step (1), stirring for 1-2 h, adding the silicon source dilute acid solution in the step (2), and stirring the mixed solution at 25-35 ℃ for reaction for 4-12 h;
the template agent is triblock copolymer P123, F127 or F108, the dilute acid is one of hydrochloric acid, sulfuric acid and phosphoric acid, the concentration of the dilute acid solution is 0.2-1 mol/L, the mass volume ratio of the template agent to the dilute acid solution is (1-2): 1, the solid-liquid ratio g of the metal oxide/TS-1 molecular sieve catalyst to the template agent dilute acid solution is 1:10-15, and the solid-liquid ratio g of the metal oxide/TS-1 molecular sieve catalyst to the silicon source dilute acid solution is (1-6): 3-15;
(4) Adjusting the pH value of the reaction product in the step (3) to 2-6, then transferring the reaction product to a polytetrafluoroethylene autoclave for hydrothermal crystallization, centrifuging the reaction liquid, collecting a solid product, washing the solid product to be neutral by deionized water and ethanol, drying and roasting to obtain the catalyst for purifying the tail gas of the submerged arc furnace;
the hydrothermal crystallization temperature is 100-180 ℃, the time is 10-72 h, the drying is carried out at 120 ℃ for 12h, and the roasting is carried out at 350-600 ℃ for 3-6 h.
The invention also aims to apply the catalyst prepared by the method to remove PH in tail gas of submerged arc furnace 3 、H 2 S、AsH 3 、NH 3 Is a kind of medium.
The beneficial effects of the invention are as follows:
(1) At present, no method for simultaneously catalyzing, oxidizing and removing PH in tail gas of submerged arc furnace exists 3 、H 2 S、AsH 3 、NH 3 A preparation method of the core-shell catalyst; (2) The core-shell catalyst prepared by the invention has stable structure, good hydrothermal stability and excellent catalytic performance, and compared with the traditional TS-1 molecular sieve, the catalyst has better catalytic effect and higher removal efficiency; (3) The catalyst of the invention has the advantages of simple preparation method, easy operation and low cost.
Drawings
FIG. 1 shows CuO-Fe according to an embodiment of the present invention 2 O 3 The removal effect diagram of phosphine, hydrogen sulfide, arsine and ammonia of the TS-1@SBA-15 core-shell catalyst;
FIG. 2 shows CuO-CeO according to an embodiment of the present invention 2 The removal effect diagram of phosphine, hydrogen sulfide, arsine and ammonia of the TS-1@SBA-15 core-shell catalyst;
FIG. 3 shows a CuO-La of an embodiment of the present invention 2 O 3 The removal effect diagram of phosphine, hydrogen sulfide, arsine and ammonia of the TS-1@SBA-15 core-shell catalyst;
FIG. 4 shows NiO-CeO according to an embodiment of the present invention 2 The removal effect diagram of phosphine, hydrogen sulfide, arsine and ammonia of the TS-1@SBA-15 core-shell catalyst;
FIG. 5 shows Fe according to an embodiment of the present invention 2 O 3 -ZrO 2 Phosphine, hydrogen sulfide, arsine and ammonia of/TS-1@SBA-15 core-shell catalystRemoving an effect diagram;
FIG. 6 shows CeO according to an embodiment of the present invention 2 -La 2 O 3 The removal effect diagram of phosphine, hydrogen sulfide, arsine and ammonia of the TS-1@SBA-15 core-shell catalyst;
FIG. 7 is a graph showing the effect of removing phosphine, hydrogen sulfide, arsine and ammonia from the catalyst of comparative example 1 of the present invention.
Detailed Description
The invention will be described in further detail with reference to specific examples, but the scope of the invention is not limited to the description.
The activity of the catalyst in the examples below was determined by pH 3 、H 2 S、AsH 3 And NH 3 Expressed as the removal rate of NH 3 The subject group was previously tested for the relevant activity evaluation, and the conversion rate at 100℃was optimal, so that the stability test was conducted at 100 ℃.
The activity test of the catalyst is carried out in a reactor under the following reaction conditions: PH value 3 Concentration of 910mg/m 3 、H 2 S concentration 456mg/m 3 、AsH 3 Concentration 696mg/m 3 、NH 3 The concentration is 379mg/m 3 1% of oxygen and 1% of nitrogen as balance gas, and the reaction space velocity (GHSV) is 20000h -1 The reaction temperature was 100 ℃.
Example 1
(1) Adding TS-1 molecular sieve into the mixed solution containing copper nitrate and ferric nitrate, mixing and stirring for 4 hours, steaming at 80 ℃ for 0.5 hours, then placing the sample in a blast drying oven for drying at 100 ℃ for 12 hours, and roasting the dried sample at 550 ℃ for 5 hours to obtain the metal oxide/TS-1 molecular sieve catalyst which is named as CuO-Fe 2 O 3 TS-1, wherein copper accounts for 40% of the mass of the TS-1 molecular sieve, and iron accounts for 10% of the mass of the TS-1 molecular sieve;
(2) Mixing tetraethoxysilane with 0.3mol/L HCl solution according to the ratio of 3.5g to 1mL, stirring for 4h at room temperature, standing and aging for 24h;
(3) Mixing template P123 with 0.4mol/L HCl solution according to the ratio of 1.25g to 1mL to prepare template dilute acid solution, and performing the step (1) of CuO-Fe 2 O 3 /TS-1 catalyst is added into the mixture and stirred for 1h, then the silicon source diluted acid solution in the step (2) is added, the mixed solution is stirred for 5h at 30 ℃, and CuO-Fe is added 2 O 3 The solid-to-liquid ratio g/mL of the catalyst/TS-1 and the template agent dilute acid solution is 1:10, and CuO-Fe 2 O 3 The solid-to-liquid ratio g of the TS-1 catalyst to the silicon source dilute acid solution is 5:10;
(4) Adjusting pH=4 of the mixed solution obtained in the step (3) by adopting ammonia water, then transferring the mixed solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal crystallization for 12 hours at 170 ℃, centrifuging the reaction solution, collecting a solid product, washing the solid product with deionized water and ethanol to be neutral, drying the solid product for 12 hours at 100 ℃, roasting the solid product for 5 hours at 550 ℃, tabletting, grinding and screening the roasted sample powder to obtain a catalyst with 40-60 meshes, and recording the catalyst as CuO-Fe 2 O 3 /TS-1@SBA-15。
The catalyst is used for treating pH-containing materials 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 1, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 The 100% removal rate of (2) reaches 270min, 330min, 360min and 120min respectively.
Example 2
(1) Adding TS-1 molecular sieve into the mixed solution containing copper nitrate and cerium nitrate, mixing and stirring for 3h, steaming at 70 ℃ for 1h, then placing the sample in a blast drying oven for drying at 100 ℃ for 12h, and roasting the dried sample at 500 ℃ for 5h to obtain the metal oxide/TS-1 molecular sieve catalyst which is named as CuO-CeO 2 TS-1, wherein copper accounts for 20% of the mass of the TS-1 molecular sieve, and cerium accounts for 5% of the mass of the TS-1 molecular sieve;
(2) Mixing tetraethoxysilane with 0.2mol/L HCl solution according to the ratio of 2g to 1mL, stirring for 5h at room temperature, standing and aging for 12h;
(3) Mixing template P123 with 0.6mol/L HCl solution according to the ratio of 2g to 1mL to prepare template dilute acid solution, and performing the step (1) of CuO-CeO 2 Adding the TS-1 catalyst into the mixture, stirring the mixture for 2 hours, then adding the silicon source diluted acid solution obtained in the step (2), stirring the mixed solution at 30 ℃ for 5 hours, and stirring the CuO-CeO 2 The solid-to-liquid ratio g/mL of the catalyst/TS-1 and the template agent dilute acid solution is 1:12, and CuO-CeO 2 The solid-to-liquid ratio g of the TS-1 catalyst to the silicon source dilute acid solution is 1:3;
(4) Adjusting pH=4.5 of the mixed solution obtained in the step (3) by adopting ammonia water, then transferring the mixed solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal crystallization for 30 hours at 150 ℃, centrifuging the reaction solution, collecting a solid product, washing the solid product with deionized water and ethanol to be neutral, drying the solid product at 100 ℃ for 12 hours, roasting the solid product at 600 ℃ for 3 hours, tabletting, grinding and screening roasted sample powder to obtain a catalyst with 40-60 meshes, and recording the catalyst as CuO-CeO 2 /TS-1@SBA-15。
The catalyst is used for treating pH-containing materials 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 2, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 The 100% removal rate of (2) respectively reaches 360min, 420min, 480min and 210min.
Example 3
(1) Adding TS-1 molecular sieve into the mixed solution containing copper nitrate and lanthanum nitrate, mixing and stirring for 3h, steaming at 60 ℃ for 1.5h, then placing the sample in a blast drying oven for drying at 100 ℃ for 12h, and roasting the dried sample at 450 ℃ for 6h to obtain the metal oxide/TS-1 molecular sieve catalyst which is named as CuO-La 2 O 3 TS-1, wherein copper accounts for 20% of the mass of the TS-1 molecular sieve, and lanthanum accounts for 5% of the mass of the TS-1 molecular sieve;
(2) Ethyl orthosilicate was added to 0.8mol/L H in a ratio of 3g to 1mL 2 SO 4 Mixing the solutions, stirring at room temperature for 3h, standing and aging for 15h;
(3) Template F127 was mixed with 0.6mol/LH in a 1.5 g/1 mL ratio 2 SO 4 Mixing the solution to obtain a template agent dilute acid solution, and mixing the CuO-La in the step (1) 2 O 3 Adding the TS-1 catalyst, stirring for 1h, then adding the silicon source diluted acid solution in the step (2), stirring the mixed solution at 25 ℃ for 8h, and stirring the CuO-La 2 O 3 The solid-to-liquid ratio g/mL of the catalyst/TS-1 and the template agent dilute acid solution is 1:15, and CuO-La 2 O 3 The solid-to-liquid ratio g of the TS-1 catalyst to the silicon source dilute acid solution is 2:9;
(4) Adopting ammonia water to the mixed solution obtained in the step (3)Adjusting pH to be=5, transferring into a polytetrafluoroethylene autoclave, carrying out hydrothermal crystallization at 120 ℃ for 40 hours, centrifuging the reaction solution, collecting a solid product, washing with deionized water and ethanol to be neutral, drying at 100 ℃ for 12 hours, roasting at 500 ℃ for 5 hours, tabletting, grinding and screening the roasted sample powder to obtain a catalyst with 40-60 meshes, and recording as CuO-La 2 O 3 /TS-1@SBA-15。
The catalyst is used for treating pH-containing materials 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 3, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 The 100 percent removal rate of the catalyst reaches 330min, 410min, 440min and 210min respectively.
Example 4
(1) Adding TS-1 molecular sieve into mixed solution containing nickel nitrate and cerium nitrate, mixing and stirring for 5h, steaming at 50deg.C for 1.5h, then placing the sample in a forced air drying oven for drying at 100deg.C for 12h, and roasting the dried sample at 400deg.C for 6h to obtain metal oxide/TS-1 molecular sieve catalyst, which is named NiO-CeO 2 TS-1, wherein nickel accounts for 15% of the mass of the TS-1 molecular sieve, and cerium accounts for 0.5% of the mass of the TS-1 molecular sieve;
(2) Ethyl orthosilicate was added to 1mol/L H in a ratio of 4g to 1mL 2 SO 4 Mixing the solutions, stirring at room temperature for 5h, standing and aging for 30h;
(3) Template P123 was added to 0.8mol/L H in a 1 g/1 mL ratio 2 SO 4 Mixing the solutions to obtain a template agent dilute acid solution, and mixing NiO-CeO in the step (1) 2 Adding the TS-1 catalyst into the mixture, stirring the mixture for 2 hours, then adding the silicon source diluted acid solution obtained in the step (2), stirring the mixed solution at 35 ℃ for 4 hours, and stirring the NiO-CeO 2 The solid-to-liquid ratio g/mL of the catalyst/TS-1 and the template agent dilute acid solution is 1:14, and NiO-CeO 2 The solid-to-liquid ratio g of the TS-1 catalyst to the silicon source dilute acid solution is 6:15;
(4) Adjusting the pH value of the mixed solution obtained in the step (3) to be=5.5 by adopting ammonia water, then transferring the mixed solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal crystallization for 36 hours at 160 ℃, centrifuging the reaction solution, collecting a solid product, washing the solid product to be neutral by using deionized water and ethanol, drying the solid product at 100 ℃ for 12 hours,roasting at 600 deg.c for 5 hr, tabletting, grinding and sieving to obtain 40-60 mesh catalyst, named NiO-CeO 2 /TS-1@SBA-15。
The catalyst is used for treating pH-containing materials 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 4, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 The 100% removal rate of (2) reaches 270min, 330min, 400min and 160min respectively.
Example 5
(1) Adding TS-1 molecular sieve into mixed solution containing ferric nitrate and zirconium nitrate, mixing and stirring for 2h, steaming at 80deg.C for 0.5h, drying the sample in a blast drying oven at 100deg.C for 12h, and roasting the dried sample at 350deg.C for 6h to obtain metal oxide/TS-1 molecular sieve catalyst, denoted Fe 2 O 3 -ZrO 2 TS-1, wherein iron accounts for 20% of the mass of the TS-1 molecular sieve, and zirconium accounts for 3% of the mass of the TS-1 molecular sieve;
(2) Mixing tetraethoxysilane with 0.5mol/L HCl solution according to the ratio of 5g to 1mL, stirring for 8h at room temperature, standing and aging for 18h;
(3) Mixing template F127 with 0.2mol/L HCl solution according to the ratio of 1.2g to 1mL to prepare a template dilute acid solution, and carrying out the step (1) of Fe 2 O 3 -ZrO 2 Adding the TS-1 catalyst, stirring for 2h, then adding the silicon source diluted acid solution in the step (2), stirring the mixed solution at 35 ℃ for 4h, and adding Fe 2 O 3 -ZrO 2 The solid-to-liquid ratio g/mL of the TS-1 catalyst to the template agent dilute acid solution is 1:13, fe 2 O 3 -ZrO 2 The solid-to-liquid ratio g of the TS-1 catalyst to the silicon source dilute acid solution is 5:12;
(4) Adjusting the pH value of the mixed solution obtained in the step (3) to be=6 by adopting ammonia water, then transferring the mixed solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal crystallization for 36 hours at 120 ℃, centrifuging the reaction solution, collecting a solid product, washing the solid product to be neutral by using deionized water and ethanol, drying the solid product at 100 ℃ for 12 hours, roasting the solid product at 550 ℃ for 5 hours, tabletting, grinding and screening roasted sample powder to obtain a catalyst with 40-60 meshes, and marking the catalyst as Fe 2 O 3 -ZrO 2 /TS-1@SBA-15。
The catalyst is used for treating pH-containing materials 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 5, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 The 100% removal rate of (2) respectively reaches 240min, 270min, 360min and 150min.
Example 6
(1) Adding TS-1 molecular sieve into mixed solution containing cerium nitrate and lanthanum nitrate, mixing and stirring for 3h, steaming at 50deg.C for 1.5h, then placing the sample in a forced air drying oven for drying at 100deg.C for 12h, and roasting the dried sample at 600deg.C for 3h to obtain metal oxide/TS-1 molecular sieve catalyst, denoted CeO 2 -La 2 O 3 TS-1, wherein cerium accounts for 10% of the mass of the TS-1 molecular sieve, and lanthanum accounts for 5% of the mass of the TS-1 molecular sieve;
(2) Ethyl orthosilicate was added to 0.3mol/L H in a 1g to 1mL ratio 3 PO 4 Mixing the solutions, stirring at room temperature for 5h, standing and aging for 18h;
(3) Template F108 was added to 0.2mol/L H at a ratio of 1.7g to 1mL 3 PO 4 Mixing the solutions to obtain a template agent dilute acid solution, and mixing the CeO in the step (1) 2 -La 2 O 3 Adding the TS-1 catalyst into the mixture, stirring the mixture for 2 hours, then adding the silicon source diluted acid solution obtained in the step (2), stirring the mixed solution at 35 ℃ for 4 hours, and stirring the CeO 2 -La 2 O 3 The solid-to-liquid ratio g/mL of the catalyst/TS-1 and the template agent dilute acid solution is 1:11, and CeO 2 -La 2 O 3 The solid-to-liquid ratio g of the TS-1 catalyst to the silicon source dilute acid solution is 3:8;
(4) Adjusting pH=4 of the mixed solution obtained in the step (3) by adopting ammonia water, then transferring the mixed solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal crystallization for 36 hours at 120 ℃, centrifuging the reaction solution, collecting a solid product, washing the solid product with deionized water and ethanol to be neutral, drying the solid product at 100 ℃ for 12 hours, roasting the solid product at 550 ℃ for 5 hours, tabletting, grinding and screening the roasted sample powder to obtain a catalyst with 40-60 meshes, and recording the catalyst as CeO 2 -La 2 O 3 /TS-1@SBA-15。
The catalyst is used for the treatmentRegulating pH 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 6, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 The 100% removal rate of (2) respectively reaches 180min, 240min, 330min and 180min.
Comparative example 1
(1) Adding TS-1 molecular sieve into copper nitrate solution, mixing and stirring for 4h, steaming at 80deg.C for 0.5h, drying at 100deg.C for 12h, calcining at 550deg.C for 5h to obtain metal oxide/TS-1 molecular sieve catalyst, denoted CuO/TS-1, and treating pH-containing catalyst 3 、H 2 S、AsH 3 、NH 3 The results are shown in FIG. 7, from which the pH can be seen 3 、H 2 S、AsH 3 、NH 3 100% removal of (C) was achieved at 150min, 210min, 240min and 120min, respectively, indicating that the CuO/TS-1 catalyst was pH sensitive 3 、H 2 S、AsH 3 、NH 3 The removal effect is less ideal than that of the core-shell catalyst prepared by the invention.
Claims (7)
1. Catalyst for purifying tail gas of submerged arc furnace and simultaneously removing PH in tail gas of submerged arc furnace 3 、H 2 S、AsH 3 、NH 3 Is applied to the application of the system;
the preparation method of the catalyst for purifying the tail gas of the submerged arc furnace comprises the following steps:
(1) Adding a TS-1 molecular sieve into a metal salt solution, mixing and stirring for 2-5 hours, and drying and roasting after rotary steaming to obtain a metal oxide/TS-1 molecular sieve catalyst;
(2) Adding a silicon source into a dilute acid solution, stirring at room temperature, standing and aging to obtain a silicon source dilute acid solution;
(3) Dissolving a template agent in a dilute acid solution to obtain a template agent dilute acid solution, adding the metal oxide/TS-1 molecular sieve catalyst obtained in the step (1), stirring for 1-2 h, adding the silicon source dilute acid solution obtained in the step (2) for hydrolysis, and stirring the mixed solution at 25-35 ℃ for reacting for 4-12 h;
(4) Adjusting the pH value of the reaction product in the step (3) to 2-6, then transferring the reaction product to a polytetrafluoroethylene autoclave for hydrothermal crystallization, centrifuging the reaction liquid, collecting a solid product, washing the solid product to be neutral by deionized water and ethanol, drying and roasting to obtain the catalyst for purifying the tail gas of the submerged arc furnace;
the metal salt is metal I salt and metal II salt, wherein the metal I salt is one of copper salt, ferric salt and nickel salt, the metal II salt is one of cerium salt, zirconium salt and lanthanum salt, and the metal I accounts for 10-40% of the mass of the TS-1 molecular sieve; the metal II accounts for 0.5 to 5 percent of the mass of the TS-1 molecular sieve;
in the step (2), the mass volume ratio g of the silicon source and the diluted acid solution is (0.5-5) 1, the mass volume ratio g of the template agent and the diluted acid solution in the step (3) is (1-2) 1, the solid-liquid ratio g of the metal oxide/TS-1 molecular sieve catalyst and the template agent diluted acid solution is (1:10-15), and the solid-liquid ratio g of the metal oxide/TS-1 molecular sieve catalyst and the silicon source diluted acid solution is (1-6) 3-15.
2. The use according to claim 1, characterized in that: in the step (1), the rotary steaming is carried out at the temperature of 40-80 ℃ for 0.5-1.5 h.
3. The use according to claim 1, characterized in that: the roasting in the step (1) and the step (4) is carried out for 3 to 6 hours at the temperature of 350 to 600 ℃.
4. The use according to claim 1, characterized in that: the silicon source is one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate, the stirring time of the silicon source in a dilute acid solution is 3-12 h, and the silicon source is kept stand and aged for 4-36 h.
5. The use according to claim 1, characterized in that: the dilute acid in the step (2) and the step (3) is one of hydrochloric acid, sulfuric acid and phosphoric acid, and the concentration of the dilute acid solution is 0.2-1 mol/L.
6. The use according to claim 1, characterized in that: the template agent is triblock copolymer P123, F127 or F108.
7. The use according to claim 1, characterized in that: the hydrothermal crystallization temperature is 100-180 ℃ and the time is 10-72 h.
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| CN105233806A (en) * | 2015-10-20 | 2016-01-13 | 昆明理工大学 | Preparation method of adsorbent for purifying hydrogen sulfide, hydrogen phosphide and arsenic hydride simultaneously |
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| CN112337504A (en) * | 2020-11-11 | 2021-02-09 | 昆明理工大学 | Core-shell catalyst, preparation method thereof and method for treating industrial tail gas |
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| CN105233806A (en) * | 2015-10-20 | 2016-01-13 | 昆明理工大学 | Preparation method of adsorbent for purifying hydrogen sulfide, hydrogen phosphide and arsenic hydride simultaneously |
| CN110841641A (en) * | 2019-11-23 | 2020-02-28 | 青岛联信催化材料有限公司 | Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof |
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