CN110124653B - Catalyst for decomposing hydrogen sulfide and preparation method and application thereof - Google Patents
Catalyst for decomposing hydrogen sulfide and preparation method and application thereof Download PDFInfo
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- CN110124653B CN110124653B CN201810136780.0A CN201810136780A CN110124653B CN 110124653 B CN110124653 B CN 110124653B CN 201810136780 A CN201810136780 A CN 201810136780A CN 110124653 B CN110124653 B CN 110124653B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 26
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 238000001241 arc-discharge method Methods 0.000 claims description 3
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 29
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 239000011651 chromium Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910003074 TiCl4 Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 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
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the field of hydrogen sulfide decomposition, and discloses a catalyst for decomposing hydrogen sulfide, a preparation method and application thereof, wherein the catalyst comprises a carrier and an active metal component loaded on the carrier, the carrier contains carbon nano tubes, the active metal component is at least one selected from Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn and Cd, and the content of the carbon nano tubes is 5-90 wt% and the content of the active metal component is 1-50 wt% in terms of oxides based on the total weight of the catalyst. When the catalyst for decomposing hydrogen sulfide provided by the invention is used for decomposing hydrogen sulfide into elemental sulfur and hydrogen, the catalyst has higher hydrogen sulfide conversion rate compared with the catalyst provided by the prior art.
Description
Technical Field
The invention relates to the field of hydrogen sulfide decomposition, in particular to a catalyst for decomposing hydrogen sulfide and a preparation method and application thereof.
Background
Hydrogen sulfide (H)2S) is a highly toxic and malodorous acidic gas, which not only can cause corrosion of materials such as metal, but also can easily cause catalyst poisoning and inactivation in chemical production; in addition, hydrogen sulfide can also harm human health and cause environmental pollution. Therefore, in the case of performing a detoxification treatment of a large amount of hydrogen sulfide gas generated in industrial fields such as petroleum, natural gas, coal, and mineral processing, a solution is urgently needed in view of process requirements, equipment maintenance, environmental requirements, and the like.
Currently, the hydrogen sulfide is treated by the Claus process, which partially oxidizes hydrogen sulfide to produce sulfur and water. Although the method solves the problem of harmlessness of hydrogen sulfide, a large amount of hydrogen resources are lost.
With the increase of the processing amount of high-sulfur crude oil in China, the amount of the hydrogen sulfide-containing acidic tail gas which is a byproduct of an oil refining hydrofining unit is increased year by year, and the amount of hydrogen required by hydrofining is increased; in addition, hydrogen is used as a main raw material in chemical process such as oil hydrocracking, low-carbon alcohol synthesis, synthetic ammonia and the like, and the demand amount is also considerable. Therefore, the direct decomposition of the hydrogen sulfide is an ideal hydrogen sulfide resource utilization technical route, the hydrogen sulfide is harmless, the hydrogen and the elemental sulfur can be produced, the cyclic utilization of the hydrogen resource in the petroleum processing process can be realized, and the emission of a large amount of carbon dioxide brought by the conventional hydrocarbon reforming hydrogen production can be reduced.
At present, the hydrogen sulfide decomposition method mainly comprises the following steps: high temperature decomposition, electrochemical, photocatalytic, and low temperature plasma methods. Among the aforementioned methods, the pyrolysis method is relatively mature in industrial technology, but the thermal decomposition of hydrogen sulfide strongly depends on the reaction temperature and is limited by the thermodynamic equilibrium, and the conversion rate of hydrogen sulfide is only 20% even if the reaction temperature is 1000 ℃ or higher. In addition, the high temperature conditions place high demands on reactor materials, which also increases operating costs. In addition, since the thermal decomposition conversion of hydrogen sulfide is low, a large amount of hydrogen sulfide gas needs to be separated from the tail gas and circulated in the system, thereby reducing the efficiency of the apparatus and increasing the energy consumption, which all bring difficulties to large-scale industrial application thereof. Although the adoption of the membrane technology can effectively separate products, thereby breaking balance limitation and improving the conversion rate of hydrogen sulfide, the thermal decomposition temperature often exceeds the limit heat-resistant temperature of the membrane, so that the structure of the membrane material is damaged. The electrochemical method has the defects of multiple operation steps, serious equipment corrosion, poor reaction stability, low efficiency and the like. The photocatalytic method for decomposing hydrogen sulfide mainly refers to the research of photocatalytic water decomposition, and the research focuses on the aspects of developing high-efficiency semiconductor photocatalysts and the like. The method for decomposing the hydrogen sulfide by utilizing the solar energy has the advantages of low energy consumption, mild reaction conditions, simple operation and the like, and is a relatively economic method. However, this method has problems such as a small treatment amount, low catalytic efficiency, and easy deactivation of the catalyst.
Compared with other decomposition methods, the low-temperature plasma method has the advantages of simple operation, small device volume, high energy efficiency and the like, and the involved reaction has high controllability and can be flexibly applied under the conditions of small treatment capacity and difficult centralized treatment. In addition, the hydrogen sulfide decomposition device has the characteristics of high energy density and shortened reaction time, can realize effective decomposition of hydrogen sulfide at a lower temperature, and is suitable for occasions with different scales, dispersed layouts and variable production conditions. Besides, the low-temperature plasma method recovers hydrogen resources while recovering sulfur, and can realize resource utilization of hydrogen sulfide.
CN102408095A uses medium to block discharge and light catalyst to decompose hydrogen sulfide, and its method is to pack solid catalyst with light catalytic activity in plasma zone, however, this method has the disadvantage that sulfur produced by hydrogen sulfide decomposition will deposit under catalyst bed.
CN103495427A discloses a method for preparing a supported metal sulfide catalyst by using low-temperature plasma, which is characterized in that hydrogen sulfide gas or gas containing hydrogen sulfide is ionized by gas discharge to form uniformly distributed low-temperature plasma, and the low-temperature plasma is directly interacted with a supported metal salt precursor to generate metal sulfide. Because the catalyst is prevented from being exposed to overhigh temperature, the prepared catalyst does not have the phenomenon of thermal agglomeration, thereby having smaller particle size and higher dispersity. However, this prior art provides a catalyst which, when used in the decomposition reaction of hydrogen sulfide, does not have a high conversion of hydrogen sulfide.
Disclosure of Invention
The invention aims to overcome the defect of low hydrogen sulfide conversion rate of a catalyst for catalyzing hydrogen sulfide to decompose and generate elemental sulfur and hydrogen provided by the prior art, and provides a novel catalyst for decomposing hydrogen sulfide.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for decomposing hydrogen sulfide, comprising a carrier and an active metal component supported on the carrier, wherein the carrier contains carbon nanotubes, the active metal component is at least one selected from the group consisting of Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn and Cd, and the content of the carbon nanotubes is 5 to 90 wt% and the content of the active metal component is 1 to 50 wt% in terms of an oxide, based on the total weight of the catalyst.
A second aspect of the present invention provides a method for producing the hydrogen sulfide decomposing catalyst of the first aspect described above, the method comprising: the carrier and the raw material containing the active metal component are contacted in the presence of a solvent.
A third aspect of the present invention provides the use of the hydrogen sulfide decomposing catalyst of the first aspect described above in a hydrogen sulfide decomposition reaction in a dielectric barrier discharge plasma reactor.
When the catalyst for decomposing hydrogen sulfide is used for decomposing hydrogen sulfide into elemental sulfur and hydrogen, the catalyst provided by the invention has higher hydrogen sulfide conversion rate compared with the catalyst provided by the prior art; particularly, when the catalyst for decomposing hydrogen sulfide provided by the invention is used for the decomposition reaction of hydrogen sulfide in a low-temperature plasma reactor with dielectric barrier discharge, the catalyst can obtain obviously higher hydrogen sulfide conversion rate on the premise of relatively lower energy consumption.
In addition, the method for preparing the catalyst for decomposing the hydrogen sulfide has the advantages of simple operation and low preparation cost.
Drawings
Fig. 1 is a schematic structural view of a low-temperature plasma reactor used in a test example of the present invention.
Description of the reference numerals
1. Inner cylinder 2, outer cylinder
11. Reactor inlet 21, heat transfer medium inlet
12. Gas product outlet 22 and heat-conducting medium outlet
13. Liquid product outlet
3. Center electrode
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, in a first aspect of the present invention, there is provided a catalyst for decomposing hydrogen sulfide, comprising a carrier and an active metal component supported on the carrier, wherein the carrier contains carbon nanotubes, the active metal component is at least one selected from the group consisting of Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn and Cd, and the content of the carbon nanotubes is 5 to 90 wt% and the content of the active metal component is 1 to 50 wt% in terms of an oxide, based on the total weight of the catalyst.
Preferably, the active metal component is a mixture of a first component and a second component, and the first component is Ti and/or Zr, and the second component is selected from at least one of V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn and Cd. The inventors of the present invention have found that a catalyst containing the first component and the second component of the present invention as active metal components has a higher conversion rate of hydrogen sulfide when used in a decomposition reaction of hydrogen sulfide. More preferably, the second component is at least one selected from the group consisting of Mo, W, Mn, Co, Ni and Cr.
According to a preferred embodiment, in the mixture comprising the first component and the second component, the content of the first component is 7 to 35% by weight calculated on element and the content of the second component is 65 to 93% by weight calculated on element. The amounts of the first component and the second component are based on the total weight of the mixture.
According to another preferred embodiment, in the mixture comprising the first component and the second component, the content of the first component is 12 to 30% by weight calculated on element and the content of the second component is 70 to 88% by weight calculated on element.
Preferably, the content of the carbon nano tube is 10-70 wt% and the content of the active metal component is 3-45 wt% in terms of oxide, based on the total weight of the catalyst; more preferably, the content of the carbon nanotubes is 10 to 50 wt% and the content of the active metal component is 5 to 40 wt% in terms of oxide, based on the total weight of the catalyst.
In particular, in the catalyst of the present invention, when the active metal component is a mixture of a first component and a second component, and the first component is Ti and/or Zr, the second component is at least one selected from Mo, W, Mn, Co, Ni and Cr, and the first component is present in an amount of 12 to 30 wt% by element, the second component is present in an amount of 70 to 88 wt% by element, and the support contains carbon nanotubes in an amount of 10 to 50 wt% by total weight of the catalyst, and the active metal component is present in an amount of 5 to 40 wt% by oxide, the catalyst has a more stable catalytic efficiency in catalyzing a decomposition reaction of hydrogen sulfide.
According to a preferred embodiment, the support also contains silica and/or alumina as an additive.
Preferably, the content of the additive (the total content of the silicon oxide and the aluminum oxide) is 1-60 wt% based on the total weight of the catalyst; more preferably 10 to 55 wt%.
In particular, the inventors of the present invention have found that when the catalyst of the present invention further contains silica and/or alumina as an additive, the catalyst provided by the present invention enables higher conversion of hydrogen sulfide when used in a hydrogen sulfide decomposition reaction in a dielectric barrier discharge plasma reactor.
Preferably, the carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
In the present invention, it is preferable that the carbon nanotube is produced by at least one method selected from the group consisting of a catalytic pyrolysis method, an arc discharge method, a template method, and a laser evaporation method.
The carbon nanotubes of the present invention may also be commercially available products.
The present invention is not particularly limited with respect to the specific operation method of the catalytic pyrolysis method, the arc discharge method, the template method and the laser evaporation method, and may be an operation method which is conventional in the art.
The carbon nanotubes may be subjected to pretreatment conventionally used in the art, such as acid treatment, etc., and the present invention is not particularly limited to a specific operation method, and those skilled in the art should not be construed as limiting the present invention.
As described above, the second aspect of the present invention provides a method for producing the hydrogen sulfide decomposing catalyst of the first aspect, comprising: the carrier and the raw material containing the active metal component are contacted in the presence of a solvent.
Preferably, the contacting conditions include: the temperature is 0-60 ℃, and the time is 1-24 h.
Preferably, the solvent is selected from at least one of water, methanol, ethanol, dimethylsulfoxide, tetrahydrofuran, pyridine, acetonitrile, n-propanol, and dimethylformamide.
The method of the contact of the present invention may be, for example, a dipping method.
As mentioned above, a third aspect of the present invention provides the use of the catalyst of the first aspect in a hydrogen sulfide decomposition reaction in a dielectric barrier discharge plasma reactor.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used were commercially available unless otherwise specified.
The composition of the catalysts in the following examples was obtained by X-ray photoelectron spectroscopy (XPS).
The hydrogen sulfide conversion in the following examples was calculated according to the following formula:
percent conversion of hydrogen sulfide ═ moles of converted hydrogen sulfide/moles of initial hydrogen sulfide × 100%
The energy consumption for decomposing hydrogen sulfide in the following examples was measured by an oscilloscope and calculated using lissajous figures.
Example 1
To 200mL of DMF was added 2.5g of single-walled carbon nanotubes (available from Beijing)German island gold science and technology Co., Ltd.), 0.3g of TiCl40.5g of alumina and 0.6g of chromium nitrate (anhydrate) were stirred at 40 ℃ for 6h, then dried in a drying oven at 100 ℃ for 8h and calcined at 260 ℃ for 2h to give catalyst Cat 1.
The composition of Cat1 was found to be: the total content of Ti and Cr in terms of oxides, based on the total weight of the catalyst, was 14.6% by weight, and the weight ratio of the contents of Ti and Cr elements was 1: 3.89, the content of alumina is 14.3 weight percent, and the balance is carbon nano tubes.
Example 2
This example was carried out in a similar manner to example 1, except that:
in this example, the solvent was methanol, the carrier was multi-walled carbon nanotubes (available from Beijing Deke island technologies, Ltd.) and alumina, and the active metal component was ZrCl4And manganese nitrate under conditions of stirring at 35 ℃ for 10 hours, this example gives catalyst Cat 2.
The composition of Cat2 was found to be: the total content of Zr and Mn in terms of oxide was 26.9 wt%, based on the total weight of the catalyst, and the elemental content weight ratio of Zr and Mn was 1: 5.59, the content of the alumina is 20.3 weight percent, and the balance is the carbon nano tube.
Example 3
This example was carried out in a similar manner to example 1, except that:
the solvent in this example is methanol, the support is multi-walled carbon nanotubes and silica (obtained from silica sol), and the active metal component is TiCl4And (NH)4)6Mo7O24(containing 4 molecules of water) under stirring at 25 ℃ for 12h, this example gives catalyst Cat 3.
The composition of Cat3 was found to be: the total content of Ti and Mo in terms of oxide was 34.6 wt%, based on the total weight of the catalyst, and the weight ratio of the contents of Ti and Mo elements was 1: 2.98, the content of silicon oxide is 25.7 weight percent, and the balance is carbon nano tubes.
Example 4
This example was carried out in a similar manner to example 1, except that:
the active metal component in this example consists of TiCl4And (NH)4)6W12O39Obtained, this example gives the catalyst Cat 4.
The composition of Cat4 was found to be: the total content of Ti and W in terms of oxides was 15.7 wt%, based on the total weight of the catalyst, and the weight ratio of the element contents of Ti and W was 1: 4.27, the content of alumina is 18.6 weight percent, and the balance is carbon nano tubes.
Example 5
This example was carried out in a similar manner to example 1, except that:
the active metal component in this example consists of TiCl4And nickel nitrate (containing 6 molecules of water), this example yielded catalyst Cat 5.
The composition of Cat5 was found to be: the total content of Ti and Ni in terms of oxide was 19.7 wt% based on the total weight of the catalyst, and the weight ratio of the element contents of Ti and Ni was 1: 3.76, the content of the alumina is 22.7 weight percent, and the balance is the carbon nano tube.
Example 6
This example was carried out in a similar manner to example 3, except that:
the active metal component in this example consists of ZrCl4And cobalt nitrate (containing 6 molecules of water), this example gave catalyst Cat 6.
The composition of Cat6 was found to be: the total content of Zr and Co in terms of oxide was 24.6 wt% based on the total weight of the catalyst, and the weight ratio of the contents of Zr and Co elements was 1: 5.21, the content of the silicon oxide is 26.3 weight percent, and the balance is the carbon nano tube.
Example 7
This example was carried out in a similar manner to example 1, except that:
the amount of alumina added in this example was such that the alumina content in the resulting catalyst was 58.7 wt%.
The procedure is as in example 1 except that catalyst Cat7 is obtained.
The composition of Cat7 was found to be: the total content of Ti and Cr in terms of oxides, based on the total weight of the catalyst, was 14.1 wt%, and the weight ratio of the contents of Ti and Cr elements was 1: 3.63, the content of the alumina is 58.7 weight percent, and the balance is the carbon nano tube.
Example 8
This example was carried out in a similar manner to example 1, except that:
in this example, no alumina was included and the amount of single-walled carbon nanotubes was 3 g.
The procedure is as in example 1 except that catalyst Cat8 is obtained.
The composition of Cat8 was found to be: the total content of Ti and Cr in terms of oxides is 13.5 wt%, based on the total weight of the catalyst, and the weight ratio of the contents of Ti and Cr elements is 1: 3.45, and the balance of carbon nanotubes.
Example 9
This example was carried out in a similar manner to example 2, except that:
ZrCl in this example4And manganese nitrate were added in such an amount that the catalyst Cat9 obtained in this example had a composition: the total content of Zr and Mn in terms of oxide was 44.3 wt%, based on the total weight of the catalyst, and the elemental content weight ratio of Zr and Mn was 1: 5.26, the content of alumina is 17.5 weight percent, and the balance is carbon nano tubes.
Example 10
This example was carried out in a similar manner to example 3, except that:
in this example, TiCl4And (NH)4)6Mo7O24The amount of addition (containing 4 molecules of water) was such that the composition of catalyst Cat10 obtained in this example was: the total content of Ti and Mo in terms of oxide was 34.4 wt%, based on the total weight of the catalyst, and the weight ratio of the contents of Ti and Mo elements was 1: 1.85, the content of silicon oxide is 25.0 weight percent, and the balance is carbon nano tubes.
Example 11
This example was carried out in a similar manner to example 3, except that:
in this example, TiCl4And (NH)4)6Mo7O24The amount of addition (containing 4 molecules of water) was such that the composition of catalyst Cat11 obtained in this example was: the total content of Ti and Mo in terms of oxide was 34.0 wt% based on the total weight of the catalyst, and the content weight ratio of the elements Ti and Mo was 1: 18.5, the content of the silicon oxide is 25.2 weight percent, and the balance is the carbon nano tube.
Example 12
This example was carried out in a similar manner to example 3, except that:
the active metal components of this example consisted of manganese Nitrate and (NH)4)6Mo7O24(containing 4 molecules of water), and the composition of the catalyst Cat12 obtained in this example was: the total content of Mn and Mo in terms of oxide was 35.6 wt%, based on the total weight of the catalyst, and the element content weight ratio of Mn and Mo was 1: 3.76, the content of the silicon oxide is 25.5 weight percent, and the balance is the carbon nano tube.
Example 13
This example was carried out in a similar manner to example 3, except that:
the active metal component of this example consists of (NH)4)6Mo7O24(containing 4 molecules of water), and the composition of the catalyst Cat13 obtained in this example was: the total content of Mo in terms of oxide was 36.7 wt%, the content of silica was 24.8 wt%, and the balance was carbon nanotubes, based on the total weight of the catalyst.
Example 14
This example was carried out in a similar manner to example 1, except that:
the active metal component in this example consists of TiCl4And iron nitrate (containing 9 molecules of water), this example gave catalyst Cat 14.
The composition of Cat14 was found to be: the total content of Ti and Fe in terms of oxides is 14.8 wt%, based on the total weight of the catalyst, and the weight ratio of the contents of Ti and Fe elements is 1: 3.82, the content of alumina is 14.7 weight percent, and the balance is carbon nano tubes.
Example 15
This example was carried out in a similar manner to example 1, except that:
the active metal component in this example consists of TiCl4And copper nitrate (containing 3 molecules of water), this example gave catalyst Cat 15.
The composition of Cat15 was found to be: the total content of Ti and Cu in terms of oxide was 15.0 wt%, based on the total weight of the catalyst, and the elemental content weight ratio of Ti and Cu was 1: 3.85, the content of alumina is 14.4 weight percent, and the balance is carbon nano tubes.
Example 16
This example was carried out in a similar manner to example 1, except that:
the active metal component in this example consists of TiCl4And zinc nitrate (containing 6 molecules of water), this example gives catalyst Cat 16.
The composition of Cat16 was found to be: the total content of Ti and Zn in terms of oxides, based on the total weight of the catalyst, was 14.6 wt%, and the weight ratio of the elemental contents of Ti and Zn was 1: 3.84, the content of alumina is 14.6 weight percent, and the balance is carbon nano tubes.
Comparative example 1
This comparative example was carried out in a similar manner to example 1, except that:
the support in this comparative example was only alumina and no carbon nanotubes, resulting in catalyst D-Cat 1.
Results the composition of D-Cat1 was: the total content of Ti and Cr in terms of oxides is 15.1 wt%, based on the total weight of the catalyst, and the weight ratio of the contents of Ti and Cr elements is 1: 3.81 and the balance of aluminum oxide.
Comparative example 2
This comparative example was carried out in a similar manner to example 1, except that:
the carriers in this comparative example were alumina and carbon nanotubes, and the amounts of alumina and carbon nanotubes were such that the composition of the prepared catalyst D-Cat2 was: the total content of Ti and Cr in terms of oxides is 15.7 wt%, based on the total weight of the catalyst, and the weight ratio of the contents of Ti and Cr elements is 1: 3.85, the content of the carbon nano tube is 1.3 percent by weight, and the balance is alumina.
Test example
Test example a low-temperature plasma reactor shown in fig. 1 was used to perform a decomposition reaction of hydrogen sulfide, and specifically, the structure of the low-temperature plasma reactor shown in fig. 1 was:
the reactor comprises:
an inner cylinder 1 provided with a reactor inlet 11, a gas product outlet 12 and a liquid product outlet 13, wherein all the side walls of the inner cylinder are formed by a barrier medium, the material forming the barrier medium is hard glass, and 200mL of the catalyst obtained in the previous examples and comparative examples is filled in the inner cylinder of the reactor in each test;
the outer cylinder 2 is nested outside the inner cylinder, and a heat-conducting medium inlet 21 and a heat-conducting medium outlet 22 are respectively arranged on the outer cylinder;
the central electrode 3 is arranged at the central axis position of the inner cylinder, and the material forming the central electrode is a stainless steel metal rod;
the space between the inner wall of the outer cylinder and the outer wall of the inner cylinder is filled with heat-conducting medium (specifically LiCl and AlCl with the mol ratio of 1:1 in a molten state)3) The heat conducting medium also serves as a liquid grounding electrode;
a distance L between the outer side wall of the central electrode and the inner side wall of the blocking medium1And thickness D of barrier medium1The ratio of (A) to (B) is 6: 1;
the position of the gas product outlet is relative to the height H of the bottom of the inner cylinder1And the length L of the discharge region containing the barrier medium2The proportion relation between the components is as follows: h1：L2＝1：30；
The volume of the inner cylinder of the reactor in this example was 500 mL.
Gas containing hydrogen sulfide enters the inner cylinder of the reactor from the upper part of the inner cylinder of the reactor, a gas product is led out from a gas product outlet positioned at the lower part of the inner cylinder of the reactor, and elemental sulfur is led out from a liquid product outlet positioned at the bottom of the reactor; and the heat-conducting medium is introduced from the lower part of the outer barrel of the reactor and is led out from the upper part of the outer barrel of the reactor.
The operation steps of the low-temperature plasma reactor are as follows:
nitrogen gas is introduced into the inner cylinder of the low-temperature plasma reactor from the reactor inlet to purge the discharge region of air, and the gas is withdrawn from the gaseous product outlet and the liquid product outlet. Meanwhile, a heat-conducting medium is introduced into the outer cylinder from the heat-conducting medium inlet, the introduced heat-conducting medium is led out from the heat-conducting medium outlet, and the temperature of the heat-conducting medium is kept at 150 ℃.
Then introducing H into the inner cylinder of the low-temperature plasma reactor from the inlet of the reactor2S/Ar mixed gas, in which H2The volume fraction of S was 20%, and the flow rate of the mixed gas was controlled so that the average residence time of the gas in the discharge zone was 12.5S. H2And (3) introducing the S/Ar mixed gas into the reactor for 30min, switching on an alternating-current high-voltage power supply, and adjusting the voltage and the frequency to form a plasma discharge field between the central electrode and the liquid grounding electrode. Wherein the discharge conditions are as follows: the voltage was 20.5kV, the frequency was 7.5kHz, and the current was 1.05A. The hydrogen sulfide gas is ionized in the discharge area and decomposed into hydrogen and elemental sulfur, and the elemental sulfur generated by discharge slowly flows down along the inner cylinder wall and flows out from the liquid product outlet. The gas flows out from the gas product outlet after the reaction.
Test H was carried out for 10min, 20min and 60min after the decomposition reaction was continued2S conversion, the results are listed in table 1.
And the results of energy consumption for decomposition of hydrogen sulfide are also shown in Table 1, "eV/H2S molecule "means 1 molecule of H per decomposition2S required energy.
TABLE 1
As can be seen from the results of table 1, the catalyst for decomposing hydrogen sulfide provided by the present invention allows the conversion rate of hydrogen sulfide to be significantly improved when used in the decomposition reaction of hydrogen sulfide.
In addition, the catalyst for decomposing hydrogen sulfide provided by the invention can ensure that the conversion rate of hydrogen sulfide in the decomposition reaction of hydrogen sulfide is stably maintained at a high level.
The catalyst for decomposing the hydrogen sulfide provided by the invention can ensure that the energy consumption for decomposition in the decomposition reaction of the hydrogen sulfide is low.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A catalyst for decomposing hydrogen sulfide by dielectric barrier discharge comprises a carrier and an active metal component loaded on the carrier, wherein the carrier contains carbon nano tubes, the active metal component is a mixture of a first component and a second component, the first component is Ti and/or Zr, the second component is at least one selected from Mo, W, Mn, Co, Ni and Cr, the content of the carbon nano tubes is 10-70 wt% based on the total weight of the catalyst, and the content of the active metal component is 3-45 wt% based on oxides.
2. The catalyst according to claim 1, wherein in the mixture containing the first component and the second component, the content of the first component by element is 7 to 35% by weight, and the content of the second component by element is 65 to 93% by weight.
3. The catalyst according to claim 1, wherein in the mixture containing the first component and the second component, the content of the first component is 12 to 30% by weight in terms of element, and the content of the second component is 70 to 88% by weight in terms of element.
4. The catalyst according to any one of claims 1 to 3, wherein the carbon nanotubes are contained in an amount of 10 to 50 wt% and the active metal component is contained in an amount of 5 to 40 wt% in terms of oxide, based on the total weight of the catalyst.
5. A catalyst according to any one of claims 1 to 3, wherein the support further comprises silica and/or alumina as an additive.
6. The catalyst according to claim 5, wherein the additive is present in an amount of 1 to 60 wt.%, based on the total weight of the catalyst.
7. The catalyst of claim 5, wherein the additive is present in an amount of 10 to 55 wt.%, based on the total weight of the catalyst.
8. The catalyst according to any of claims 1-3, wherein the carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
9. The catalyst according to claim 1, wherein the carbon nanotube is prepared by at least one method selected from the group consisting of a catalytic pyrolysis method, an arc discharge method, a templating method, and a laser evaporation method.
10. A method of preparing the catalyst of any one of claims 1-9, the method comprising: the carrier and the raw material containing the active metal component are contacted in the presence of a solvent.
11. The method of claim 10, wherein the conditions of the contacting comprise: the temperature is 0-60 ℃, and the time is 1-24 h.
12. The method of claim 10, wherein the solvent is selected from at least one of water, methanol, ethanol, dimethylsulfoxide, tetrahydrofuran, pyridine, acetonitrile, n-propanol, and dimethylformamide.
13. Use of a catalyst according to any one of claims 1 to 9 in a hydrogen sulphide decomposition reaction in a dielectric barrier discharge plasma reactor.
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