CN114950493A - Molybdenum-based sulfide supported catalyst and in-situ preparation method and application thereof - Google Patents
Molybdenum-based sulfide supported catalyst and in-situ preparation method and application thereof Download PDFInfo
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- CN114950493A CN114950493A CN202210673728.5A CN202210673728A CN114950493A CN 114950493 A CN114950493 A CN 114950493A CN 202210673728 A CN202210673728 A CN 202210673728A CN 114950493 A CN114950493 A CN 114950493A
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- molybdenum
- supported catalyst
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- sulfide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 47
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 26
- 239000011733 molybdenum Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 238000011068 loading method Methods 0.000 claims abstract description 23
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000004073 vulcanization Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000011549 displacement method Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 229940094933 n-dodecane Drugs 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 239000003921 oil Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a molybdenum-based sulfide supported catalyst and an in-situ preparation method and application thereof x SupportWherein x is>2, loading auxiliary agent metal ions on the MoS x On the carrier, finally, the molybdenum-based sulfide supported catalyst can be prepared by heating and in-situ vulcanization treatment in protective atmosphere. The preparation method of the supported catalyst has simple process, avoids the random distribution of the active components of the auxiliary agent on the surface of the carrier through double in-situ reactions, namely in-situ loading and in-situ vulcanization, effectively improves the dispersion and the utilization rate of the auxiliary agent, and the auxiliary agent stays at the Edge of a sulfur vacancy of molybdenum sulfide to form an auxiliary agent-Edge catalytic active center, thereby providing a simple, high-efficiency and environment-friendly method for preparing the high-activity sulfide supported catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a molybdenum-based sulfide supported catalyst, an in-situ preparation method thereof and application thereof in hydrodesulfurization reaction.
Background
The carrier not only supports the catalyst but also has a function of dispersing the active component in addition to supporting the active component at a site where the substance is subjected to a chemical reaction. The preparation method of the existing metal sulfide supported catalyst mainly comprises the following steps: firstly, an impregnation method, in which a catalyst carrier is added into an active component aqueous solution, and is soaked for a period of time, so that the carrier and the active component in an impregnation solution reach an adsorption equilibrium state, and at the moment, the carrier is dried and roasted to prepare the catalyst, for example, patent CN114073980A discloses a method for preparing a hydrodesulfurization catalyst by loading polyoxometallate on a molecular sieve and then carrying out vulcanization; a second thermal fusion method; melting each component of the catalyst under a high temperature condition into a uniformly distributed mixed state, an oxide solid solution or an alloy solid solution, cooling and crushing to prepare the catalyst, for example, patent CN114073970A discloses a vulcanization type hydrodesulfurization catalyst, heating and refluxing an active metal compound and a vulcanizing agent, and then loading on a carrier to calcine to obtain the vulcanization type hydrodesulfurization catalyst; the chemical vapor deposition method is a process technology in which one or more compounds containing film-forming elements and elementary gases are introduced into a reaction chamber in which a substrate is placed, and a solid film is deposited on the surface of a substrate by means of a space vapor chemical reaction, for example, patent CN114231945A discloses a method for preparing a molybdenum disulfide film by using a chemical vapor deposition method, in which sulfur powder is sublimated at a high temperature to react with vapor phase molybdenum trioxide, and a molybdenum disulfide film is generated on the substrate. In the roasting operation process, metal salt is needed to be decomposed at high temperature, and the formed metal oxide species and a carrier generate stronger interaction, even form a compound with the carrier, so that the metal oxide species cannot be completely sulfurized in the sulfurization process, and the catalyst has less active phase and lower activity.
Disclosure of Invention
In order to overcome the defects, the invention discloses a molybdenum-based sulfide supported catalyst and an in-situ preparation method and application thereof. The preparation method of the supported catalyst is simple in process, avoids the random distribution of the active components of the auxiliary agent on the surface of the carrier through double in-situ reactions, namely in-situ loading and in-situ vulcanization, effectively improves the dispersion and utilization rate of the auxiliary agent, and the auxiliary agent stays at the Edge of a sulfur vacancy of molybdenum sulfide to form an auxiliary agent-Edge catalytic active center, thereby providing a simple, efficient and environment-friendly method for preparing the high-activity sulfide supported catalyst.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
an in-situ process for preparing the Mo-base sulfide carried catalyst includes loading Mo salt on carrier, adding S source and sulfuric acid, and converting the Mo salt to the sulfur-enriched Mo sulfide to obtain MoS x A carrier, wherein x>2, loading auxiliary agent metal ions on the MoS x On the carrier, finally, the molybdenum-based sulfide supported catalyst can be prepared by heating and in-situ vulcanization treatment in protective atmosphere.
Preferably, the carrier is selected from one or more of alumina, silica, activated carbon and molecular sieve.
Preferably, the molybdenum salt is molybdate, and the sulfur source is one or more of sodium sulfide, potassium sulfide, thiourea and ammonium sulfide.
Preferably, the assistant metal ions are one or more of Co, Ni, Fe and Re.
Preferably, in the molybdenum-based sulfide supported catalyst, the molar ratio of the promoter metal to molybdenum is 0.01-1, and further preferably 0.3-0.7; the loading amount of the active component is 5-50 wt%, and the further preferable loading amount is 10-30 wt%.
Preferably, in the heating in-situ vulcanization process, the protective atmosphere is one or a mixture of a plurality of gases of nitrogen, helium and argon, the temperature is 300-700 ℃, and the time is 0.1-24 hours.
The invention also provides the molybdenum-based sulfide supported catalyst prepared by the in-situ preparation method.
The invention also provides the application of the molybdenum-based sulfide supported catalyst, and the molybdenum-based sulfide supported catalyst is used for hydrodesulfurization reaction.
The invention has the beneficial effects that:
the invention designs a method for preparing a metal sulfide supported catalyst in situ, namely, firstly preparing a sulfur-rich molybdenum sulfide/carrier precursor by in situ reaction, then directionally enabling an auxiliary agent to be effectively and uniformly dispersed on the surface of the catalyst by utilizing the adsorbability of sulfur vacancies to auxiliary agent metal ions, and after in situ vulcanization, enabling the auxiliary agent to stay at the Edge of the sulfur vacancies of the molybdenum sulfide to form an auxiliary agent-Edge catalytic active center. Compared with the traditional impregnation loading method, the method has the advantages that through double in-situ reactions, namely in-situ loading and in-situ vulcanization, the random distribution of active components on the surface of the carrier is avoided, particularly the auxiliary agent, the dispersion and the utilization rate of the auxiliary agent are effectively improved, the formation of an active center is promoted, and the excellent catalytic activity and the reusability are shown.
Drawings
FIG. 1 is a gas chromatogram obtained by sampling and analyzing samples at various time points during the catalytic reaction in example 2.
Detailed Description
The present invention is further illustrated in detail by the following examples in conjunction with the technical solutions.
The reagents used in the examples were all analytical grade, water was deionized water.
The molar ratio of S/Mo in the sulfur-rich molybdenum sulfide is more than 2.
Example 1
Will 2And 4g of sodium molybdate dihydrate is loaded on 7.5g of alumina, and an aqueous solution containing 12g of sodium sulfide, absolute ethyl alcohol and a sulfuric acid solution are sequentially added to carry out in-situ reaction to prepare the sulfur-rich molybdenum sulfide/alumina. Adding the sulfur-rich molybdenum sulfide/aluminum oxide into a solution of 0.5g of cobalt nitrate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 400 ℃ for 1h in a nitrogen atmosphere to obtain Co-Mo-S/Al with the load of 20 wt% 2 O 3 A supported catalyst.
Adding 0.6g of benzothiophene, 0.1g of the prepared catalyst and 15.0g of n-dodecane into a high-pressure reaction kettle, loading a device, removing air in the kettle by adopting a displacement method, heating to 225 ℃, adjusting the pressure of hydrogen to 4.0MPa, reacting for 4 hours, wherein the conversion rate reaches 100%, the selectivity of ethylbenzene is 100%, the desulfurization rate reaches 100%, and the catalytic activity is unchanged after 8 times of cyclic reaction.
Example 2
2.4g of sodium molybdate dihydrate is loaded on 7.5g of silicon dioxide, and aqueous solution containing 12g of sodium sulfide, absolute ethyl alcohol and sulfuric acid solution are sequentially added to carry out in-situ reaction to prepare the molybdenum sulfide/silicon dioxide rich in sulfur. Adding the sulfur-rich molybdenum sulfide/silicon dioxide into a solution of 0.75g of cobalt nitrate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 500 ℃ for 0.5h in a nitrogen atmosphere to obtain Co-Mo-S/SiO with the load of 20 wt% 2 A supported catalyst.
0.6g of dibenzothiophene, 0.1g of the catalyst prepared above and 15.0g of n-dodecane are added into a high-pressure reaction kettle, a device is installed, air in the kettle is removed by adopting a displacement method, then the temperature is raised to 250 ℃, the hydrogen pressure is adjusted to be 4.0MPa, after reaction is carried out for 6 hours (a gas chromatogram obtained by sampling and analyzing at each time point is shown in figure 1), the conversion rate reaches 100%, the desulfurization rate reaches 100%, the reaction is carried out for 10 times in a circulating manner, and the catalytic activity is not changed.
Example 3
2.4g of sodium molybdate dihydrate is loaded on 7.5g of activated carbon, and aqueous solution containing 12g of potassium sulfide, absolute ethyl alcohol and sulfuric acid solution are sequentially added to carry out in-situ reaction to prepare the sulfur-rich molybdenum sulfide/activated carbon. And adding the sulfur-rich molybdenum sulfide/activated carbon into a solution of 0.75g of nickel nitrate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 700 ℃ for 0.1h in a nitrogen atmosphere to obtain the Ni-Mo-S/C supported catalyst with the load of 20 wt%.
Adding 0.6g of benzothiophene, 0.2g of the prepared catalyst and 15.0g of n-dodecane into a high-pressure reaction kettle, loading a device, removing air in the kettle by adopting a displacement method, heating to 225 ℃, adjusting the pressure of hydrogen to be 4.0MPa, reacting for 4 hours, wherein the conversion rate reaches 100%, the desulfurization rate reaches 100%, and the catalytic activity is unchanged after 7 times of cyclic reaction.
Example 4
And loading 1.2g of sodium molybdate dihydrate on 7.5g of molecular sieve ZSM-5, sequentially adding an aqueous solution containing 6g of ammonium sulfide, absolute ethyl alcohol and a sulfuric acid solution, and carrying out in-situ reaction to obtain the sulfur-rich molybdenum sulfide/molecular sieve. And adding the sulfur-rich molybdenum sulfide/molecular sieve into a solution of 0.75g of cobalt nitrate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 400 ℃ for 1h in a nitrogen atmosphere to obtain the Co-Mo-S/ZSM-5 supported catalyst with the load of 10 wt%.
Adding 0.6g of dibenzothiophene, 0.1g of the prepared catalyst and 15.0g of n-dodecane into a high-pressure reaction kettle, loading a device, removing air in the kettle by adopting a displacement method, heating to 225 ℃, adjusting the pressure of hydrogen to 4.0MPa, reacting for 6 hours, wherein the conversion rate reaches 100%, the desulfurization rate reaches 100%, and the catalytic activity is unchanged after 8 times of cyclic reaction.
Example 5
And loading 1.2g of sodium molybdate dihydrate on 7.5g of molecular sieve ZSM-5, sequentially adding an aqueous solution containing 6g of ammonium sulfide, absolute ethyl alcohol and a sulfuric acid solution, and carrying out in-situ reaction to obtain the sulfur-rich molybdenum sulfide/molecular sieve. And adding the sulfur-rich molybdenum sulfide/molecular sieve into a solution of 0.75g ammonium perrhenate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 400 ℃ for 1h in a nitrogen atmosphere to obtain the Re-Mo-S/ZSM-5 supported catalyst with the load of 10 wt%.
Adding 0.6g of dibenzothiophene, 0.1g of the prepared catalyst and 15.0g of n-dodecane into a high-pressure reaction kettle, loading the mixture into a device, removing air in the kettle by adopting a displacement method, heating to 225 ℃, adjusting the pressure of hydrogen to be 4.0MPa, reacting for 6 hours until the conversion rate reaches 100%, the desulfurization rate reaches 100%, and reacting for 8 times in a circulating manner without change in activity.
Example 6
2.4g of sodium molybdate dihydrate is loaded on 3.7g of alumina, and aqueous solution containing 12g of sodium sulfide, absolute ethyl alcohol and sulfuric acid solution are sequentially added for in-situ reaction to prepare the sulfur-rich molybdenum sulfide/alumina. Adding the sulfur-rich molybdenum sulfide/aluminum oxide into a solution of 0.75g of cobalt nitrate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 600 ℃ for 0.5h in a nitrogen atmosphere to obtain Co-Mo-S/Al with the load of 40 wt% 2 O 3 A supported catalyst.
The above 2.0g of catalyst and quartz sand were charged into a fixed bed microreactor and subjected to airtightness inspection, and then heated to 250 ℃ under nitrogen protection and held for 1 hour. Then, the reaction was started by switching to hydrogen while feeding 6mL/h of a pyrolysis gasoline having a sulfur content of 638ppm under a pressure of 2.5MPa, a hydrogen-oil volume ratio of 250:1 and a temperature of 250 ℃. After the reaction is stable for 18h, the sulfur content in the product is 5ppm, the continuous operation is carried out for 72h, and the sulfur content in the product is maintained below 6 ppm.
Example 7
Loading 12g of sodium molybdate dihydrate on 75g of alumina, sequentially adding an aqueous solution containing 60g of sodium sulfide, absolute ethyl alcohol and a sulfuric acid solution, and carrying out in-situ reaction to obtain the sulfur-rich molybdenum sulfide/alumina. Adding the sulfur-rich molybdenum sulfide/aluminum oxide into a solution of 7.5g of cobalt nitrate, uniformly stirring, standing, evaporating the liquid to dryness, and carrying out in-situ reaction at 400 ℃ for 1h in a nitrogen atmosphere to prepare Co-Mo-S/Al with the load of 20 wt% by amplifying by 10 times 2 O 3 A supported catalyst.
Mixing the above Co-Mo-S/Al 2 O 3 Loading 2.0g of supported catalyst and quartz sand into a fixed bed microreactor, checking the gas tightness, heating to 250 ℃ under the protection of nitrogen, keeping for 1 hour, switching to hydrogen, feeding blend diesel oil with the sulfur content of 975ppm at 6mL/h, and starting to react under the conditions of the pressure of 2.5MPa and the volume of hydrogen oilThe ratio of 250:1 and the temperature of 275 ℃, after the reaction is stable for 18 hours, the sulfur content in the product is 8ppm, the continuous operation is carried out for 72 hours, and the sulfur content in the product is maintained below 10 ppm.
Comparative example 1
Taking the existing traditional impregnation loading method as a reference (Applied Catalysis B: Environmental,2021,297: 120449; Journal of Catalysis,2022,407:19), ammonium molybdate and cobalt nitrate are impregnated and loaded according to the molar ratio of Co/Mo of 1:2, and then are dried for 6 hours at 100 ℃ and roasted for 4 hours at 500 ℃, and finally the catalyst is vulcanized by adopting a high-temperature vulcanization method to obtain the catalyst.
0.6g of dibenzothiophene, 0.1g of the prepared catalyst and 15.0g of n-dodecane are added into a high-pressure reaction kettle, a device is installed, air in the kettle is removed by adopting a displacement method, then the temperature is raised to 340 ℃, the hydrogen pressure is adjusted to be 4.0MPa, and after 6 hours of reaction, the conversion rate reaches 92% and the desulfurization rate reaches 90%. It is clear that the activity of the catalyst prepared in situ according to the invention is significantly higher than that of the catalysts prepared by the prior impregnation methods.
Claims (9)
1. An in-situ preparation method of a molybdenum-based sulfide supported catalyst is characterized by comprising the following steps: firstly, molybdenum salt is loaded on a carrier, and then a sulfur source and sulfuric acid are added to convert the molybdenum salt into molybdenum sulfide rich in sulfur to form MoS x A support, wherein x>2, loading auxiliary agent metal ions on the MoS x On the carrier, finally, the molybdenum-based sulfide supported catalyst can be prepared by heating and in-situ vulcanization treatment in protective atmosphere.
2. The in-situ preparation method of the molybdenum-based sulfide supported catalyst according to claim 1, wherein: the carrier is selected from one or more of alumina, silica, activated carbon and molecular sieve.
3. The in-situ preparation method of the molybdenum-based sulfide supported catalyst according to claim 1, wherein: the molybdenum salt is molybdate, and the sulfur source is one or more of sodium sulfide, potassium sulfide, thiourea and ammonium sulfide.
4. The in-situ preparation method of the molybdenum-based sulfide supported catalyst according to claim 1, wherein: the assistant metal ions are one or more of Co, Ni, Fe and Re.
5. The method of in situ preparation of molybdenum-based sulfide supported catalyst according to claim 1, wherein: in the molybdenum-based sulfide supported catalyst, the molar ratio of the auxiliary metal to molybdenum is 0.01-1, and the loading amount of the active component is 5-50 wt%.
6. The method of in situ preparation of molybdenum-based sulfide supported catalyst according to claim 5, wherein: in the molybdenum-based sulfide supported catalyst, the molar ratio of the auxiliary metal to molybdenum is 0.3-0.7, and the loading amount of the active component is 10-30 wt%.
7. The method of in situ preparation of molybdenum-based sulfide supported catalyst according to claim 1, wherein: in the heating in-situ vulcanization process, the protective atmosphere is one or a mixture of a plurality of gases of nitrogen, helium and argon, the temperature is 300-700 ℃, and the time is 0.1-24 hours.
8. The molybdenum-based sulfide supported catalyst prepared by the in situ preparation method of any one of claims 1 to 7.
9. Use of the molybdenum-based sulfide supported catalyst of claim 8, wherein: it is used in hydrodesulfurization reactions.
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