CN115382559B - Double-function catalyst for hydrodeoxygenation reaction and preparation method and application thereof - Google Patents
Double-function catalyst for hydrodeoxygenation reaction and preparation method and application thereof Download PDFInfo
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- CN115382559B CN115382559B CN202211051338.0A CN202211051338A CN115382559B CN 115382559 B CN115382559 B CN 115382559B CN 202211051338 A CN202211051338 A CN 202211051338A CN 115382559 B CN115382559 B CN 115382559B
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- catalyst
- molybdenum disulfide
- reaction
- solution
- metal boride
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 32
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 3
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 abstract description 23
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 239000002028 Biomass Substances 0.000 description 13
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 10
- 238000011549 displacement method Methods 0.000 description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 10
- 229940094933 n-dodecane Drugs 0.000 description 10
- 230000002572 peristaltic effect Effects 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 2
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 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
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- IOOGPFMMGKCAGU-UHFFFAOYSA-N tetrasulfur Chemical compound S=S=S=S IOOGPFMMGKCAGU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/04—Sulfides
- C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
- C07C2527/051—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a double-function catalyst for hydrodeoxygenation reaction, a preparation method and application thereof. The catalyst consists of metal boride and molybdenum disulfide, wherein the molar ratio of the metal boride to the molybdenum disulfide is 0.1-2.0. The catalyst metal boride has high dispersity, fully contacts molybdenum disulfide, and can effectively exert the bifunctional property of the catalyst; meanwhile, the catalyst preparation process is simple, high-temperature vulcanization or reduction operation is not needed, and particle agglomeration and emission of toxic and harmful gases are avoided. The catalyst is prepared by the following steps: the metal salt reacts with sodium borohydride to prepare metal boride precipitate, and the metal boride-molybdenum disulfide dual-function catalyst is obtained by utilizing the high affinity of the surface defect of the metal boride precipitate and the molybdenum disulfide to be compounded. The synthesized catalyst can obviously reduce the hydrodeoxygenation reaction temperature of biological oil products and improve the selectivity of the products.
Description
Technical Field
The invention relates to a hydrodeoxygenation catalyst, in particular to a bifunctional catalyst for hydrodeoxygenation reaction, and a preparation method and application thereof.
Background
With the exhaustion of fossil resources and the increase of environmental problems caused by the utilization of fossil resources, the development of novel energy sources is receiving extensive attention from the whole society. The biomass energy is used as an internationally recognized novel zero-carbon energy source, has the characteristics of green, environment protection and reproducibility, and has important significance in reducing the dependence on fossil resources and protecting the environment. The biomass raw material has higher C/H ratio, and the fuel oil (bio-oil) prepared after liquefaction has high energy density, is easy to store and transport on a large scale, and is the most potential petroleum alternative energy source. However, the high oxygen content of the oil (about 35% -40%) causes the defects of low heat value, high viscosity, poor thermal stability and the like, and the oxygen content of the oil is required to be reduced by a catalytic hydrodeoxygenation technology so as to be converted into high-grade fuel, so that the construction of the high-activity hydrodeoxygenation catalyst is a key of the quality improvement and high-value utilization of biomass oil.
The molybdenum-based bimetallic sulfide has higher activity than that of a single metal sulfide, has been used in industrial hydrodesulfurization reaction, and is also a catalyst with good hydrodeoxygenation activity. Document 1 [ APPL CATAL A-GEN,2010,372:199 ] compares the studies of alumina-supported molybdenum sulfide, nickel sulfide and nickel molybdenum sulfide catalytic hydrodeoxygenation, with the bimetallic nickel molybdenum sulfide exhibiting the highest catalytic activity and deoxygenation product yield. Document 2 [ nat.chem.,2017,9:810 ] reports that monoatomic Co (tetrasulfur coordination) modified molybdenum disulfide catalysts exhibit good low temperature activity in catalyzing hydrodeoxygenation reactions of lignin oils, a typical compound. Chinese invention CN101831315a discloses a process for hydrodeoxygenation of renewable raw materials, the catalyst comprising an active phase constituted by at least one element selected from group VIB and group VIII elements, both elements being in sulphide form. Chinese invention CN114570392a discloses an alumina supported bimetallic sulfide catalyst prepared by impregnating Al with a metal solution containing Mo, co 2 O 3 And (3) carrying out heat treatment on the surface of the carrier to obtain an oxidation state precursor, and then carrying out vulcanization treatment on the precursor to obtain the supported sulfide catalyst. Chinese invention CN113663696a discloses a preparation method and application of Co-Mo-S hydrodeoxygenation catalyst, which uses cheap ammonium molybdate as raw material to prepare molybdenum trisulfide, then loads cobalt nitrate onto the molybdenum trisulfide, then carries out thermal decomposition, and Co is in-situ vulcanized to obtain the bimetallic sulfide catalyst.
Molybdenum-based bimetallic catalysts typically contain two types of active centers, with the main catalyst molybdenum disulfide adsorbing primarily oxygenates and hydrogenolyzing C-O bonds; the sulfide auxiliary agent adsorbs and dissociates hydrogen, and provides active hydrogen for the deoxidization reaction carried out on the main catalyst, wherein the hydrogen supply capacity is one of important factors influencing the hydrodeoxygenation activity of the catalyst, however, the sulfide auxiliary agent has weaker hydrogen dissociation capacity, and further improvement of the catalytic hydrodeoxygenation activity of the molybdenum-based bimetallic sulfide is limited. Although common metals such as Ni, co, noble metals Pt, pd and the like have higher hydrogen activating capability, for example, chinese invention CN109675589A discloses a metal composite molybdenum disulfide hydrodeoxygenation catalyst and a preparation method, a precursor of the metal component needs to be reduced at high temperature to be converted into a metal state, the operation easily causes particle agglomeration, the number of active centers is reduced, and meanwhile, the metal also possibly reacts with sulfur-containing organic matters in materials and water generated by hydrodeoxygenation to cause structural change and reduce the hydrogen activating capability.
Disclosure of Invention
Aiming at the technical problems of complicated preparation process, weak hydrogen activating capability and low catalytic hydrodeoxygenation activity of the molybdenum-based bimetallic catalyst, the invention provides the bifunctional catalyst for hydrodeoxygenation reaction, and the preparation method and application thereof.
The technical scheme of the invention is as follows:
a bifunctional catalyst for hydrodeoxygenation reaction, which consists of metal boride and molybdenum disulfide, wherein the molar ratio of the metal boride to the molybdenum disulfide is 0.1-2.0.
Further, the metal in the metal boride is one or more of cobalt, nickel, iron and copper.
The preparation method of the bifunctional catalyst for hydrodeoxygenation reaction comprises the following steps:
(1) Preparing molybdenum disulfide;
(2) Dispersing metal salt in the solution A, then dropwise adding an aqueous solution of sodium borohydride into the metal salt solution for reaction, and separating and washing a solid product after the reaction;
(3) Adding the solid product and molybdenum disulfide into the solution B, fully mixing and standing, separating, washing and drying in vacuum to obtain the metal boride-molybdenum disulfide dual-function catalyst.
Further, the molybdenum disulfide is prepared by adopting a precipitation method, a decomposition method, a ball milling method or a hydrothermal synthesis method, and preferably a hydrothermal synthesis method.
Further, the dispersion of the metal salt is performed under an atmospheric condition of one or more of air, oxygen, nitrogen, argon, helium, preferably nitrogen.
Further, the metal salt is one or more than two soluble salts containing cobalt, nickel, iron and copper.
Further, the solution A and the solution B are independently selected from one or more than two of water, methanol, ethanol, n-propanol or isopropanol.
Further, in the step (2), the reaction temperature is 0-60 ℃ and the reaction time is 0.5-3 h.
Further, the separation modes in the step (2) and the step (3) are centrifugation, suction filtration or sedimentation, and centrifugal separation is preferred.
Further, in the step (3), the mixing mode is natural diffusion, vibration, stirring or ultrasonic strengthening dispersion, preferably ultrasonic strengthening dispersion.
Further, in the step (3), the standing is preferably performed at a temperature of 20-200 ℃ for a time of 0.5-16 hours.
Further, in the step (3), the vacuum drying is performed at the temperature of 25-100 ℃ for 0.5-24 hours.
The double-function catalyst can be used in hydrodeoxygenation reaction of biological oil products, can obviously reduce reaction temperature and improve product selectivity.
The invention has the beneficial effects that:
the metal boride alloy has strong hydrogen dissociation activity, can provide sufficient hydrogen dissociation, and effectively plays the double-function catalytic property of the catalyst. The catalyst has simple preparation process, no need of high temperature vulcanization and reduction operation, and avoids large agglomeration of particles and emission of toxic and harmful gases. The high free energy of boride surface defect promotes the effective combination of boride and molybdenum disulfide, and the synthesized catalyst has sufficient two-phase contact, high metal boride dispersity, excellent catalytic hydrodeoxygenation activity and product selectivity.
Drawings
FIG. 1 is an XRD pattern of a nickel boride-molybdenum disulfide bifunctional catalyst obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
The reagents used in the examples were all analytically pure and the water was deionized water. The preparation method of the molybdenum disulfide comprises the following steps: 0.88g of ammonium paramolybdate and 1.14g of thiourea are dissolved in 100mL of water, the pH is adjusted to 0.12 by using hydrochloric acid, after 24 hours of hydrothermal reaction at 200 ℃, the product is washed and dried in vacuum to obtain molybdenum disulfide.
Example 1
In a 100mL three-necked flask, 20mL of water and 0.29g of nickel nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continues to react for 10min, centrifugal washing is carried out, the precipitate and 0.53g of molybdenum disulfide are dispersed in 50mL of absolute ethyl alcohol, ultrasonic dispersion is carried out for 30min and transferred into a hydrothermal kettle, crystallization is carried out for 3h at 90 ℃, and then the precipitate is centrifugally separated, washed with water, washed with alcohol and dried for 6h at 60 ℃ in vacuum, thus obtaining the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 180 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the selectivity of methylcyclohexane is 99.3%, the selectivity of methylcyclohexanol is 0.3%, and after 5 times of cyclic reaction, the conversion rate of reactants and the selectivity change rate of main products are all less than 1%.
Example 2
In a 100mL three-necked flask, 20mL of water and 0.29g of cobalt nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continues to react for 10min, centrifugal water washing is carried out, the precipitate and 0.53g of molybdenum disulfide are dispersed in 50mL of absolute ethyl alcohol, and ultrasonic dispersion is carried outTransferring the mixture for 30min to a 200mL hydrothermal kettle, crystallizing the mixture at 90 ℃ for 3h, and centrifugally separating, washing the precipitate with water, washing the precipitate with alcohol, and drying the precipitate at 60 ℃ in vacuum for 6h to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 160 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the toluene selectivity is 99.8%, the methyl cyclohexanol selectivity is 0%, and after 5 times of cyclic reaction, the conversion rate of the reactants and the selectivity change rate of the main product are both less than 0.5%.
Example 3
In a 100mL three-necked flask, 20mL of water and 0.24g of ferric nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continues to react for 10min, centrifugal washing, dispersing the precipitate and 0.53g of molybdenum disulfide in 50mL of absolute ethyl alcohol, transferring the solution to a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, crystallizing for 3h at 90 ℃, centrifugally separating the precipitate, washing with water, washing with alcohol, and vacuum drying at 60 ℃ for 6h to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 200 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 99%, the toluene selectivity is 93.8%, the methyl cyclohexanol selectivity is 0.3%, and the reactant conversion rate and the main product selectivity change rate are both less than 2% after 5 times of cyclic reaction.
Example 4
In a 100mL three-necked flask, 20mL of water and 0.19g of copper nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continued to react for 10min, the precipitate and 0.53g of molybdenum disulfide were dispersed in 50mL of absolute ethanol after centrifugal water washing, and the solution was super-heatedAnd transferring the dispersion for 30min into a 200mL hydrothermal kettle, crystallizing for 3h at 90 ℃, and centrifugally separating, washing with alcohol, and vacuum drying for 6h at 60 ℃ to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 250 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 96%, the toluene selectivity is 95.8%, the methyl cyclohexanol selectivity is 0.1%, and the reactant conversion rate and the main product selectivity change rate are both less than 2.5% after 5 times of cyclic reaction.
Example 5
In a 100mL three-necked flask, 20mL of water and 0.29g of nickel nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continues to react for 10min, centrifugal washing, dispersing the precipitate and 0.32g of molybdenum disulfide in 50mL of absolute ethyl alcohol, transferring the solution to a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, crystallizing for 3h at 90 ℃, centrifugally separating the precipitate, washing with water, washing with alcohol, and vacuum drying at 60 ℃ for 6h to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 180 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the selectivity of methylcyclohexane is 99.9%, the selectivity of methylcyclohexanol is 0.1%, and after 5 times of cyclic reaction, the conversion rate of reactants and the selectivity change rate of main products are all less than 1%.
Example 6
In a 100mL three-necked flask, 20mL of water and 0.29g of nickel nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the reaction was continued for 10 minutes, the solution (0.4 mol/L) was washed with water by centrifugation, and then the precipitate and 0.53g of molybdenum disulfide were dispersed in 50mAnd (3) in the L absolute ethyl alcohol, transferring the L absolute ethyl alcohol to a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, and carrying out crystallization for 3h at 90 ℃, and then carrying out centrifugal separation, water washing, alcohol washing and vacuum drying at 60 ℃ on the precipitate for 6h to obtain the black catalyst.
15g of n-dodecane, 1.38g of a typical oxygen-containing compound guaiacol in biomass oil and 0.1g of the catalyst prepared by the method are added into a high-pressure reaction kettle, the device is assembled, air in the kettle is discharged by adopting a displacement method, then the temperature is increased to 180 ℃ at the speed of 10 ℃/min, the rotating speed is regulated to 600r/min, the hydrogen pressure is 3.0MPa, after 3 hours of reaction, the conversion rate of the guaiacol reaches 100%, the cyclohexane selectivity is 99.1%, the cyclohexanol selectivity is 0.5%, and after 5 times of cyclic reaction, the conversion rate of reactants and the selectivity change rate of main products are all less than 1%.
Example 7
In a 100mL three-necked flask, 20mL of water and 0.13g of nickel chloride were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continues to react for 10min, centrifugal washing, dispersing the precipitate and 0.53g of molybdenum disulfide in 50mL of absolute ethyl alcohol, transferring the solution to a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, crystallizing for 3h at 90 ℃, centrifugally separating the precipitate, washing with water, washing with alcohol, and vacuum drying at 60 ℃ for 6h to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 180 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the selectivity of methylcyclohexane is 99.9%, the selectivity of methylcyclohexanol is 0%, and after 5 times of cyclic reaction, the conversion rate of the reactants and the selectivity change rate of main products are less than 1%.
Example 8
In a 100mL three-necked flask, 20mL of water and 0.29g of nickel nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.2 mol/L) was reacted for 10 minutes, the solution was washed with water by centrifugation, and then the precipitate was separated from 0.53g of molybdenum disulfideDispersing in 50mL absolute ethyl alcohol, transferring to a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, crystallizing at 90 ℃ for 3h, centrifuging and separating precipitate, washing with water, washing with alcohol, and vacuum drying at 60 ℃ for 6h to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 180 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the selectivity of methylcyclohexane is 98.8%, the selectivity of methylcyclohexanol is 0.4%, and after 5 times of cyclic reaction, the conversion rate of reactants and the selectivity change rate of main products are all less than 1%.
Example 9
In a 100mL three-necked flask, 20mL of water and 0.29g of nickel nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 After the solution (0.4 mol/L) continues to react for 10min, centrifugal washing, dispersing the precipitate and 0.53g of molybdenum disulfide in 50mL of absolute ethyl alcohol, transferring the solution to a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, crystallizing for 3h at 150 ℃, centrifugally separating the precipitate, washing with water, washing with alcohol, and vacuum drying at 60 ℃ for 6h to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 180 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the selectivity of methylcyclohexane is 99.8%, the selectivity of methylcyclohexanol is 0%, and after 5 times of cyclic reaction, the conversion rate of the reactants and the selectivity change rate of main products are less than 1%.
Example 10
In a 100mL three-necked flask, 20mL of water and 0.29g of nickel nitrate were added, and the mixture was stirred at 600r/min under nitrogen protection, and 5mL of NaBH was slowly pumped by a peristaltic pump 4 The solution (0.4 mol/L) was reacted for 10 minutes, and after washing with water by centrifugation, the reaction mixture was washed with waterAnd dispersing the precipitate and 0.53g of molybdenum disulfide in 50mL of anhydrous water, transferring the 50mL of anhydrous water into a 200mL hydrothermal kettle after ultrasonic dispersion for 30min, crystallizing for 3h at 90 ℃, and carrying out centrifugal separation, water washing, alcohol washing and vacuum drying at 60 ℃ on the precipitate to obtain the black catalyst.
Adding 15g of n-dodecane, 2.4g of typical oxygen-containing compound p-methylphenol in biomass oil and 0.1g of the catalyst prepared by the method into a high-pressure reaction kettle, installing the device, exhausting air in the kettle by adopting a displacement method, then raising the temperature from room temperature to 180 ℃ at a speed of 10 ℃/min, adjusting the rotating speed to 600r/min, controlling the hydrogen pressure to 3.0MPa, reacting for 3 hours, wherein the conversion rate of the p-methylphenol reaches 100%, the selectivity of methylcyclohexane is 97.7%, the selectivity of methylcyclohexanol is 1.3%, and after 5 times of cyclic reaction, the conversion rate of reactants and the selectivity change rate of main products are both less than 2%.
Claims (7)
1. The application of the bifunctional catalyst for hydrodeoxygenation reaction in hydrodeoxygenation reaction of biological oil products is characterized in that the catalyst consists of metal boride and molybdenum disulfide, and the molar ratio of the metal boride to the molybdenum disulfide is 0.1-2.0;
the metal in the metal boride is one or more of cobalt, nickel, iron and copper;
the preparation method of the bifunctional catalyst comprises the following steps:
(1) Preparing molybdenum disulfide;
(2) Dispersing metal salt in the solution A, then dropwise adding an aqueous solution of sodium borohydride into the metal salt solution for reaction, and separating and washing a solid product after the reaction;
(3) Adding the solid product and molybdenum disulfide into the solution B, fully mixing and standing, separating, washing and drying in vacuum to obtain the metal boride-molybdenum disulfide dual-function catalyst.
2. The use according to claim 1, wherein the molybdenum disulfide is prepared by precipitation, decomposition, ball milling or hydrothermal synthesis.
3. The use according to claim 1, wherein the dispersion of the metal salt is carried out under atmospheric conditions of one or more of air, oxygen, nitrogen, argon, helium.
4. The use according to claim 1, wherein the metal salt is one or more soluble salts containing cobalt, nickel, iron, copper.
5. The use according to claim 1, wherein the solution a and the solution B are independently selected from one or more of water, methanol, ethanol, n-propanol and isopropanol.
6. The use according to claim 1, wherein in step (2), the reaction is carried out at a temperature of 0 to 60 ℃ for a time of 0.5 to 3 hours; the separation mode is centrifugation, suction filtration or sedimentation.
7. The use according to claim 1, wherein in step (3) the mixing is by natural diffusion, shaking, stirring or ultrasonically enhanced dispersion; the standing temperature is 20-200 ℃ and the time is 0.5-16 h; the separation mode is centrifugation, suction filtration or sedimentation; the temperature of vacuum drying is 25-100 ℃ and the time is 0.5-24 h.
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