CN112973706B - 一种镍基催化剂及其制备与应用 - Google Patents
一种镍基催化剂及其制备与应用 Download PDFInfo
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- CN112973706B CN112973706B CN201911288025.5A CN201911288025A CN112973706B CN 112973706 B CN112973706 B CN 112973706B CN 201911288025 A CN201911288025 A CN 201911288025A CN 112973706 B CN112973706 B CN 112973706B
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- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003292 glue Substances 0.000 claims abstract description 9
- 239000000741 silica gel Substances 0.000 claims abstract description 9
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 35
- 150000002816 nickel compounds Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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 7
- 238000005732 thioetherification reaction Methods 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 3
- 229910052749 magnesium Inorganic materials 0.000 claims 3
- 239000011777 magnesium Substances 0.000 claims 3
- 229910052726 zirconium Inorganic materials 0.000 claims 3
- 229910017052 cobalt Inorganic materials 0.000 claims 2
- 239000010941 cobalt Substances 0.000 claims 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 2
- MPONAPFARZGDTH-UHFFFAOYSA-N Cl.OS(O)=O Chemical class Cl.OS(O)=O MPONAPFARZGDTH-UHFFFAOYSA-N 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical class [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- -1 metatungstate Chemical compound 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005470 impregnation Methods 0.000 abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 6
- 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 6
- 239000002243 precursor Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种镍基催化剂及其制备与应用。催化剂以镍为主要活性组分，同时含助剂一组分，包括氧化锆、氧化铁、氧化钴中的一种或两种以上，助剂二组分，包括氧化钛、氧化锡、氧化钨、氧化钼、氧化镁中的一种或两种以上，采用浸渍的方法制备，以硅胶和铝胶为粘结剂，经浸渍、烘干、焙烧、成型、焙烧后得到催化剂。催化剂在油品加氢脱硫反应中具有很好的活性。
Description
技术领域
本发明涉及一种镍基催化剂及其制备与应用。具体地说，涉及一种利用等体积浸渍法制备以金属镍为主要活性组分的催化剂，该催化剂用于汽油加氢脱硫反应。
背景技术
为了降低汽柴油中硫对大气及环境的污染，世界各国对汽油、柴油的硫含量都制定了严格的法规。传统的汽油加氢脱硫工艺在深度脱硫的同时辛烷值损失较大，目前国外已经陆续开发出新的生产超低硫汽油的工艺技术，其中以美国的CD TECH公司开发的CDHydro&CDHDS工艺和法国的Axens公司开发的Prime G+工艺具有广阔的应用前景。采用的工艺路线是在缓和的临清条件下催化油品中的二烯烃与硫醇发生硫醚化反应生成较大分子的硫醚，同时对汽油中的二烯烃进行选择性加氢饱和，而后将汽油通过精馏的工艺分为轻重两种组分，轻组分为超低硫汽油富含烯烃较高辛烷值的调和组分，重组分进行深度加氢脱硫，这两种工艺均可以生产出超低硫和极少辛烷值损失的汽油。
目前国外对该技术的研究主要集中在工艺方面，而对硫醚化反应所用的催化剂报道较少。大多采用具有选择性加氢功能的Pt和Pd等贵金属元素，这类催化剂往往具有较强的烯烃饱和活性，并且其成本也较高。而镍基催化剂由于价格相对低廉，活性适中，近年来备受研究者的关注。在硫醚化反应方面，有研究报道了Ni/Al2O3催化剂【石油炼制与化工，2010,41,37-42】和Mo-Ni/Al2O3催化剂【石油学报，2015,31,18-24】。然而，催化剂的活性和选择性仍然不能令人满意。
发明内容
为实现上述目的，本发明提供了一种简单的等体积浸渍的方法，将助剂浸渍在高比表面积的镍化合物上，从而获得更高的催化活性，同时，助活性组分与镍紧密接触，产生协同效应，获得最佳的反应选择性和催化剂稳定性。
本发明采取的技术方案为：
本发明一方面提供一种镍基催化剂，所述催化剂由活性组分、助剂I、助剂II和粘结剂组成；所述活性组分为镍，在催化剂中镍元素的含量为50-80wt％；所述助剂I为氧化锆、氧化铁、氧化钴中的一种或两种以上；在催化剂中的总含量为1-10wt％；所述助剂II为氧化钛、氧化锡、氧化钨、氧化钼、氧化镁中的一种或两种以上，在催化剂中的总含量为1-10wt％；所述催化剂以不溶性镍化合物为载体，经浸渍助剂I和助剂II后，干燥、焙烧(优选空气)，再加入粘结剂成型、焙烧得到；所述不溶性镍化合物为草酸镍、碳酸镍、碱式碳酸镍、氢氧化镍、氧化镍或氧化亚镍。
所述草酸镍、碳酸镍、碱式碳酸镍、氢氧化镍、氧化镍、氧化亚镍比表面积高于20m2/g。
本发明另一方面提供上述镍基催化剂的制备方法，包括以下步骤：
(1)催化剂前体的制备：将助剂一中的一种或多种可溶性盐，与助剂二中的一种或多种可溶性盐溶于水中，制成混合溶液，向其中加入不溶性镍的化合物，搅拌均匀后静置6-24h，再经过80-150℃干燥，然后在250-550℃焙烧0.5-4h，得到催化剂前体；
(2)催化剂成型：向催化剂前体中加入粘结剂，搅拌均匀后，采用挤压成型或挤条成型或滚动成型的方法制备出成型颗粒，再经过80-150℃干燥，然后在250-650℃焙烧0.5-4h，得到镍基催化剂；
(3)镍基催化剂在使用前需在氢气气氛中于150-500℃还原0.5-5h。
所述不溶性镍化合物为草酸镍、碳酸镍、碱式碳酸镍、氢氧化镍、氧化镍、氧化亚镍；所述助剂一的可溶性盐为锆、铁、钴的氯化盐、氯化亚盐、硝酸盐、硝酸亚盐、磷酸盐、硫酸盐、硫酸亚盐及氧氯化锆；所述助剂二的可溶性盐为钛、锡、钨、钼、镁的氯化盐、氯化亚盐、硝酸盐、硝酸亚盐、磷酸盐、硫酸盐、硫酸亚盐及钨酸盐、偏钨酸盐、钼酸盐；
所述粘结剂由铝胶与硅胶混合构成，以氧化铝与氧化硅计算粘结剂在催化剂中的总含量为5-30wt％，粘结剂中氧化硅与氧化铝的质量比为0.1-10；所述的硅胶中二氧化硅含量为10-50wt％，所述的铝胶中三氧化二铝含量为5-20wt％。
所述成型颗粒为球形、粒状、齿形、环形、片状、条形，直径、长度、厚度均在1-10mm的催化剂颗粒。
本发明再一方面提供上述镍基催化剂的应用，所述催化剂可应用于油品的加氢脱硫反应，具体地可用于汽油中硫醇催化硫醚化反应。
所述催化反应在固定床反应器中进行，反应温度为80-150℃，氢气压力0.1-2MPa，氢油体积比为100-10000，反应空速为0.1-10h-1。
本发明制备的镍基催化剂在油品加氢脱硫反应中的应用，不限于固定床反应器，也可用于反应精馏反应系统，同时实现脱硫及产品精制。
本发明催化剂以镍为主要活性组分，同时含助剂一组分，包括氧化锆、氧化铁、氧化钴中的一种或两种以上，助剂二组分，包括氧化钛、氧化锡、氧化钨、氧化钼、氧化镁中的一种或两种以上，采用浸渍的方法制备，以硅胶和铝胶为粘结剂，经浸渍、烘干、焙烧、成型、焙烧后得到催化剂。催化剂在油品加氢脱硫反应中具有很好的活性，催化剂使用前需经过还原。具有如下优点：
(1)合成方法简单，活性组分处于纳米尺度的高分散状态，镍催化剂具有高活性，能够在温和的条件下催化油品中的硫醇发生硫醚化反应生成较大分子的硫醚，实现汽油加氢脱硫。
(2)催化剂中的助催化剂，能够避免镍纳米粒子在还原以及使用过程中因烧结而失活，提高了催化剂的稳定性。
(3)催化剂中使用了多金属对镍组分进行修饰，具有协同作用，提高了催化剂的反应选择性。
下面通过具体实施例对本发明进行详细说明，但这些实施例并不对本发明的内容构成限制。
实施例1
催化剂1的制备：氧氯化锆3g(助剂I)，氯化亚锡3g(助剂II)，加入80ml水中，搅拌溶解，加入比表面积为50m2/g的草酸镍100g，搅拌均匀后静置12h，120℃干燥过夜，450℃焙烧2h，得到前体。
取前体20g，加入含二氧化硅40wt％的硅胶5g，含氧化铝13wt％的铝胶10g，充分混捏后将样品挤压成直径2mm的条状，120℃干燥过夜，450℃焙烧2h，得到镍基催化剂1，使用前在氢气气氛中于400℃还原3h。
实施例2
催化剂2的制备：硝酸铁3g，偏钨酸铵3g，加入80ml水中，搅拌溶解，加入比表面积为50m2/g的草酸镍100g，搅拌均匀后静置12h，120℃干燥过夜，450℃焙烧2h，得到前体。
取前体20g，加入含二氧化硅40wt％的硅胶5g，含氧化铝13wt％的铝胶10g，充分混捏后将样品挤压成直径2mm的条状，120℃干燥过夜，450℃焙烧2h，得到镍基催化剂2，使用前在氢气气氛中于400℃还原3h。
实施例3
催化剂3的制备：硝酸铁3g，钼酸铵3g，加入80ml水中，搅拌溶解，加入比表面积为50m2/g的草酸镍100g，搅拌均匀后静置12h，120℃干燥过夜，450℃焙烧2h，得到前体。
取前体20g，加入含二氧化硅40wt％的硅胶5g，含氧化铝13wt％的铝胶10g，充分混捏后将样品挤压成直径2mm的条状，120℃干燥过夜，450℃焙烧2h，得到镍基催化剂3，使用前在氢气气氛中于400℃还原3h。
对比例1
催化剂4制备(只加入助剂I，不加入助剂II)：制备过程同实施例1，不加入氯化亚锡，得到催化剂4。
对比例2
催化剂5制备(只加入助剂II，不加入助剂I)：制备过程同实施例1，不加入氧氯化锆，得到催化剂5。
对比例3
催化剂6制备：催化剂6制备过程同实施例1，镍化合物载体采用比表面积为10m2/g的草酸镍，得到催化剂6。
对比例4
催化剂7制备：氧化铝负载型催化剂，将硝酸镍、硝酸铁、偏钨酸铵配置成混合溶液，然后浸渍于Al2O3载体上，其中镍的负载量为40wt％，铁的负载量为2wt％，钨的负载量为2wt％，经过120℃干燥过夜、500℃焙烧2h，得到催化剂7，使用前于氢气中400℃还原3h。
对比例5
催化剂8制备：制备过程同实施例1，不加入助剂I和助剂II，得到催化剂8。
应用例1实施例和对比例所得催化剂的反应性能评价
采用固定床加氢反应装置，以含硫醇汽油为原料评价催化剂的性能。反应器中装填催化剂1g，在120℃、1.0MPa氢气、原料流量3ml/h、氢气流量60ml/min的条件下评价催化剂性能。反应每2小时取样一次。以硫醇转化率表示催化剂活性。各种催化剂的反应评价结果列于表1。
表1催化剂反应性能评价
表1中，实施例1-3制备的镍基催化剂1、镍基催化剂2、镍基催化剂3，在14h内硫醇转化率保持在90％附近，且没有明显衰减。
对比例3由较小比表面积载体制备的催化剂6和对比例4(常规方法)制备的催化剂7，硫醇转化率均较低，低于50％。当载体镍化合物比表面积为10m2/g时，所得催化剂6催化性能下降明显，说明镍化合物比表面积对催化剂活性有较大影响。
对比例5制备的催化剂8中未加入助剂I和助剂II，初始活性不高且失活较快。
相对于未同时加入助剂I和助剂II的催化剂4和催化剂5，同时含有助剂I和助剂II的镍基催化剂1、镍基催化剂2、镍基催化剂3活性更高，且稳定性较好，表明助剂I与助剂II共同作用能够有效地提高催化活性和稳定性。催化剂4初始活性较高但是稳定性不好，催化剂失活较快，催化剂5失活较慢，但是整体活性不高，硫醇转化率低于镍基催化剂1、镍基催化剂2、镍基催化剂3。
另外，对比常规的浸渍法制备催化剂7，本发明技术方案制备的催化剂活性显著提高，稳定性更好，表明本发明的合成方法得到的催化剂性能更为优异。
从以上反应结果可以看到，本发明的镍基催化剂1、镍基催化剂2、镍基催化剂3在硫醚化反应中具有很好的反应性能，硫醇转化率较高且稳定。
测试例
采用物理吸附的方法测试上述催化剂的比表面积；用XRD(X射线衍射)的方法测试催化剂粒径并用谢乐公式计算镍纳米粒径。
表2催化剂性能表征比较
由表中数据可见，本申请提供的催化剂制备方法得到的镍基催化剂1、镍基催化剂2、镍基催化剂3和催化剂8，在使用前，镍粒子均处于纳米尺度的分散状态；而在使用14h后，镍基催化剂1、镍基催化剂2、镍基催化剂3的比表面积和镍纳米粒子粒径未见明显变化，而催化剂8的比表面积明显变小，镍粒径明显增大，表明助剂I和助剂II的加入能够有效稳定镍纳米粒子。
应用例2不同镍化合物为载体制备的催化剂性能比较
分别以比表面积高于20m2/g的碳酸镍、碱式碳酸镍、氢氧化镍、氧化镍、氧化亚镍为载体制备催化剂，制备过程同实施例1，所得催化剂标记为催化剂9-13，催化剂反应性能评价方式同应用例，催化剂的反应评价结果列于表3。
表3不同载体催化剂评价结果
从以上反应结果可以看到，使用不同镍化合物为载体制备的催化剂在硫醚化反应中均具有较好的反应性能，其中以草酸镍为载体制备的催化剂催化性能最优。
Claims (8)
1.一种镍基催化剂的制备方法，其特征在于：
所述催化剂由活性组分、助剂I、助剂II和粘结剂组成；
所述活性组分为镍，在催化剂中镍元素的含量为50-80wt％；
所述助剂I为氧化锆、氧化铁、氧化钴中的一种或两种以上；在催化剂中的总含量为1-10wt％；
所述助剂II为氧化钛、氧化锡、氧化钨、氧化钼、氧化镁中的一种或两种以上，在催化剂中的总含量为1-10wt％；
所述催化剂以不溶性镍化合物为载体，经浸渍助剂I和助剂II后，干燥、焙烧、再加入粘结剂成型、焙烧得到；
所述不溶性镍化合物为草酸镍、碳酸镍、碱式碳酸镍、氢氧化镍、氧化镍或氧化亚镍；
所述不溶性镍化合物的比表面积高于20m2/g；
所述镍基催化剂的制备方法包括以下步骤：
(1)催化剂前体的制备：将助剂I中的一种或多种可溶性盐，与助剂II中的一种或多种可溶性盐溶于水中，制成混合溶液，向其中加入不溶性镍的化合物，搅拌均匀后静置6-24h，再经过80-150℃干燥，然后在250-550℃焙烧0.5-4h，得到催化剂前体；
(2)催化剂成型：向催化剂前体中加入粘结剂，搅拌均匀后，采用挤压成型或挤条成型或滚动成型的方法制备出成型颗粒，再经过80-150℃干燥，然后在250-650℃焙烧0.5-4h，得到镍基催化剂；
(3)镍基催化剂在使用前需在氢气气氛中于150-500℃还原0.5-5h。
2.根据权利要求1所述的制备方法，其特征在于：
所述助剂I的可溶性盐为锆、铁或钴的可溶性盐；
所述助剂II的可溶性盐为钛、锡、钨、钼、镁的可溶性盐。
3.根据权利要求1所述的制备方法，其特征在于：
所述锆、铁、钴的可溶性盐为锆、铁、钴的氯化盐、氯化亚盐、硝酸盐、硝酸亚盐、磷酸盐、硫酸盐、硫酸亚盐及氧氯化锆；
所述钛、锡、钨、钼、镁的可溶性盐为钛、锡、钨、钼、镁的氯化盐、氯化亚盐、硝酸盐、硝酸亚盐、磷酸盐、硫酸盐、硫酸亚盐及钨酸盐、偏钨酸盐、钼酸盐。
4.根据权利要求1所述的制备方法，其特征在于：所述成型颗粒为球形、粒状、齿形、环形、片状、条形，直径、长度、厚度均在1-10mm的催化剂颗粒。
5.根据权利要求1所述的制备方法，其特征在于：
所述粘结剂由铝胶与硅胶混合构成，以氧化铝与氧化硅计算粘结剂在催化剂中的总含量为5-30wt％，粘结剂中氧化硅与氧化铝的质量比为0.1-10；
所述硅胶中二氧化硅含量为10-50wt％，所述的铝胶中三氧化二铝含量为5-20wt％。
6.权利要求1-5任一项所述制备方法制得的镍基催化剂在油品的加氢脱硫反应中的应用。
7.根据权利要求6所述的应用，其特征在于：所述反应为汽油中硫醇催化硫醚化反应。
8.根据权利要求6所述的应用，其特征在于：所述催化反应在固定床反应器中进行，反应温度为80-150℃，氢气压力0.1-2MPa，氢油体积比为100-10000，反应空速为0.1-10h-1。
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