CN112973717A - Hydrofining catalyst and preparation method thereof - Google Patents
Hydrofining catalyst and preparation method thereof Download PDFInfo
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- CN112973717A CN112973717A CN202011490415.3A CN202011490415A CN112973717A CN 112973717 A CN112973717 A CN 112973717A CN 202011490415 A CN202011490415 A CN 202011490415A CN 112973717 A CN112973717 A CN 112973717A
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- alumina carrier
- metal
- organic solvent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000002283 diesel fuel Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- -1 VIB group metal oxide Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- 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
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- 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
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth 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
- 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
-
- B01J35/615—
-
- B01J35/633—
-
- 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
Abstract
The present invention relates to the field of hydrogenation catalysts. A hydrorefining catalyst and its preparing process are disclosed. The preparation method comprises the following steps: (1) uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, adjusting the pH value of the obtained slurry to 5-10, stirring at room temperature of-90 ℃ for 0.5-24 hours, filtering, drying, and roasting at 550-800 ℃ for 2-5 hours to obtain a composite alumina carrier; (2) dipping the composite alumina carrier in an organic solvent to obtain active metal, and drying; (3) and (3) roasting the product obtained in the step (2) in an inert atmosphere at the roasting temperature of 300-700 ℃ for 0.5-5 hours to obtain the hydrofining catalyst. The preparation method can effectively improve the physicochemical property of the carrier, obviously improve the dispersion degree of the active metal on the surface of the catalyst, and is suitable for the preparation of hydrodemetallization, hydrodesulfurization and hydroconversion catalysts.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a preparation method of a hydrofining catalyst and the prepared hydrofining catalyst.
Background
With the increasing strictness of environmental regulations, new diesel oil standards put more strict requirements on the sulfur mass fraction, the aromatic hydrocarbon mass fraction and the cetane number of diesel oil products. The yield of the catalytic cracking diesel oil is about 30 percent of the total yield of the diesel oil, and the catalytic cracking diesel oil cannot be directly used as the diesel oil due to low cetane number, high mass fractions of sulfur, nitrogen and colloid, dark color of an oil product and poor stability. The hydrogenation process is one of the most effective process means for improving the quality of oil products, and the hydrogenation catalyst is the most important and key technology in the hydrogenation process.
CN1133723C discloses a distillate oil hydrorefining catalyst and a preparation method thereof, wherein, alumina pellets containing 5-15 wt% of silicon dioxide are used as carriers and contain MoO321-28 wt%, NiO 2-8 wt% and CoO 0.03-2.0 wt%, and two-stage spray soaking is adopted. The catalyst has higher hydrodesulfurization and hydrodenitrogenation activities at the same time, and is suitable for hydrofining of inferior distillate oil containing more sulfur and nitrogen at the same time.
WO2007084438 discloses a selective hydrodesulphurisation catalyst comprising 8-30 wt% of molybdenum selected from group VIB, 2-8 wt% of cobalt selected from group VIII, and a suitable amount of organic substance as complexing agent on a silicon carrier. When the catalyst is used for treating catalytic cracking gasoline raw materials, the olefin saturation rate is low.
CN1123765.1 discloses a diesel hydrotreating catalyst, which contains a carrier and indium and/or tungsten and nickel and/or cobalt loaded on the carrier, and is characterized in that the carrier is composed of alumina and zeolite, the weight ratio of the alumina to the zeolite is 90:10-50:50, the alumina is alumina compounded by small-pore alumina and large-pore alumina according to the weight ratio of 75:25-50:50, wherein the small-pore alumina is alumina with the diameter of less than 80 angstrom pores accounting for more than 95% of the total pore volume, and the large-pore alumina is alumina with the diameter of 60-600 angstrom pores accounting for more than 70% of the total pore volume.
CN1049679C disclosesThe diesel oil hydro-conversion catalyst takes alumina and Y-shaped molecular sieve as carriers, contains at least one VIB group metal and at least one VIll group metal, and is characterized in that the catalyst carrier comprises 40-90 w% of alumina, 0-20 w% of amorphous silica-alumina and 5-40 w% of molecular sieve, wherein the pore volume of the Y-shaped molecular sieve is 0.40-0.52ml/g, and the specific surface area is 750-900 m-2Unit cell constant 2.420-2.500nm, SiO2/A12O3In the ratio of 7-15, the content of VIB group metal oxide in the catalyst is 10-30 w%, and the content of VIll group metal oxide in the catalyst is 2-15 w%. It is suitable for the hydrogenation conversion of 150-400 deg.C petroleum fraction, especially for the conversion of catalytic cracking Light Cycle Oil (LCO) with high sulfur, nitrogen and aromatic hydrocarbon contents and low cetane number, and features that under the milder condition, the contents of sulfur, nitrogen and aromatic hydrocarbon are reduced and the cetane number of the product is greatly raised.
CN1289828A discloses a new compound prepared from gamma-Al2O3Or by containing SiO2gamma-Al of (2)2O3The hydrofining catalyst as carrier has W, Mo, Ni and P as active components. With SiO2Modified Al2O3The hydrogenation catalyst which is a carrier has improved performance, but the carrier has lower acid content and fewer strong acid centers, is not beneficial to ring opening and breaking of nitrogen heterocycles, and has poor denitrification activity.
Disclosure of Invention
The invention aims to overcome the defects of poor dispersion degree of active components and poor catalytic denitrification activity in the existing prepared hydrogenation catalyst, and provides a hydrofining catalyst and a preparation method thereof. The method can effectively improve the stability of the catalyst and improve the dispersion degree of the active metal.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a hydrorefining catalyst, which comprises the following steps:
(1) uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, adjusting the pH value of the obtained slurry to 5-10, stirring at room temperature of-90 ℃ for 0.5-24 hours, filtering, drying, and roasting at 550-800 ℃ for 2-5 hours to obtain a composite alumina carrier;
(2) dipping the composite alumina carrier in an organic solvent to obtain active metal, and drying;
(3) and (3) roasting the product obtained in the step (2) in an inert atmosphere at the roasting temperature of 300-700 ℃ for 0.5-5 hours to obtain the hydrofining catalyst.
The second aspect of the invention provides a hydrofining catalyst prepared by the preparation method.
By adopting the technical scheme, the alumina carrier is modified by adopting the auxiliary active component, so that the stability of the carrier can be effectively improved; the organic solvent dipping method can obviously improve the dispersion degree of the active metal on the surface of the catalyst, thereby obviously improving the desulfurization and denitrification effects of the hydrofining catalyst. The hydrogenation catalyst provided by the invention is particularly suitable for hydrodemetallization, hydrodesulfurization and hydroconversion reactions.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following examples are intended to further illustrate the present invention and to assist the reader in better understanding the nature and advantages of the present invention, but are not to be construed as limiting the scope of the invention in any way.
In a first aspect, the present invention provides a process for preparing a hydrorefining catalyst, comprising the steps of:
(1) uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, adjusting the pH value of the obtained slurry to 5-10, stirring at room temperature of-90 ℃ for 0.5-24 hours, filtering, drying, and roasting at 550-800 ℃ for 2-5 hours to obtain a composite alumina carrier;
(2) dipping the composite alumina carrier in an organic solvent to obtain active metal, and drying;
(3) and (3) roasting the product obtained in the step (2) in an inert atmosphere at the roasting temperature of 300-700 ℃ for 0.5-5 hours to obtain the hydrofining catalyst.
In some embodiments provided herein, step (1) is used to prepare a composite aluminaA support, which can be modified to provide improved performance ultimately to the resulting hydrogenation catalyst. Preferably, the specific surface area of the alumina carrier is 70-400m2The pore volume is 0.2-1.5 mL/g. To be able to provide better carrier performance.
In some embodiments of the invention, the co-active component-containing compound can be used to achieve the addition of a co-active component to an alumina support, as needed to tailor the alumina support to better suit the performance of a hydrogenation catalyst. Preferably, the auxiliary active component is one or more selected from RE, Mg and Ca. That is, one or more elements selected from RE, Mg and Ca are introduced into the alumina carrier.
In some embodiments of the invention, the co-active component may be incorporated into the alumina support by using the co-active component-containing compound. Preferably, the compound containing a co-active ingredient may be selected from soluble salts of the co-active ingredient, such as sulphate, nitrate or chloride salts. More preferably one or more of RE, Mg and Ca, and sulfate, nitrate or chloride of the elements.
In some embodiments of the present invention, the amount of each raw material fed in step (1) is enough to satisfy the content required in the finally obtained composite alumina carrier, and preferably, the ratio of the alumina carrier: the weight ratio of the compounds containing the auxiliary active components is 1: (0.01-0.3), wherein the compound containing the auxiliary active component is calculated by oxide. Preferably, the weight ratio may be 1 (0.1-0.3), may be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, and may range between any two of the above values.
In some embodiments of the present invention, the pH adjustment in step (1) may be performed by adding a precipitant, such as an alkaline substance, preferably ammonia water, to avoid introducing impurity elements.
In some embodiments provided by the present invention, step (2) is used for supporting the active metal, and the active metal required by the hydrofining catalyst of the present invention is supported on the composite alumina carrier. Preferably, in the step (2), the active metal is a group VIII and/or a group VIB metal, the group VIII metal is at least one of Fe, Ni, and Co, and the group VIB metal is W and/or Mo. The dosage of the active metal is further preferably 0.1 wt% -30 wt% of the VIII group metal calculated by metal oxide and 0.08 wt% -20 wt% of the VIB group metal calculated by metal oxide relative to the composite alumina carrier. Preferably, the group VIII metal is used in an amount of 5 wt% to 20 wt% and the group VIB metal is used in an amount of 5 wt% to 20 wt%.
In some embodiments provided by the present invention, preferably, in step (3), the impregnating process includes: dissolving the precursor of the active metal in the organic solvent, then mixing with the composite zirconia carrier, and keeping for 0.5-12 hours under stirring or standing, wherein the composite zirconia carrier: the solid-liquid weight ratio of the organic solvent is 1: (0.5-5); preferably, the number of said impregnations is at least 1. The precursor of the active metal may be selected from compounds containing the active metal which are soluble in the organic solvent, and may be, for example, ferric chloride, ammonium molybdate, cobalt nitrate, ammonium metatungstate, nickel nitrate. Wherein, after the impregnation process is finished, drying is carried out for 10-15 hours at the temperature of 80-120 ℃, and the organic solvent is removed. The precursor of the active metal is used in an amount satisfying the addition amount of the active metal.
In some embodiments provided herein, preferably, the organic solvent has a normal boiling point of preferably 40 to 100 ℃. Preferably, the organic solvent may be one or more of alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane. Preferably, the organic solvent is one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and chloroform. The organic solvent and the amount used for impregnating the active metal in the step (3) can help to improve the dispersion degree of the active metal on the surface of the catalyst.
In some embodiments provided by the present invention, preferably, in the step (4), the calcination temperature is 450-650 ℃, and the calcination time is 1-4 hours.
The second aspect of the invention provides a hydrofining catalyst prepared by the method.
In some embodiments provided herein, the catalyst obtained has a specific surface area of 250-400m2G, preferably 270-300m2(ii)/g; the pore volume is 0.4-0.6mL/g, preferably 0.4-0.5 mL/g. The hydrofining catalyst comprises the following components: based on the total amount of the catalyst, the content of alumina is 25-75 wt%, the content of the auxiliary active elements (calculated by oxide) is 1-25 wt%, the content of VIII group metals (calculated by metal oxide) is 0.1-30 wt%, and the content of VIB group metals (calculated by metal oxide) is 0.08-20 wt%. The composition of the hydrofining catalyst can be measured by a fluorescence analysis method and can also be calculated by preparation feeding.
The invention also provides a method for hydrorefining catalytic cracking diesel, which comprises the following steps: the catalytic cracking diesel oil is subjected to hydrofining reaction in the presence of a hydrofining catalyst, and the hydrofining catalyst is the distillate oil hydrofining catalyst.
The catalytic cracking diesel oil may be diesel oil produced from a catalytic cracking process of petroleum refining. The conditions of the hydrofinishing reaction may be: the temperature is 300--1The volume ratio of the hydrogen to the raw material catalytic cracking diesel oil is 200-500: 1.
By using the hydrofining catalyst, the hydrodesulfurization rate of catalytic cracking diesel oil reaches 100%, and the denitrification rate is more than 94.0%.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the specific surface area and the pore volume of the catalyst are measured by a BET test method;
the sulfur content in the raw oil and the hydrogenation product is measured by a gas chromatography method;
the hydrodesulfurization rate is 1- (the content of sulfur in the raw oil-the content of sulfur in the hydrogenated product)/the content of sulfur in the raw oil is multiplied by 100 percent;
the hydrogenation denitrification rate is 1- (the content of nitrogen in the raw oil-the content of nitrogen in the hydrogenation product)/the content of nitrogen in the raw oil is multiplied by 100%.
Example 1
650g of alumina (86% by weight in terms of solids content, Al)2O3559g), 240mL of rare earth chloride solution (the content of rare earth oxide is 250g/L, and the rare earth oxide is converted into 60g of rare earth oxide), 3200g of deionized water are mixed, the pH value of the mixture is adjusted to 5.5 by using dilute ammonia water, the mixture is stirred and aged for 2 hours at room temperature, and after filtration, the mixture is dried for 12 hours at 120 ℃ and roasted for 2 hours at 750 ℃, so that the composite alumina carrier is obtained. Alumina: the weight ratio of the rare earth oxide is 1: 0.11.
339g of ferric chloride and 272g of ammonium molybdate are dissolved in 800g of ethanol (with the purity of 99.9%) to prepare an impregnation solution, the obtained impregnation solution and the composite alumina carrier (relative to the composite alumina carrier, the dosage of ferric oxide is 10 wt%, and the dosage of molybdenum oxide is 20 wt%) are uniformly mixed (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1: 2), the mixture is kept at room temperature for 12 hours, and then the obtained product is dried for 24 hours at 100 ℃ and is calcined for 4 hours at 500 ℃ in a nitrogen atmosphere. Catalyst A1 was obtained. The analytical results of catalyst A1 are shown in Table 1.
Example 2
547g of alumina (86% by weight in terms of solids content, Al)2O3470.4g), 203g of magnesium chloride (85.5 g of converted magnesium oxide) and 2000g of deionized water, adjusting the pH value of the mixture to 7.5 by using dilute ammonia water, stirring and aging the mixture for 1 hour at 40 ℃, drying the dried mixture for 12 hours at 120 ℃ after filtering, and roasting the dried mixture for 3 hours at 650 ℃ to obtain the composite alumina carrier. Alumina: the weight ratio of magnesium oxide is 1: 0.18.
280g of cobalt nitrate Co (NO)3)2·6H2O and 160g of ammonium metatungstate are dissolved in 900g of ethanol (the purity is 99.9%) to prepare an impregnation solution, the obtained impregnation solution is uniformly mixed with the composite alumina carrier (relative to the composite alumina carrier, the dosage of cobalt oxide is 8 wt%, and the dosage of tungsten oxide is 15 wt%) (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1: 2), the mixture is kept at room temperature for 8 hours, and then the obtained product is dried at 120 ℃ for 6 hours and is calcined at 550 ℃ for 2 hours in a nitrogen atmosphere. Catalyst A2 was obtained. The analytical results of catalyst A2 are shown in Table 1.
Example 3
465g of alumina (86% by weight in terms of solids content, Al)2O3399.9g), 99g calcium chloride (converted to calcium oxide 49.9) and 5600g deionized water, the pH value of the mixture was adjusted to 6.5 with dilute ammonia water, the mixture was stirred and aged at 60 ℃ for 1 hour, after filtration, the mixture was dried at 120 ℃ for 12 hours and calcined at 550 ℃ for 5 hours to obtain a composite alumina carrier. Alumina: the weight ratio of calcium oxide is 1: 0.12.
489g of nickel nitrate and 68g of ammonium molybdate were dissolved in 600g of cyclohexane (purity: 99.9%) to prepare an impregnation solution, the obtained impregnation solution was uniformly mixed with the above composite alumina support (the amount of nickel oxide was 20 wt% and the amount of molybdenum oxide was 5 wt% relative to the composite alumina support) (the solid-liquid weight ratio of the composite alumina support to the organic solvent was 1: 2), the mixture was kept at room temperature for 12 hours, and then the obtained product was dried at 120 ℃ for 6 hours and calcined at 600 ℃ for 3 hours under a nitrogen atmosphere. Catalyst A3 was obtained. The analytical results of catalyst A3 are shown in Table 1.
Example 4
442g of alumina (86% by weight in terms of solids content, Al)2O3380.1g), 240g of magnesium sulfate (converted to magnesium oxide 40g) and 4600g of deionized water, adjusting the pH value of the mixture to 7.5 by using dilute ammonia water, stirring and aging at 60 ℃ for 1.5 hours, filtering, drying at 120 ℃ for 12 hours, and roasting at 700 ℃ for 2 hours to obtain the composite alumina carrier. Alumina: the weight ratio of magnesium oxide is 1: 0.10.
175g of cobalt nitrate Co (NO)3)2·6H2O and 272g of ammonium molybdate are dissolved in 1000g of cyclohexane (with the purity of 99.9%) to prepare an impregnation solution, the obtained impregnation solution is uniformly mixed with the composite alumina carrier (relative to the composite alumina carrier, the dosage of cobalt oxide is 5 wt%, and the dosage of molybdenum oxide is 20 wt%) (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1: 3), the mixture is kept at room temperature for 24 hours, and then the obtained product is dried at 120 ℃ for 6 hours and is calcined at 650 ℃ for 3 hours in a nitrogen atmosphere. Catalyst A4 was obtained. The analytical results of catalyst A4 are shown in Table 1.
Example 5
523g of alumina (86% strength by weight in terms of solids, Al)2O3449.8g), 480mL of rare earth chloride solution (rare earth oxide containingThe amount of 250g/L is converted into 120g of rare earth oxide), 2700g of deionized water are mixed, the pH value of the mixture is adjusted to 8.5 by using dilute ammonia water, the mixture is stirred and aged for 1.5 hours at the temperature of 90 ℃, the mixture is dried for 12 hours at the temperature of 120 ℃ after being filtered, and the mixture is roasted for 2 hours at the temperature of 700 ℃ to obtain the composite alumina carrier. Alumina: the weight ratio of the rare earth oxide is 1: 0.27.
526g of cobalt nitrate Co (NO)3)2·6H2O and 106g of ammonium metatungstate are dissolved in 1000g of butanone (the purity is 99.9%) to prepare an impregnation solution, the obtained impregnation solution is uniformly mixed with the composite alumina carrier (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1: 2, the dosage of cobalt oxide is 15 wt% and the dosage of tungsten oxide is 10 wt% relative to the composite alumina carrier), the mixture is kept at room temperature for 24 hours, and then the obtained product is dried at 120 ℃ for 6 hours and is calcined at 550 ℃ for 3 hours in a nitrogen atmosphere. Catalyst A5 was obtained. The analytical results of catalyst A5 are shown in Table 1.
Comparative example 1
339g of ferric chloride and 272g of ammonium molybdate are dissolved in 800g of deionized water to prepare an impregnation solution, the obtained impregnation solution and an alumina carrier are uniformly mixed, the mixture is kept at room temperature for 12 hours, then the obtained product is dried for 24 hours at 100 ℃, and is roasted for 4 hours at 500 ℃ in an air atmosphere. Comparative catalyst D1 was obtained. The results of the catalyst analysis are shown in Table 1.
Comparative example 2
650g of alumina (86% by weight in terms of solids content, Al)2O3559g), 240mL of rare earth chloride solution (the content of rare earth oxide is 250g/L, and the rare earth oxide is converted into 60g of rare earth oxide), 3200g of deionized water are mixed, the pH value of the mixture is adjusted to 5.5 by using dilute ammonia water, the mixture is stirred and aged for 2 hours at room temperature, and after filtration, the mixture is dried for 12 hours at 120 ℃ and roasted for 2 hours at 750 ℃, so that the composite alumina carrier is obtained. Alumina: the weight ratio of the rare earth oxide is 1: 0.11.
339g of ferric chloride and 272g of ammonium molybdate are dissolved in 800g of deionized water to prepare an impregnation solution, the obtained impregnation solution is uniformly mixed with the composite alumina carrier (relative to the composite alumina carrier, the dosage of ferric oxide is 12 wt%, and the dosage of molybdenum oxide is 23 wt%) (the solid-liquid weight ratio of the composite alumina carrier to water is 1: 2), the mixture is kept at room temperature for 12 hours, and then the obtained product is dried at 100 ℃ for 24 hours and is calcined at 500 ℃ for 4 hours in an air atmosphere. Comparative catalyst D2 was obtained. The results of the catalyst analysis are shown in Table 1.
TABLE 1
The results in table 1 show that the catalyst prepared by the method of the invention has higher specific surface area and pore volume, and higher metal dispersity on the surface of the carrier.
Examples 6 to 10
The catalysts A1-A5 were subjected to hydrodesulfurization and denitrification reactions in accordance with the feed oils and evaluation conditions provided in Table 2. The reaction evaluation results are shown in Table 3.
TABLE 2
| Raw oil | Catalytic diesel fuel |
| Density at 20 ℃ in kg/m3 | 975 |
| S, ppm (by mass) | 6500 |
| N, ppm (by mass) | 880 |
| Partial pressure of hydrogen, MPa | 6.0 |
| Temperature, C | 340 |
| Volumetric space velocity h-1 | 2.0 |
| Volume ratio of hydrogen to oil | 300 |
Comparative examples 3 to 4
Catalysts D1-D2 were subjected to hydrodesulfurization and denitrogenation in the same manner as in examples 6-10. The reaction evaluation results are shown in Table 3.
TABLE 3
The results in table 3 show that the catalyst provided by the invention has higher catalytic hydrogenation activity, and the catalytic diesel hydrogenation performance of the catalyst is obviously superior to that of a comparative catalyst.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
It should be noted that the technical features described in the above embodiments may be combined in any manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, various different embodiments of the present invention can be combined arbitrarily, and the same should be regarded as the disclosure of the present invention as long as it does not depart from the idea of the present invention.
Claims (10)
1. A preparation method of a hydrofining catalyst comprises the following steps:
(1) uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, adjusting the pH value of the obtained slurry to 5-10, stirring at room temperature of-90 ℃ for 0.5-24 hours, filtering, drying, and roasting at 550-800 ℃ for 2-5 hours to obtain a composite alumina carrier;
(2) dipping the composite alumina carrier in an organic solvent to obtain active metal, and drying;
(3) and (3) roasting the product obtained in the step (2) in an inert atmosphere at the roasting temperature of 300-700 ℃ for 0.5-5 hours to obtain the hydrofining catalyst.
2. The method according to claim 1, wherein the auxiliary active component is selected from one or more of RE, Mg and Ca.
3. A method according to claim 1 or claim 2, wherein the compound comprising the co-active ingredient is selected from soluble salts of the co-active ingredient, the soluble salts being sulphates, nitrates or chlorides.
4. A process according to any one of claims 1 to 3, characterised in that the alumina support: the weight ratio of the compounds containing the auxiliary active components is 1: (0.01-0.3), wherein the compound containing the auxiliary active component is calculated by oxide.
5. The method according to any one of claims 1-4, characterized in that the active metal is a group VIII and/or a group VIB metal, the group VIII metal being at least one of Fe, Ni, Co, the group VIB metal being W and/or Mo;
preferably, the amount of the VIII group metal calculated by metal oxide is 0.1-30 wt%, and the amount of the VIB group metal calculated by metal oxide is 0.08-20 wt% relative to the composite alumina carrier.
6. The method according to any one of claims 1 to 5, wherein one or more auxiliary agents selected from P, B, Ti and Zr are further added into the organic solvent.
7. The method according to any one of claims 1-6, wherein the impregnating comprises: dissolving the precursor of the active metal in the organic solvent, then mixing with the composite alumina carrier, and keeping for 0.5-12 hours under stirring or standing, wherein the composite alumina carrier: the solid-liquid weight ratio of the organic solvent is 1: (0.5-5);
preferably, the number of said impregnations is at least 1.
8. The method according to any one of claims 1 to 7, wherein the organic solvent has a normal boiling point of 40 to 100 ℃;
preferably, the organic solvent is selected from one or more of alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester and halogenated alkane; preferably, the organic solvent is one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and chloroform.
9. The method as claimed in any one of claims 1 to 8, wherein the calcination temperature in step (3) is 450 ℃ and 650 ℃ and the calcination time is 1 to 4 hours.
10. A hydrorefining catalyst obtained by the production method according to any one of claims 1 to 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248412A (en) * | 1990-03-30 | 1993-09-28 | Cosmo Research Institute | Process for producing catalyst composition for use in hydrodesulfurization of hydrocarbon oil and process for hydrodesulfurizing hydrocarbon oil |
| JP2001162168A (en) * | 1999-09-29 | 2001-06-19 | Petroleum Energy Center | Hydrogenation catalyst and method for hydrogenation treatment of heavy hydrocarbon oil by using that catalyst |
| US7390766B1 (en) * | 2003-11-20 | 2008-06-24 | Klein Darryl P | Hydroconversion catalysts and methods of making and using same |
| CN101563437A (en) * | 2006-12-19 | 2009-10-21 | 埃克森美孚研究工程公司 | High activity supported distillate hydroprocessing catalysts |
| CN103007949A (en) * | 2011-09-27 | 2013-04-03 | 中国石油天然气集团公司 | Method for preparing hydrogenation catalyst |
| CN106607102A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and application thereof |
| CN106607039A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN107442129A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its preparation method and application |
| CN107812525A (en) * | 2016-09-12 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of hydrogenating catalyst composition and the method for hydrotreating |
| CN107961795A (en) * | 2016-10-20 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst and preparation method thereof and sulphided state Hydrobon catalyst |
-
2020
- 2020-12-16 CN CN202011490415.3A patent/CN112973717B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248412A (en) * | 1990-03-30 | 1993-09-28 | Cosmo Research Institute | Process for producing catalyst composition for use in hydrodesulfurization of hydrocarbon oil and process for hydrodesulfurizing hydrocarbon oil |
| JP2001162168A (en) * | 1999-09-29 | 2001-06-19 | Petroleum Energy Center | Hydrogenation catalyst and method for hydrogenation treatment of heavy hydrocarbon oil by using that catalyst |
| US7390766B1 (en) * | 2003-11-20 | 2008-06-24 | Klein Darryl P | Hydroconversion catalysts and methods of making and using same |
| CN101563437A (en) * | 2006-12-19 | 2009-10-21 | 埃克森美孚研究工程公司 | High activity supported distillate hydroprocessing catalysts |
| CN103007949A (en) * | 2011-09-27 | 2013-04-03 | 中国石油天然气集团公司 | Method for preparing hydrogenation catalyst |
| CN106607102A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and application thereof |
| CN106607039A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN107442129A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its preparation method and application |
| CN107812525A (en) * | 2016-09-12 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of hydrogenating catalyst composition and the method for hydrotreating |
| CN107961795A (en) * | 2016-10-20 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst and preparation method thereof and sulphided state Hydrobon catalyst |
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