CN112973717B - Hydrofining catalyst and preparation method thereof - Google Patents
Hydrofining catalyst and preparation method thereof Download PDFInfo
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- CN112973717B CN112973717B CN202011490415.3A CN202011490415A CN112973717B CN 112973717 B CN112973717 B CN 112973717B CN 202011490415 A CN202011490415 A CN 202011490415A CN 112973717 B CN112973717 B CN 112973717B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 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 79
- 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
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 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
- 239000011148 porous material Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 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
- 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
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 16
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004523 catalytic cracking Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 9
- 229910052717 sulfur Inorganic materials 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
- 239000003921 oil Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 230000000694 effects Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- -1 VIB metal oxide Chemical class 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000011575 calcium Substances 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
- 238000011156 evaluation Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 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
- 230000003197 catalytic effect Effects 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
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 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
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen 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
- 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons 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
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 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
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 150000002894 organic compounds Chemical class 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
- 238000007670 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
- 239000000377 silicon dioxide 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
- 239000000126 substance 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
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 hydrofining 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, regulating the pH value of the obtained slurry to be 5-10, stirring for 0.5-24 hours at the temperature of room temperature to 90 ℃, filtering, drying, and roasting for 2-5 hours at the temperature of 550-800 ℃ to obtain a composite alumina carrier; (2) Dipping the composite alumina carrier into an organic solvent to impregnate active metal, and drying; (3) Roasting the product obtained in the step (2) in an inert atmosphere at a roasting temperature of 300-700 ℃ for 0.5-5 hours to obtain the hydrofining catalyst. The preparation method can effectively improve the physicochemical properties of the carrier, remarkably improve the dispersity of the active metal on the surface of the catalyst, and is suitable for preparing 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 hydrofining catalyst prepared by the preparation method.
Background
As environmental regulations become more stringent, new diesel standards place more stringent demands on sulfur mass fraction, aromatic mass fraction, and cetane number in diesel products. The yield of the catalytic cracking diesel oil is about 30% of the total yield of the diesel oil, and the diesel oil cannot be directly used as the diesel oil due to low cetane number, high mass fractions of sulfur, nitrogen and colloid, deep color and poor stability of the oil product. The hydrogenation process is one of the most effective technological means for improving the quality of oil, and the hydrogenation catalyst is the most important and key technology in the hydrogenation process.
CN1133723C discloses a distillate hydrofining catalyst and a preparation method thereof, wherein alumina pellets containing 5-15wt% of silicon dioxide are used as a carrier, and MoO is contained 3 21-28wt%, niO 2-8wt%, coO 0.03-2.0wt% and two-stage spray leaching. The catalyst has higher hydrodesulfurization and hydrodenitrogenation activities at the same time, and is suitable for hydrofining of inferior distillate oil with more sulfur and nitrogen.
WO2007084438 discloses a selective hydrodesulfurization catalyst comprising 8-30 wt.% molybdenum from group VIB, 2-8 wt.% cobalt from group VIII, and a suitable amount of an organic compound as complexing agent supported on a silicon carrier. The catalyst is used for treating the catalytic cracking gasoline raw material, and the olefin saturation rate is low.
CN1123765.1 discloses a diesel hydrotreating catalyst, which comprises a carrier and indium and/or tungsten and nickel and/or cobalt supported on the carrier, and is characterized in that the carrier is composed of alumina and zeolite, the weight ratio of alumina to zeolite is 90:10-50:50, the alumina is formed by compounding 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 pore volume 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 pore volume of 60-600 angstrom pores accounting for more than 70% of the total pore volume.
CN1049679C discloses a diesel oil hydro-conversion catalyst, which takes alumina and Y-type molecular sieve as carriers and 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 wt% of alumina, 0-20 wt% of amorphous silica-alumina, 5-40 wt% of molecular sieve, wherein the Y-type molecular sieve pore volume is 0.40-0.52ml/g, and the specific surface is 750-900m 2 Per g, unit cell constant 2.420-2.500nm, siO 2 /A1 2 O 3 The ratio of the catalyst to the VIB metal oxide is 7-15, the content of the VIB metal oxide in the catalyst is 10-30w%, and the content of the VILL metal oxide is 2-15w%. It is suitable for the hydro-conversion of petroleum fraction at 150-400 deg.C, especially for the conversion of catalytically cracked Light Cycle Oil (LCO) with high contents of S, N and aromatic hydrocarbon and lower hexadecane kang value, and features less S, N and aromatic hydrocarbon under mild conditionThe content of hydrocarbon greatly improves the cetane number of the product.
CN1289828A discloses a method of using gamma-Al 2 O 3 Or by containing SiO 2 gamma-Al of (2) 2 O 3 The catalyst is a hydrofining catalyst with a carrier, and W, mo, ni, P is taken as an active component. In SiO form 2 Modified Al 2 O 3 The hydrogenation catalyst performance of the carrier is improved to a certain extent, but the carrier has lower acid content and less strong acid center, is not beneficial to ring opening fracture of nitrogen heterocycle, and has poor denitrification activity.
Disclosure of Invention
The invention aims to overcome the defects of poor dispersity of active components and poor catalytic denitrification activity in the conventional prepared hydrogenation catalyst, and provides a hydrofining catalyst and a preparation method thereof. The method can effectively improve the stability of the catalyst and the dispersity of the active metal.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing a hydrofining catalyst, comprising the following specific steps:
(1) Uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, regulating the pH value of the obtained slurry to be 5-10, stirring for 0.5-24 hours at the temperature of room temperature to 90 ℃, filtering, drying, and roasting for 2-5 hours at the temperature of 550-800 ℃ to obtain a composite alumina carrier;
(2) Dipping the composite alumina carrier into an organic solvent to impregnate active metal, and drying;
(3) Roasting the product obtained in the step (2) in an inert atmosphere at a 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.
According to the technical scheme, the auxiliary active component is adopted to carry out modification treatment on the alumina carrier, so that the stability of the carrier can be effectively improved; the dispersion degree of the active metal on the surface of the catalyst can be obviously improved by adopting an organic solvent impregnation method, so that the desulfurization and denitrification effects of the hydrofining catalyst are obviously improved. 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 provided to further illustrate the invention and are intended to aid the reader in better understanding the benefits that the essence of the invention resides in and is brought about, but should not be construed as limiting the scope of the invention in any way.
The first aspect of the present invention provides a method for preparing a hydrofining catalyst, comprising the steps of:
(1) Uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, regulating the pH value of the obtained slurry to be 5-10, stirring for 0.5-24 hours at the temperature of room temperature to 90 ℃, filtering, drying, and roasting for 2-5 hours at the temperature of 550-800 ℃ to obtain a composite alumina carrier;
(2) Dipping the composite alumina carrier into an organic solvent to impregnate active metal, and drying;
(3) Roasting the product obtained in the step (2) in an inert atmosphere at a 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 alumina support, and modification of the support may be accomplished to provide a final performance improvement to the resulting hydrogenation catalyst. Preferably, the specific surface area of the alumina carrier is 70-400m 2 Per g, pore volume is 0.2-1.5mL/g. To be able to provide better carrier properties.
In some embodiments of the invention, the co-active component containing compounds can be used to effect the addition of a co-active component to an alumina support, as required to achieve better adaptation of the alumina support to the performance of the hydrogenation catalyst. Preferably, the auxiliary active component is one or more selected from Re, mg and Ca. Namely, 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 an alumina support by using the co-active component containing compound. Preferably, the co-active component containing compound may be selected from soluble salts of the co-active component, such as sulphate, nitrate or chloride salts. More preferably, it is one or more of Re, mg and Ca.
In some embodiments of the present invention, the amount of each raw material in step (1) may be such that the amount of each raw material to be added is as desired in the finally obtained composite alumina carrier, preferably the alumina carrier: the weight ratio of the compound containing the auxiliary active component is 1: (0.01-0.3), wherein the co-active ingredient-containing compound is in the form of an oxide. Preferably, the weight ratio may be 1 (0.1-0.3), and may be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, and any two of the foregoing.
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, to avoid the introduction of impurity elements.
In some embodiments provided herein, step (2) is used to support the active metal, and the active metal required by the hydrofinishing catalyst of the present invention is supported on the composite alumina support. Preferably, in the step (2), the active metal is a metal of group VIII and/or group VIB, the metal of group VIII is at least one of Fe, ni, co, and the metal of group VIB is W and/or Mo. The amount of the active metal is further preferably 0.1wt% to 30wt% of the group VIII metal in terms of metal oxide and 0.08wt% to 20wt% of the group VIB metal in terms of metal oxide, relative to the composite alumina carrier. Preferably, the group VIII metal is used in an amount of 5wt% to 20wt% and the group VIB metal is used in an amount of 5wt% to 20wt%.
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 alumina carrier, and keeping for 0.5-12 hours under stirring or standing, wherein the composite alumina carrier is prepared by the following steps: the solid-liquid weight ratio of the organic solvent is 1: (0.5-5); preferably, the number of impregnations is at least 1. The precursor of the active metal may be selected from compounds soluble in the organic solvent containing the active metal, and may be, for example, ferric chloride, ammonium molybdate, cobalt nitrate, ammonium metatungstate, nickel nitrate. And after the soaking process is finished, drying is carried out, the temperature is 80-120 ℃, the time is 10-15 hours, and the organic solvent is removed. The precursor of the active metal is used in an amount which satisfies the addition amount of the active metal.
In some embodiments provided herein, preferably, the organic solvent has a normal boiling point of preferably 40-100 ℃. Preferably, the organic solvent may be one or more of alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, and haloalkane. Preferably, the organic solvent is preferably 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 dispersity of the active metal on the surface of the catalyst.
In some embodiments provided herein, preferably, in step (4), the firing temperature is 450-650 ℃ and the firing time is 1-4 hours.
In a second aspect, the present invention provides a hydrofinishing catalyst prepared by the above method.
In some embodiments provided herein, the catalyst obtained has a specific surface area of 250-400m 2 Preferably 270-300m 2 /g; the pore volume is 0.4-0.6 mL/g, preferably 0.4-0.5 mL/g. The hydrofining catalyst comprises the following components: the catalyst comprises, based on the total amount of the catalyst, 25-75wt% of alumina, 1-25wt% of a co-active element (calculated as oxide), 0.1-30wt% of a group VIII metal (calculated as metal oxide), and 0.08-20wt% of a group VIB metal (calculated as metal oxide). The composition of the hydrofining catalyst can be determined by a fluorescence analysis method, and can also be calculated by preparing and feeding materials.
The invention also provides a hydrofining method of the catalytic cracking diesel, which comprises the following steps: and carrying out hydrofining reaction on the catalytic cracking diesel in the presence of a hydrofining catalyst, wherein the hydrofining catalyst is the distillate oil hydrofining catalyst.
The catalytic cracking diesel may be a diesel produced from a catalytic cracking process for petroleum refining. The conditions for the hydrofinishing reaction may be: the temperature is 300-400 ℃, the hydrogen partial pressure is 5-7MPa, and the volume space velocity of the raw material catalytic cracking diesel is 1-4h -1 The volume ratio of hydrogen to the raw material catalytic cracking diesel is 200-500:1.
The hydrogenation refining catalyst of the invention has the hydrogenation desulfurization rate of the catalytic cracking diesel reaching 100% and the denitrification rate of over 94.0%.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the specific surface area and 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;
hydrodesulfurization ratio% = 1- (sulfur content in feedstock-sulfur content in hydrogenation product)/sulfur content in feedstock x 100%;
hydrodenitrogenation ratio% = 1- (nitrogen content in feed oil-nitrogen content in hydrogenation product)/nitrogen content in feed oil x 100%.
Example 1
650g of alumina (86 wt% solids, al) 2 O 3 559 g), 240mL of rare earth chloride solution (the rare earth oxide content is 250g/L, the rare earth oxide content is converted into 60 g), 3200g of deionized water are mixed, the pH value of the mixture is regulated to 5.5 by dilute ammonia water, the mixture is stirred and aged for 2 hours at room temperature, the mixture is dried for 12 hours at 120 ℃ after being filtered, and the mixture is roasted for 2 hours at 750 ℃ to obtain the composite alumina carrier. 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 (purity is 99.9%) to prepare an impregnating solution, the impregnating solution is uniformly mixed with the composite alumina carrier (the dosage of ferric oxide is 10wt percent and the dosage of molybdenum oxide is 20wt percent relative to the composite alumina carrier) (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1:2), the mixture is kept at 12 h at room temperature, and then the obtained product is dried at 100 ℃ for 24 hours and baked at 500 ℃ for 4 hours under nitrogen atmosphere. Catalyst A1 was obtained. The results of the analysis of catalyst A1 are shown in Table 1.
Example 2
547g of alumina (86 wt% solids, al) 2 O 3 470.4 g), 203g of magnesium chloride (converted into 85.5g of 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 for 1 hour at 40 ℃, filtering, drying for 12 hours at 120 ℃, and roasting for 3 hours at 650 ℃ to obtain the composite alumina carrier. Alumina: the weight ratio of the magnesium oxide is 1:0.18.
280g of cobalt nitrate Co (NO) 3 ) 2 ·6H 2 O and 160g of ammonium metatungstate are dissolved in 900g of ethanol (purity is 99.9%) to prepare an impregnating solution, the impregnating solution is uniformly mixed with the composite alumina carrier (the dosage of cobalt oxide is 8wt percent and the dosage of tungsten oxide is 15wt percent relative to the composite alumina carrier) (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1:2), the mixture is kept at 8 h at room temperature, and then the obtained product is dried at 120 ℃ for 6 hours and baked at 550 ℃ for 2 hours under a nitrogen atmosphere. Catalyst A2 was obtained. The results of the analysis of catalyst A2 are shown in Table 1.
Example 3
465g of alumina (86 wt% solids, al) 2 O 3 399.9 g), 99g of calcium chloride (converted into calcium oxide 49.9) and 5600g of deionized water, adjusting the pH of the mixture to 6.5 with dilute ammonia water, stirring and aging for 1 hour at 60 ℃, filtering, drying for 12 hours at 120 ℃, and roasting for 5 hours at 550 ℃ to obtain the composite alumina carrier. Alumina: the weight ratio of the 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 impregnating solution, the impregnating solution was uniformly mixed with the above-mentioned composite alumina carrier (the amount of nickel oxide was 20wt% and the amount of molybdenum oxide was 5wt% relative to the composite alumina carrier) (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent was 1:2), and the resultant was kept at 12 h at room temperature, dried at 120℃for 6 hours, and calcined at 600℃for 3 hours under a nitrogen atmosphere. Catalyst A3 was obtained. The results of the analysis of catalyst A3 are shown in Table 1.
Example 4
442g of alumina (solids content 86wt%, al) 2 O 3 380.1 g), 240g of magnesium sulfate (40 g converted to magnesium oxide) and 4600g of deionized water, adjusting the pH of the mixture to 7.5 with dilute ammonia, aging for 1.5 hours at 60 ℃, filtering, drying for 12 hours at 120 ℃, and roasting for 2 hours at 700 ℃ to obtain the composite alumina carrier. Alumina: the weight ratio of the magnesium oxide is 1:0.10.
175g of cobalt nitrate Co (NO) 3 ) 2 ·6H 2 O and 272g of ammonium molybdate are dissolved in 1000g of cyclohexane (purity 99.9%) to prepare an impregnating solution, the impregnating solution is uniformly mixed with the composite alumina carrier (the dosage of cobalt oxide is 5wt percent and the dosage of molybdenum oxide is 20wt percent relative to the composite alumina carrier) (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1:3), the mixture is kept at 24 h at room temperature, and then the obtained product is dried at 120 ℃ for 6 hours and baked at 650 ℃ for 3 hours under a nitrogen atmosphere. Catalyst A4 was obtained. The results of the analysis of catalyst A4 are shown in Table 1.
Example 5
523g of alumina (86 wt% solids, al) 2 O 3 449.8 g), 480mL of rare earth chloride solution (the rare earth oxide content is 250g/L, the rare earth oxide is converted into 120 g), 2700g of deionized water are mixed, the pH value of the mixture is regulated to 8.5 by dilute ammonia water, the mixture is stirred and aged for 1.5 hours at 90 ℃, the mixture is dried for 12 hours at 120 ℃ after being filtered, and the mixture is baked for 2 hours at 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 ·6H 2 O, 106g of ammonium metatungstate are dissolved in 1000g of butanone (purity 99.9%) to prepare an impregnating solution, and the impregnating solution is mixed with the composite alumina carrier (the dosage of cobalt oxide is 15wt percent and the dosage of tungsten oxide is 10wt percent relative to the composite alumina carrier)Uniformly mixing (the solid-liquid weight ratio of the composite alumina carrier to the organic solvent is 1:2), keeping 24 h at room temperature, drying the obtained product at 120 ℃ for 6 hours, and roasting for 3 hours at 550 ℃ in a nitrogen atmosphere. Catalyst A5 was obtained. The results of the analysis 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 impregnating solution, the obtained impregnating solution is uniformly mixed with an alumina carrier, the obtained impregnating solution is kept at a room temperature for 12 h, and then the obtained product is dried at a temperature of 100 ℃ for 24 hours and baked for 4 hours under an air atmosphere of 500 ℃. Comparative catalyst D1 was obtained. The results of the catalyst analysis are shown in Table 1.
Comparative example 2
650g of alumina (86 wt% solids, al) 2 O 3 559 g), 240mL of rare earth chloride solution (the rare earth oxide content is 250g/L, the rare earth oxide content is converted into 60 g), 3200g of deionized water are mixed, the pH value of the mixture is regulated to 5.5 by dilute ammonia water, the mixture is stirred and aged for 2 hours at room temperature, the mixture is dried for 12 hours at 120 ℃ after being filtered, and the mixture is roasted for 2 hours at 750 ℃ to obtain the composite alumina carrier. 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 impregnating solution, the obtained impregnating solution is uniformly mixed with the composite alumina carrier (the dosage of ferric oxide is 12wt percent and the dosage of molybdenum oxide is 23wt percent relative to the composite alumina carrier) (the solid-liquid weight ratio of the composite alumina carrier to water is 1:2), the obtained product is kept at 12 h at room temperature, then the obtained product is dried at 100 ℃ for 24 hours, and is roasted 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 dispersity of metal on the surface of the carrier.
Examples 6 to 10
Catalysts A1-A5 were subjected to hydrodesulfurization and denitrification reactions according to the feed oil and evaluation conditions provided in Table 2. The reaction evaluation results are shown in Table 3.
TABLE 2
Comparative examples 3 to 4
Catalysts D1-D2 were subjected to hydrodesulfurization and denitrification reactions according to the methods of examples 6-10. The reaction evaluation results are shown in Table 3.
TABLE 3 Table 3
| Numbering device | Catalyst name | Hydrodesulfurization,% | Hydrodenitrogenation, percent |
| Example 6 | A1 | 100 | 90.3 |
| Example 7 | A2 | 100 | 94.4 |
| Example 8 | A3 | 100 | 97.5 |
| Example 9 | A4 | 100 | 95.5 |
| Example 10 | A5 | 100 | 94.2 |
| Comparative example 3 | D1 | 83.3 | 65.5 |
| Comparative example 4 | D2 | 89.0 | 63.0 |
The results in Table 3 show that the catalyst provided by the invention has higher catalytic hydrogenation activity, and the catalytic diesel hydrogenation performance is obviously superior to that of a comparative catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
In addition, the specific features described in the above embodiments may be combined in any manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Furthermore, any combination of the various embodiments of the present invention is possible, as long as it does not depart from the gist of the present invention, which is also regarded as the disclosure of the present invention.
Claims (8)
1. A method for preparing a hydrofinishing catalyst, the method comprising:
(1) Uniformly mixing an alumina carrier, a compound containing an auxiliary active component and water, adding ammonia water to regulate the pH value of the obtained slurry to be 5-10, stirring for 0.5-24 hours at the temperature of room temperature to 90 ℃, filtering, drying, and roasting for 2-5 hours at the temperature of 550-800 ℃ to obtain a composite alumina carrier; the alumina carrier: the weight ratio of the compound containing the auxiliary active component is 1: (0.01-0.3), wherein the co-active ingredient-containing compound is in the form of an oxide;
(2) Dipping the composite alumina carrier into an organic solvent to impregnate active metal, and drying;
(3) Roasting the product obtained in the step (2) in an inert atmosphere at a roasting temperature of 300-700 ℃ for 0.5-5 hours to obtain a hydrofining catalyst;
the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and chloroform; drying at 80-120deg.C for 10-15 hr, and removing organic solvent;
the auxiliary active component is selected from one or more of Re, mg and Ca;
the specific surface area of the catalyst is 270-300m 2 Per gram, pore volume is 0.4-0.5 mL/g;
the dipping process comprises the following steps: 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 is prepared by the following steps: the solid-liquid weight ratio of the organic solvent is 1: (0.5-5).
2. The method of claim 1, wherein the co-active component-containing compound is selected from soluble salts of the co-active component, the soluble salts being sulfate, nitrate or chloride salts.
3. The method according to claim 1 or 2, characterized in that the active metal is a group VIII and/or group VIB metal, the group VIII metal being at least one of Fe, ni, co, the group VIB metal being W and/or Mo.
4. A process according to claim 3, wherein the group VIII metal is present in an amount of 0.1 to 30wt% as metal oxide and the group VIB metal is present in an amount of 0.08 to 20wt% as metal oxide relative to the composite alumina support.
5. The method according to claim 1 or 2, wherein one or more auxiliary agents selected from P, B, ti, zr are further added to the organic solvent.
6. The method of claim 1, wherein the number of impregnations is at least 1.
7. The method according to claim 1 or 2, wherein in step (3), the firing temperature is 450 to 650 ℃ and the firing time is 1 to 4 hours.
8. A hydrofinishing catalyst prepared by the method of any one of claims 1-7.
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