CN112973712A - 加氢精制催化剂及其的制备方法 - Google Patents
加氢精制催化剂及其的制备方法 Download PDFInfo
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- CN112973712A CN112973712A CN202011490413.4A CN202011490413A CN112973712A CN 112973712 A CN112973712 A CN 112973712A CN 202011490413 A CN202011490413 A CN 202011490413A CN 112973712 A CN112973712 A CN 112973712A
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- zirconium
- catalyst
- organic solvent
- roasting
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000005470 impregnation Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 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
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 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
- 150000001335 aliphatic alkanes Chemical class 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 3
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000002283 diesel fuel Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 238000004523 catalytic cracking Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 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
- 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
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 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
- 229910052721 tungsten Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 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
- 239000011733 molybdenum Substances 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
- 239000002994 raw material Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- -1 VIB group metal oxide Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000009826 distribution Methods 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
- 150000002739 metals Chemical class 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
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/881—Molybdenum and iron
-
- 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
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及加氢催化剂领域,公开了一种加氢精制催化剂及其制备方法。包括:(1)将含锆化合物和水混合均匀,加入沉淀剂并调节得到的浆液的pH值为5‑10,然后在室温‑90℃下搅拌0.5‑12小时,过滤烘干和焙烧,得到氧化锆;(2)将氧化锆、硅源和水混合均匀,在室温‑90℃下搅拌0.5‑12小时,过滤烘干,在550‑800℃焙烧2‑5小时,得到改性氧化锆载体;(3)将改性氧化锆载体在有机溶剂中浸渍活性金属,并烘干;(4)将步骤(3)所得在惰性气氛下进行焙烧,焙烧温度为300‑700℃,焙烧时间为0.5‑5小时,得到加氢精制催化剂。能够有效改善载体的物化性质,显著提高活性金属在催化剂表面的分散度,适用于加氢脱金属、加氢脱硫及加氢转化催化剂的制备。
Description
技术领域
本发明涉及加氢催化剂领域,具体地,涉及一种加氢精制催化剂及其制备方法。
背景技术
随着环保法规的日趋严格,新的柴油标准对柴油产品中硫质量分数、芳烃质量分数和十六烷值提出了更为严格的要求。催化裂化柴油产量约占柴油总产量的30%左右,由于其十六烷值低、硫、氮和胶质的质量分数高,油品颜色深、安定性差,无法直接作为柴油使用。加氢工艺是改善油品质量最有效的工艺手段之一,加氢催化剂是加氢工艺中最为重要和关键的技术。
加氢催化剂一般由具有加氢功能的金属或金属氧化物和载体组成,常用的金属组份是VIB族和VIII金属,例如钴、钼、镍、钨等,这类催化剂一般通过浸渍法使金属活性组份负载于载体上。常用的载体为氧化锆或含硅氧化锆。为了进一步提高催化剂的活性和稳定性,常常对载体进行改进,使之更适合于劣质柴油馏分的深度加氢精制。
CN1133723C公开了一种馏分油加氢精制催化剂及其制备方法,以含二氧化硅5-15wt%的氧化锆小球为载体,含MoO321-28wt%,NiO 2-8wt%,CoO 0.03-2.0wt%,采用两段喷浸。所述的催化剂同时具有较高的加氢脱硫和加氢脱氮活性,适用于同时含硫氮较多的劣质馏分油加氢精制。
WO2007084438公开了一种选择性加氢脱硫催化剂,该催化剂含有8-30重量%的选自第VIB族的钼,2-8重量的选自第VIII族的钴,及适当量的有机物作为络合剂负载在硅载体上。使用该催化剂处理催化裂化汽油原料,烯烃饱和率低。
CN1123765.1公开了一种柴油加氢处理催化剂,该催化剂含有一种载体和负载在该载体上的锢和/或钨及镍和/或钴,其特征在于,所述载体由氧化锆和沸石组成,氧化锆与沸石的重量比为90:10-50:50,所述氧化锆是由小孔氧化锆和大孔氧化锆按照75:25-50:50的重量比复合而成的氧化锆,其中,小孔氧化锆为直径小于80埃孔的孔体积占总孔体积95%以上的氧化锆,大孔氧化锆为直径60-600埃孔的孔体积占总孔体积70%以上的氧化锆。
CN1049679C公开了一种柴油加氢转化催化剂,以氧化锆和Y型分子筛为载体,含有至少一种VIB族金属和至少一种VIll族金属,其特征在于催化剂载体组成为氧化锆40-90w%、无定形硅铝0-20w%,分子筛5-40w%,其中的Y型分子筛孔容0.40-0.52ml/g,比表面750-900m2/g,晶胞常数2.420-2.500nm,SiO2/A12O3比7-15,催化剂中VIB族金属氧化物含量为10-30w%,VIll族金属氧化物含量为2-15w%。它适合于150-400℃的石油馏分的加氢转化,特别适用于硫,氮,芳烃含量高,十六炕值较低的催化裂化轻循环油(LCO)的转化,其特点是在较缓和的条件下,降低硫、氮、芳烃含量,大幅度提高产品十六烷值。
CN1289828A公开了一种以γ-Al2O3或以含有SiO2的γ-Al2O3为载体的加氢精制催化剂,催化剂以W、Mo、Ni、P为活性组分。以SiO2改性的Al2O3为载体的加氢催化剂性能得到一定改进,但其载体酸量较低,强酸性中心较少,不利于氮杂环的开环断裂,脱氮活性不好。
发明内容
本发明的目的是为了克服现有的加氢催化剂氧化锆载体酸量低,且脱硫、脱氮的活性较低的缺陷,而提供一种加氢精制催化剂及其制备方法。
为了实现上述目的,具体地,本发明提供一种加氢催化剂的制备方法,该方法包括以下步骤:
(1)将含锆化合物和水混合均匀,加入沉淀剂并调节得到的浆液的pH值为5-10,然后在室温-90℃下搅拌0.5-12小时,过滤烘干和焙烧,得到氧化锆;
(2)将所述氧化锆、硅源和水混合均匀,在室温-90℃下搅拌0.5-12小时,过滤烘干,在550-800℃焙烧2-5小时,得到改性氧化锆载体;
(3)将所述改性氧化锆载体在有机溶剂中浸渍活性金属,并烘干;
(4)将步骤(3)得到的产物在惰性气氛下进行焙烧,焙烧温度为300-700℃,焙烧时间为0.5-5小时,得到加氢精制催化剂。
本发明还提供了由上述方法制备得到的加氢精制催化剂。
通过上述技术方案,本发明采用含硅溶液对氧化锆载体进行改性处理,一方面可以有效改善载体的孔径分布,使大孔增加,同时调节了催化剂的酸性;采用有机溶剂浸渍的方法可以显著提高活性金属在催化剂表面的分散度。本发明方法特别适用于加氢脱金属、加氢脱硫及加氢转化催化剂的制备。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
下面的实施例将对本发明作进一步说明,旨在帮助阅读者更好地理解本发明的实质所在和所带来的有益效果,但不应理解为对本发明的可实施范围的任何限定。
本发明提供一种加氢精制催化剂的制备方法,包括以下步骤:
(1)将含锆化合物和水混合均匀,加入沉淀剂并调节得到的浆液的pH值为5-10,然后在室温-90℃下搅拌0.5-12小时,过滤烘干和焙烧,得到氧化锆;
(2)将所述氧化锆、硅源和水混合均匀,在室温-90℃下搅拌0.5-12小时,过滤烘干,在550-800℃焙烧2-5小时,得到改性氧化锆载体;
(3)将所述改性氧化锆载体在有机溶剂中浸渍活性金属,并烘干;
(4)将步骤(3)得到的产物在惰性气氛下进行焙烧,焙烧温度为300-700℃,焙烧时间为0.5-5小时,得到加氢精制催化剂。
本发明提供的一些实施方式中,步骤(1)用于制备氧化锆载体。优选地,所述含锆化合物,可以选自四氯化锆、硫酸锆、硝酸锆、氧氯化锆、醋酸锆、异丙醇锆中的一种或多种。用以提供锆源。室温可以为20-35℃。所述沉淀剂可以为碱性化合物,优选为氨水,避免引入杂质元素。所述浆液的pH值根据锆源的物质不同,控制在上述范围内,提供相应获得合适的氧化锆载体。优选pH值可以是5、6、7、8、9、10,以及上述数值中任意两个数值组成的范围。其中,干燥可以是在100-120℃下进行10-15小时。焙烧可以是在600-800℃下进行2-8小时。
本发明提供的一些实施方式中,步骤(2)用于改性所述氧化锆,使用所述硅源提供硅改性,得到的改性氧化锆载体能够提供对于加氢反应更好的促进性。优选地,所述硅源可以是硅溶胶、硅胶或水玻璃,优选为硅溶胶。
在本发明提供的一些实施方式中,步骤(2)中,所述氧化锆、硅源(以氧化硅计)和去离子水按照1:(0.1-1):(1-20)混合。加入量限定可以控制以实现得到的所述改性氧化锆载体具有合适的孔结构。优选,氧化锆:硅源的重量比可以是1:0.1、1:0.2、1:0.3、1:0.4、1:0.5、1:0.6、1:07、1:0.8、1:0.9、1:1,以及上述数值中任意两个数值组成的范围;氧化锆:水的重量比可以优选为1:1-11,优选为1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11,以及上述数值中任意两个数值组成的范围。
在本发明提供的一些实施方式中,所述步骤(3)用于负载所述活性金属,在所述改性氧化锆载体上负载本发明的加氢精制催化剂所需的活性金属。优选地,步骤(3)中,所述活性金属为第VIII族和/或第VIB族金属,第VIII族金属为Fe、Ni、Co中的至少一种,第VIB族金属为W和/或Mo。所述活性金属的用量进一步地优选,相对于所述改性氧化锆载体,第VIII族金属以金属氧化物计的用量为0.1wt%-30wt%,第VIB族金属以金属氧化物计的用量为0.08wt%-20wt%。优选地,第VIII族金属的用量为5wt%-20wt%,第VIB族金属的用量为5wt%-20wt%。
在本发明提供的一些实施方式中,优选地,步骤(3)中,所述浸渍的过程包括:将所述活性金属的前驱体溶解于所述有机溶剂中,然后与所述复合氧化锆载体混合,在搅拌或静置下保持0.5-12小时,其中所述复合氧化锆载体:所述有机溶剂的固液重量比为1:(0.5-5);优选地,所述浸渍的次数至少为1次。所述活性金属的前驱体可以选自含所述活性金属的可溶于所述有机溶剂中的化合物,例如可以为氯化铁、钼酸铵、硝酸钴、偏钨酸铵、硝酸镍。其中,所述浸渍的过程完成后,进行烘干,温度为80-120℃,时间为10-15小时,去除有机溶剂。
在本发明提供的一些实施方式中,优选地,所述有机溶剂的标准沸点优选40-100℃。优选地,所述有机溶剂可以是烷烃、芳香烃、醇、酮、醚、酯、卤代烷烃中的一种或者多种。优选地,所述有机溶剂优选正己烷、环己烷、庚烷、苯、甲苯、甲醇、乙醇、异丙醇、丙酮、丁酮、三氯甲烷中的一种或多种。步骤(3)中的浸渍活性金属所采用的有机溶剂以及用量,能够有助于提高活性金属在催化剂表面的分散度,可以通过催化剂表面金属含量与锆含量的质量比,或催化反应结果体现。在本发明提供的一些实施方式中,优选地,步骤(4)中,焙烧温度为450-650℃,焙烧时间为1-4小时。
本发明第二方面提供了一种上述方法制得的加氢精制催化剂。
在本发明提供的一些实施方式中,获得的催化剂的比表面积为300-400m2/g,优选为350-400m2/g;孔容为0.4-0.7mL/g,优选为0.5-0.65mL/g;总酸量为0.4-0.6mmol/g。所述加氢精制催化剂的组成包括:基于所述催化剂的总量,氧化锆的含量为30-65wt%,氧化硅含量温5-40wt%,第VIII族金属(以金属氧化物计)的含量为0.1-30wt%,第VIB族金属(以金属氧化物计)的含量为0.08-20wt%。所述加氢精制催化剂的组成可以通过荧光分析法测定,也可以通过制备投料计算。
本发明还提供了一种催化裂化柴油加氢精制的方法,包括:将催化裂化柴油在加氢精制催化剂存在下进行加氢精制反应,所述加氢精制催化剂为本发明的馏分油加氢精制催化剂。
催化裂化柴油可以是从石油炼制的催化裂化工艺制得的柴油。加氢精制反应的条件可以是:温度为300-400℃,氢分压为5-7MPa,原料催化裂化柴油的体积空速为1-4h-1,氢气与原料催化裂化柴油的体积比为200-500:1。
使用本发明的加氢精制催化剂,催化裂化柴油的加氢脱硫率达到100%,脱氮率91.0%以上。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中:
催化剂的比表面积、孔容通过BET方法测定;
催化剂的总酸量通过吡啶红外光谱法测定;
原料油、加氢产物中的硫含量通过气相色谱法测定;
加氢脱硫率%=1-(原料油中硫含量-加氢产物中硫含量)/原料油中硫含量×100%;
加氢脱氮率%=1-(原料油中氮含量-加氢产物中氮含量)/原料油中氮含量×100%。
实施例1
取1465g氧氯化锆ZrOCl2·8H2O和2269g去离子水打浆后,用稀氨水调节混合物的pH值为7.0,室温搅拌3.0小时,过滤后将其120℃下干燥12小时,并700℃下焙烧3小时,得到氧化锆。
取氧化锆737g(以干基计算)、560g硅溶胶(氧化硅含量25%)、2800g去离子水混合,在室温下搅拌老化2小时,过滤后将其120℃下干燥12小时,在750℃焙烧2小时。得到改性氧化锆载体。氧化锆:氧化硅:水的重量比为1:0.19:3.80。
将339g氯化铁、272g钼酸铵溶于800g乙醇(纯度99.9%)中制成浸渍液,所得浸渍液与上述改性氧化锆载体(相对于改性氧化锆载体,氧化铁的用量为10wt%,氧化钼的用量为20wt%)混合均匀(改性氧化锆载体:有机溶剂的固液重量比为1:2),室温下保持12h,然后所得产物100℃烘干24小时,在氮气气氛、500℃下焙烧4小时。得到催化剂A1。催化剂A1的分析结果见表1。
实施例2
取1250g异丙醇锆和1100g去离子水打浆后,用稀氨水调节混合物的pH值为5.5,40℃搅拌3.0小时,过滤后将其120℃下干燥12小时,并600℃下焙烧5小时,得到氧化锆。
取氧化锆618g(以干基计算)、1200g硅溶胶(氧化硅含量25%)、1600g去离子水混合,在40℃下搅拌老化1小时,过滤后将其120℃下干燥12小时,在650℃焙烧3小时。得到改性氧化锆载体。氧化锆:氧化硅:水的重量比为1:0.49:2.59。
将280g硝酸钴Co(NO3)2·6H2O、160g偏钨酸铵溶于900g乙醇(纯度99.9%)中制成浸渍液,所得浸渍液与上述改性氧化锆载体(相对于改性氧化锆载体,氧化钴的用量为8wt%,氧化钨的用量为15wt%)混合均匀(改性氧化锆载体:有机溶剂的固液重量比为1:2),室温下保持8h,然后所得产物120℃烘干6小时,在氮气气氛、550℃下焙烧2小时。得到催化剂A2。催化剂A2的分析结果见表1。
实施例3
取1680g硝酸锆和574g去离子水打浆后,用稀氨水调节混合物的pH值为4.5,60℃搅拌1.0小时,过滤后将其120℃下干燥12小时,并800℃下焙烧2小时,得到氧化锆。
取氧化锆526g(以干基计算)、1400g硅溶胶(氧化硅含量25%)、4000g去离子水混合,在60℃下搅拌老化1小时,过滤后将其120℃下干燥12小时,在550℃焙烧5小时。得到改性氧化锆载体。氧化锆:氧化硅:水的重量比为1:0.67:7.6。
将489g硝酸镍、68g钼酸铵溶于600g环己烷(纯度99.9%)中制成浸渍液,所得浸渍液与上述改性氧化锆载体(相对于改性氧化锆载体,氧化镍的用量为20wt%,氧化钼的用量为5wt%)混合均匀(改性氧化锆载体:有机溶剂的固液重量比为1:2),室温下保持12h,然后所得产物120℃烘干6小时,在氮气气氛、600℃下焙烧3小时。得到催化剂A3。催化剂A3的分析结果见表1。
实施例4
取1600g硝酸锆和1000g去离子水打浆后,用稀氨水调节混合物的pH值为7.5,25℃搅拌5.0小时,过滤后将其120℃下干燥12小时,并650℃下焙烧4小时,得到氧化锆。
取氧化锆500g(以干基计算)、1480g硅溶胶(氧化硅含量25%)、2600g去离子水混合,在60℃下搅拌老化1.5小时,过滤后将其120℃下干燥12小时,在700℃焙烧2小时。得到改性氧化锆载体。氧化锆:氧化硅:水的重量比为1:0.74:5.2。
将175g硝酸钴Co(NO3)2·6H2O、272g钼酸铵溶于1000g环己烷(纯度99.9%)中制成浸渍液,所得浸渍液与上述改性氧化锆载体(相对于改性氧化锆载体,氧化钴的用量为5wt%,氧化钼的用量为20wt%)混合均匀(改性氧化锆载体:有机溶剂的固液重量比为1:3),室温下保持24h,然后所得产物120℃烘干6小时,在氮气气氛、650℃下焙烧3小时。得到催化剂A4。催化剂A4的分析结果见表1。
实施例5
取1177g氧氯化锆和1800g去离子水打浆后,用稀氨水调节混合物的pH值为9.0,25℃搅拌2.0小时,过滤后将其120℃下干燥12小时,并750℃下焙烧2.5小时,得到氧化锆。
取氧化锆523g(以干基计)、1200g硅溶胶(氧化硅含量25%)、2700g去离子水混合,在90℃下搅拌老化1.5小时,过滤后将其120℃下干燥12小时,在700℃焙烧2小时。得到改性氧化锆载体。氧化锆:氧化硅:水的重量比为1:0.57:5.16。
将526g硝酸钴Co(NO3)2·6H2O、106g偏钨酸铵溶于1000g丁酮(纯度99.9%)中制成浸渍液,所得浸渍液与上述改性氧化锆载体(相对于改性氧化锆载体,氧化钴的用量为15wt%,氧化钨的用量为10wt%)混合均匀(改性氧化锆载体:有机溶剂的固液重量比为1:2),室温下保持24h,然后所得产物120℃烘干6小时,在氮气气氛、550℃下焙烧3小时。得到催化剂A5。催化剂A5的分析结果见表1。
对比例1
取1465g氧氯化锆ZrOCl2·8H2O和2269g去离子水打浆后,用稀氨水调节混合物的pH值为7.0,室温搅拌3.0小时,过滤后将其120℃下干燥12小时,在750℃焙烧2小时,得到氧化锆。
将339g氯化铁、272g钼酸铵溶于800g乙醇(纯度99.9%)中制成浸渍液,所得浸渍液与上述氧化锆载体(相对于氧化锆,氧化铁的用量为12wt%,氧化钼的用量为23wt%)混合均匀,室温下保持12h,然后所得产物100℃烘干24小时,在氮气气氛、500℃下焙烧4小时。得到对比催化剂D1。催化剂分析见表1。
对比例2
取1465g氧氯化锆ZrOCl2·8H2O和2269g去离子水打浆后,用稀氨水调节混合物的pH值为7.0,室温搅拌3.0小时,过滤后将其120℃下干燥12小时,在750℃焙烧2小时,得到氧化锆。
取氧化锆样品737g(以干基计算)、560g硅溶胶(氧化硅含量25%)、2800g去离子水混合,在室温下搅拌老化2小时,过滤后将其120℃下干燥12小时,在750℃焙烧2小时,得到改性氧化锆载体。
将339g氯化铁、272g钼酸铵溶于800g去离子水中制成浸渍液,所得浸渍液与上述氧化锆载体(相对于改性氧化锆载体,氧化铁的用量为8.5wt%,氧化钼的用量为17wt%)混合均匀,室温下保持12h,然后所得产物100℃烘干24小时,在空气气氛、500℃下焙烧4小时。得到对比催化剂D2。催化剂分析见表1。
表1
表1结果表明,本发明方法制备方法的催化剂具有较高的酸性,较高的金属在载体表面的分散度,具有更高的加氢活性。
实施例6-10
将催化剂A1-A5按照表2提供的原料油和评价条件进行加氢脱硫和脱氮反应。反应评价结果见表3。
表2
原料油 | 催化柴油 |
20℃密度,kg/m<sup>3</sup> | 975 |
S,ppm(质量) | 6500 |
N,ppm(质量) | 880 |
氢分压,MPa | 6.0 |
温度,℃ | 340 |
体积空速,h<sup>-1</sup> | 2.0 |
氢油体积比 | 300 |
对比例3-4
按照实施例6-10中方法,将催化剂D1-D2进行加氢脱硫和脱氮反应。反应评价结果见表3。
表3
从表3的结果可以看出,本发明提供的加氢精制催化剂具有更高的加氢脱硫和脱氮活性,其催化柴油加氢性能显著优于对比催化剂。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方法中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何的方式进行组合。为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (10)
1.一种加氢精制催化剂的制备方法,该方法包括以下步骤:
(1)将含锆化合物和水混合均匀,加入沉淀剂并调节得到的浆液的pH值为5-10,然后在室温-90℃下搅拌0.5-12小时,过滤烘干和焙烧,得到氧化锆;
(2)将所述氧化锆、硅源和水混合均匀,在室温-90℃下搅拌0.5-12小时,过滤烘干,在550-800℃焙烧2-5小时,得到改性氧化锆载体;
(3)将所述改性氧化锆载体在有机溶剂中浸渍活性金属,并烘干;
(4)将步骤(3)得到的产物在惰性气氛下进行焙烧,焙烧温度为300-700℃,焙烧时间为0.5-5小时,得到加氢精制催化剂。
2.根据权利要求1所述的方法,其中,所述含锆化合物选自四氯化锆、硫酸锆、硝酸锆、氧氯化锆、醋酸锆、异丙醇锆中的一种或多种。
3.根据权利要求1或2所述的方法,其中,所述硅源为硅溶胶、硅胶或水玻璃,优选为硅溶胶。
4.根据权利要求1-3中任意一项所述的方法,其中,氧化锆:所述硅源:水的重量比为1:(0.1-1):(1-20),其中,所述硅源以氧化硅计。
5.根据权利要求1-4中任意一项所述的方法,其中,所述活性金属为第VIII族和/或第VIB族金属,优选第VIII族金属为Fe、Ni、Co中的至少一种,第VIB族金属为W和/或Mo。
6.根据权利要求1-5中任意一项所述的方法,其中,相对于所述改性氧化锆载体,第VIII族金属以金属氧化物计的用量为0.1wt%-30wt%,第VIB族金属以金属氧化物计的用量为0.08wt%-20wt%。
7.根据权利要求1-6中任意一项所述的方法,其中,所述浸渍的过程包括:将所述活性金属的前驱体溶解于所述有机溶剂中,然后与所述改性氧化锆载体混合,在搅拌或静置下保持0.5-12小时,其中所述改性氧化锆载体:所述有机溶剂的固液重量比为1:(0.5-5);优选地,所述浸渍的次数至少为1次。
8.根据权利要求1-7中任意一项所述的方法,其中,所述有机溶剂的标准沸点为40-100℃;
优选地,所述有机溶剂为烷烃、芳香烃、醇、酮、醚、酯、卤代烷烃中的一种或者多种;优选所述有机溶剂为正己烷、环己烷、庚烷、苯、甲苯、甲醇、乙醇、异丙醇、丙酮、丁酮、三氯甲烷中的一种或多种。
9.根据权利要求1-8中任意一项所述的方法,其中,焙烧温度为450-650℃,焙烧时间为1-4小时。
10.一种权利要求1-9中任意一项所述的制备方法制得的加氢精制催化剂。
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