CN1069685C - Zeolite-contained catalyst for hydrogenating hydrocarbon oil and its preparing process - Google Patents
Zeolite-contained catalyst for hydrogenating hydrocarbon oil and its preparing process Download PDFInfo
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- CN1069685C CN1069685C CN98120382A CN98120382A CN1069685C CN 1069685 C CN1069685 C CN 1069685C CN 98120382 A CN98120382 A CN 98120382A CN 98120382 A CN98120382 A CN 98120382A CN 1069685 C CN1069685 C CN 1069685C
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- Prior art keywords
- zeolite
- oxide
- heavy
- content
- catalyzer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 50
- 230000008569 process Effects 0.000 title description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000010457 zeolite Substances 0.000 claims abstract description 138
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 137
- 239000000203 mixture Substances 0.000 claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 36
- 239000011737 fluorine Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 48
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 39
- 238000002360 preparation method Methods 0.000 claims description 38
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 229910001723 mesolite Inorganic materials 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 23
- -1 aluminum compound Chemical class 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052721 tungsten Inorganic materials 0.000 claims description 18
- 239000010937 tungsten Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005336 cracking Methods 0.000 abstract description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000005864 Sulphur Substances 0.000 description 15
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000004517 catalytic hydrocracking Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- 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 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a hydrocarbon oil hydrotreating catalyst comprising zeolite. In the catalyst, the content of fluorine used as an auxiliary agent is from 0.5 to 6 wt%. Measured by the dioxide, the content of metal components in a VIB family is from 10 to 35 wt%, and the content of metal components in a VIII family is from 0.5 to 6 wt%. A catalyst carrier is a composition comprising a kind of zeolite and alumina. The composition is obtained by that a uniform mixture of zeolite of which the content of sodium oxide is not larger than 1 wt% and an aluminous compound is roasted for more than 0.5 hour under a water vapour atmosphere at 500 to 800 DEG C. The catalyst has low cracking selectivity and high isomerism selectivity.
Description
The invention relates to a kind of catalyst for hydrogenating hydrocarbon oil and preparation method thereof, more particularly, is about a kind of catalyst for hydrogenating hydrocarbon oil that contains zeolite and preparation method thereof.
The hydrogenation process of hydrocarbon ils is divided with its purpose can be divided into hydrotreatment and two processes of hydrocracking, and its catalyst system therefor is also inequality.
Hydrocracking process is a purpose so that macromolecular cracking hydrocarbon oil is become the hydrocarbon ils than small molecules.The hydrocracking catalyst system therefor generally contains a kind of carrier and the group VIB metal, the group VIII metal that load on this carrier that contains zeolite.Wherein, the described carrier that contains zeolite has stronger cracking activity as a kind of acidic components.In order to adapt to ever-increasing needs to middle distillate, in recent years, having emerged in large numbers is the purpose hydrocracking catalyst to produce intermediate oil in a large number.
US4,401,556 disclose a kind of hydrocracking catalyst, and this catalyzer contains a kind of strong hydrophobic nature crystal silicon-aluminate zeolite.This strong hydrophobic nature crystal silicon-aluminate zeolite is prepared from a kind of y-type zeolite starting raw material in 0.2～10 atmospheric water vapor in 725～870 ℃ of roastings.The heavy % of the loading capacity at least 6 of water vapor when the silica alumina ratio of described y-type zeolite starting raw material is 4.5～6,25 ℃, and P/P ° at least 0.1.The loading capacity of water vapor is lower than 5 heavy % during 25 ℃ of strong hydrophobic nature crystal silicon-aluminate zeolites that obtains after the roasting, and P/P ° less than 0.1.This catalyzer has improved the selectivity to middle distillate when having higher cracking activity and stability.
US5,288,396 contriver finds US4, character is inhomogeneous in the preparation for 401,556 disclosed catalyzer, the quality instability.Thereby US5,288,396 contriver has invented a kind of method of producing intermediate oil, the characteristics of this method have been to use a kind of hydrocracking catalyst that contains zeolite, the unit cell dimension of this zeolite is 24.20～24.40 dusts, and adopt following method preparation: (a) with at least a inorganic refractory oxides component and a kind of mixture extrusion moulding with crystal silicon-aluminate zeolite of cracking activity, the unit cell dimension of wherein said crystal silicon-aluminate zeolite is 24.40～24.95 dusts, and it is selected from by y-type zeolite, modified zeolite of Y-type, one group of forming of X zeolite and modification X zeolite.(b) steam partial pressure greater than the atmosphere of 5.0Psia in the described forming composition of roasting, make the structure cell of described crystal silicon-aluminate zeolite be contracted to 24.20～24.40.
Above-mentioned hydrocracking catalyst has high cracking activity and to the selectivity of middle distillate.In hydrocracking process, these hydrocracking catalysts are very responsive to the sulphur in the stock oil, nitrogen, the existence meeting of a large amount of sulphur, nitrogen impurity makes poisoning of catalyst very soon, therefore, requirement to stock oil is very strict, and in general, sulphur, nitrogen content in the stock oil are lower than 50ppm, be preferably lower than 20ppm, even be lower than 10ppm.
Yet sulphur, nitrogen content all are higher than 20ppm far away in the various petroleum cuts stock oils, even are higher than 50ppm far away, in actual applications, the sulphur in the raw material, nitrogen content will be reduced to below the 20ppm earlier usually, again this raw material are used for hydrocracking reaction.And hydrotreatment is exactly to be the purpose process with the sulphur, nitrogen impurity and the unsaturated hydro carbons that remove in the raw material.
The hydrotreatment catalyst system therefor generally contains a kind of heat-resistant inorganic oxide carrier and the group VIB, the VIII family hydrogenation metal component that load on this heat-resistant inorganic oxide carrier, and some hydrotreating catalyst also contains a kind of auxiliary agent fluorine, phosphorus or boron except that containing said components.This with the aluminum oxide be the hydrotreating catalyst of carrier because alumina supporter acidic components and hydrogenation active metals active ingredient coupling is improper, generally activity is lower, the hydrotreatment temperature of reaction is generally higher.
The hydrotreating catalyst that contains Zeolite support is also arranged in the prior art, and this hydrotreating catalyst generally has specific purpose.As CN1,056,514A discloses a kind of have good saturated performance of hydrofining performance, aromatic hydrocarbons and cracking performance, the hydrotreating catalyst that has advantage with low cost again.This catalyzer is by the purity of aluminum alkoxide or the alkyl aluminum hydrolysis method preparation diaspore greater than 65 heavy %, carrier, fluorine auxiliary agent and nickel, the tungsten that obtains with zeolite mixture high-temperature roasting through the cationic exchange component of living constitutes, each component concentration is fluorine 0.5～5.0 heavy %, nickel oxide 2.5～6.0 heavy %, Tungsten oxide 99.999 10～32 heavy %, all the other are carriers.That its preparation method comprises that (1) produce aluminum alkyls or aluminum alkoxide hydrolysis method, purity is even by the mixed of 1～13: 1～3 (weight) with the zeolite through cationic exchange greater than the diaspore of 65 heavy %, 500～700 ℃ of roastings 3～5 hours obtain carrier.(2) carrier that obtains with fluorine-containing solution impregnation (1), 100～130 ℃ of oven dry, 400～600 ℃ of roastings 3～5 hours obtain fluorine-containing carrier.(3) the fluorine-containing carrier that obtains with the solution impregnation (2) that contains tungsten and nickel, 100～130 ℃ of oven dry, 400～600 ℃ of roastings 3～5 hours obtain being suitable for being produced by vacuum gas oil the hydrotreatment process of the stock oil of ethylene preparing by steam cracker.
The cracking activity of the above-mentioned hydrotreating catalyst that contains zeolite is very limited its application still than higher.Because of the hydrotreatment process is not wished the macromolecule hydrocarbon that cracking is too much sometimes.For example, in the unifining process of lubricating oil, only wish to remove wherein sulphur, nitrogen impurity by hydrotreatment, simultaneously, make a part of aromatic hydrocarbons carry out saturated and ring-opening reaction, and make a part of normal paraffin wherein change into isoparaffin, when improving its viscosity index, the high yield that keeps lubricating oil, and too much scission reaction will influence the yield of lubricating oil.
The objective of the invention is to overcome the too high shortcoming of hydrotreating catalyst lytic activity that prior art contains zeolite, a kind of lower cracking selectivity that has is provided, higher hydroisomerizing optionally contains the hydrotreating catalyst of zeolite.Another object of the present invention provides this Preparation of catalysts method.
Catalyzer provided by the invention is by a kind of carrier and load on metal component of group VIB on this carrier and metal component of group VIII and auxiliary agent fluorine are formed.Wherein, the content of auxiliary agent fluorine is 0.5～6 heavy %, and in oxide compound, metal component of group VIB content is 10～35 heavy %, and metal component of group VIII content is 0.5～6 heavy %.Described carrier contains the composition of a kind of zeolite and aluminum oxide, said composition is the uniform mixture composition that roasting obtained more than 0.5 hour under 500～800 ℃ of water vapour atmospheres that sodium oxide content is not more than the compound of the zeolite of 1 heavy % and aluminium, content 1～99.95 heavy % of composition mesolite, the content of carrier mesolite is 1～80 heavy %.Described zeolite is selected from one or more in X type zeolite, y-type zeolite, mordenite and the Beta zeolite.
According to catalyzer provided by the invention, the compound of described aluminium refers to mix with described zeolite and do not stay in the compound of impurity one or more after steam-treated and/or roasting.In wherein preferred aluminum nitrate, aluminium hydroxide, the aluminum oxide one or more, more preferred aluminium hydroxide and/or aluminum nitrate.The uniform mixture of described zeolite and aluminum compound also refers to go up aluminum ions aluminium type zeolite through the ion exchange method exchange.The content of aluminum compound makes in the composition of the zeolite that obtains after steam-treated and aluminum oxide and contains zeolite 1～99.95 heavy % in the uniform mixing of described zeolite and aluminum compound.
According to embodiment preferred of the present invention, the carrier of catalyzer provided by the invention contains the composition of a kind of zeolite and aluminum oxide, said composition is that sodium oxide content is not more than the zeolite of 1 heavy % and the uniform mixture composition that roasting obtained more than 0.5 hour under 500～800 ℃ of water vapour atmospheres of aluminium hydroxide, and the content of composition mesolite is 1～80 heavy %.Also contain or do not contain a kind of heat-resistant inorganic oxide in the described carrier in addition, described carrier mesolite content is 1～80 heavy %, preferred 1～50 heavy %, more preferred 1～35 heavy %.
According to one of the present invention embodiment preferred more, the carrier of catalyzer provided by the invention contains the composition of a kind of zeolite and aluminum oxide, said composition is that sodium oxide content is not more than the zeolite of 1 heavy % and the uniform mixture composition that roasting obtained more than 0.5 hour under 500～800 ℃ of water vapour atmospheres of aluminum nitrate, content 80～99.5 heavy % of composition mesolite.Also contain a kind of heat-resistant inorganic oxide in the carrier, the content of heat-resistant inorganic oxide makes and contains zeolite 1～80 heavy %, preferred 1～50 heavy %, more preferred 1～35 heavy % in the carrier.
According to another embodiment preferred more of the present invention, the carrier of catalyzer provided by the invention contains the composition of a kind of zeolite and aluminum oxide, said composition is that sodium oxide content is not more than the aluminium type zeolite that the roasting under 500～800 ℃ of water vapour atmospheres of aluminum ions zeolite of containing of 1 heavy % obtained more than 0.5 hour, described aluminium type zeolite mesolite content 80～99.5 heavy %.Also contain a kind of heat-resistant inorganic oxide in the carrier, it is 1～80 heavy % that the content of heat-resistant inorganic oxide makes carrier mesolite content, preferred 1～50 heavy %, more preferred 1～35 heavy %.
According to catalyzer provided by the invention, described carrier can only contain the composition of described zeolite and aluminum oxide.Can also contain heat-resistant inorganic oxide in addition in the described carrier.Described heat-resistant inorganic oxide is selected from catalyst carrier for hydrgenating heat-resistant inorganic oxide commonly used, as in silicon oxide, aluminum oxide, amorphous aluminosilicate, zirconium white, titanium oxide, magnesium oxide, Thorotrast, beryllium oxide, boron oxide, the Cadmium oxide one or more.In the preferred silicon oxide of described heat-resistant inorganic oxide, aluminum oxide, the amorphous aluminosilicate one or more.
Described in moisture vapor atmosphere preferred 550～750 ℃ of the temperature of the uniform mixture of roasting zeolite and aluminum compound, preferred 0.5～8 hour of roasting time, more preferred 2～6 hours.The atmosphere of described moisture vapor can be 100% water vapor, water vapor and Air mixing gas, the gas mixture of water vapor and oxygen, and water vapor and other rare gas element, as the gas mixture of nitrogen, preferably water vapor and Air mixing gas or 100% water vapor.
Described zeolite is selected from one or more in X type zeolite, y-type zeolite, mordenite and the Beta zeolite that sodium oxide content is not more than 1 heavy %.Described y-type zeolite also comprises overstable gamma zeolite and modified Y zeolite except that comprising general y-type zeolite.Preferred y-type zeolite of described zeolite or y-type zeolite and X type zeolite, mordenite, one or more mixture in the Beta zeolite.
Described metal component of group VIB is selected from one or more in simple substance, oxide compound and the sulfide of chromium, molybdenum, tungsten.In the simple substance of preferred tungsten, oxide compound, the sulfide one or more.In oxide compound, the content of metal component of group VIB preferred 10～30 heavy %.
In simple substance, oxide compound and the sulfide of described metal component of group VIII chosen from Fe, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum one or more.In simple substance, oxide compound and the sulfide of preferred cobalt, nickel, palladium, platinum one or more.In simple substance, oxide compound and the sulfide of more preferred nickel, cobalt one or more.In oxide compound, metal component of group VIII content preferred 0.5～5 heavy %, when described group VIII metal is cobalt and/or nickel, preferred 2～5 heavy %.
The content of described auxiliary agent fluorine preferred 1～5 heavy %.
Preparation of catalysts method provided by the invention comprises successively with the solution of fluorochemicals and contains the solution impregnating carrier of group VIB, group VIII metal compound, carries out drying and roasting behind each dipping.Wherein, described carrier contains the composition of a kind of zeolite and aluminum oxide, the preparation method of said composition comprises and sodium oxide content is not more than the uniform mixture of the zeolite of 1 heavy % and aluminum compound roasting is more than 0.5 hour under 500～800 ℃ of water vapour atmospheres that the consumption of zeolite and aluminum compound makes and contains zeolite 1～99.95 heavy % in the described composition.
According to Preparation of catalysts method provided by the invention, described aluminum compound refers to mix with described zeolite, and after steam-treated and/or roasting, do not stay in the compound of impurity one or more, in wherein preferred aluminum nitrate, aluminium hydroxide, the aluminum oxide one or more, more preferred aluminium hydroxide and/or aluminum nitrate.The uniform mixture of described zeolite and aluminum compound also refers to go up aluminum ions aluminium type zeolite through the ion exchange method exchange.The consumption of aluminum compound makes in the composition of the zeolite that obtains after steam-treated and aluminum oxide and contains zeolite 1～99.5 heavy % in the uniform mixture of described zeolite and aluminum compound.
The uniform mixture of described zeolite and aluminum compound can be the uniform mixture of the two.Can also contain a kind of auxiliary agent and/or tackiness agent in the mixture.Can be earlier described mixture and an amount of extrusion aid and/or binding agent and water be mixed extruded moulding, directly roasting under water vapour atmosphere; Or roasting under water vapour atmosphere more after drying.Described extrusion aid can be selected from extrusion aid commonly used in the hydrogenation catalyst preparation process, as starchy material, and one or more in methylcellulose gum, the acid polyethylene etc.Described tackiness agent can be selected from the hydrogenation catalyst preparation process tackiness agent commonly used, as in various mineral acids, the organic acid one or more.
In the composition of zeolite that obtains through steam roasting and aluminum oxide, if zeolite content has reached 1～80 heavy %, said composition can directly be used alone as the carrier of catalyzer, also said composition can be mixed carrier as catalyzer with a kind of heat-resistant inorganic oxide, or mix with a kind of precursor of heat-resistant inorganic oxide, moulding or not moulding, be re-used as the carrier of catalyzer after dry, the roasting.When composition mesolite content weighs % greater than 80, then must mix, or mix with the precursor of heat-resistant inorganic oxide with heat-resistant inorganic oxide, moulding or not moulding are used as support of the catalyst after drying, the roasting again.Described heat-resistant inorganic oxide is selected from one or more in the heat-resistant inorganic oxide that is commonly used for hydrogenation catalyst, as can be selected from one in aluminum oxide, silicon oxide, amorphous aluminosilicate, boron oxide, magnesium oxide, zirconium white, titanium oxide, Thorotrast, beryllium oxide, the Cadmium oxide each or several.Preferred silicon oxide, aluminum oxide or their mixed thing.The precursor of heat-resistant inorganic oxide can be selected from corresponding oxyhydroxide of above-mentioned oxide compound and colloidal sol thereof in one or more, one or more in preferred hydrated aluminum oxide, silicon sol, silicon gel, the water glass.The consumption of described heat-resistant inorganic oxide makes and contains zeolite 1～80 heavy %, preferred 1～50 heavy %, more preferred 1～35 heavy % in the final support of the catalyst.
According to Preparation of catalysts method provided by the invention, the preferred sodium oxide content of described zeolite is not more than in the y-type zeolite of 1 heavy % or y-type zeolite and X type zeolite, mordenite, the Beta zeolite one or more mixture.
Described fluorine cpd are selected from fluorine-containing salt or acid, wherein preferred fluorinated ammonium and/or hydrogen fluoride.
Described group VIB metallic compound is selected from the soluble compound of group VIB metal, as in chromic salt, molybdate, tungstate, metatungstate, the alkyl metatungstate one or more, one or more in preferred ammonium metawolframate, metatungstic acid nickel, the ethyl ammonium metawolframate.
Described group VIII metal compound is selected from one or more in the group VIII metal soluble compound, as muriate, the nitrate of group VIII metal, one or more in soluble carbon hydrochlorate, the soluble complexes.Muriate, nitrate, the muriate of nickel, the nitrate of preferred cobalt, carbonate, acetate, metatungstate, Palladous chloride, the acid of chlorine palladium, Platinic chloride, one or more in chlorination four ammino platinum, chlorination four ammino palladiums, nitric acid four ammino platinum, the nitric acid four ammino palladiums.In more preferred nickelous chloride, nickelous nitrate, nickelous carbonate, nickel acetate, the metatungstic acid nickel one or more.
Described with fluorochemicals solution and contain group VIB and the solution impregnating carrier of group VIII metal compound after drying and roasting condition be drying and roasting condition commonly used in the hydrogenation catalyst preparation process.As drying temperature room temperature～300 ℃, preferred 100～200 ℃, 400～600 ℃ of maturing temperatures, roasting time 3～5 hours.
Compare with the existing hydrotreating catalyst that contains zeolite, catalyzer provided by the invention has lower cracking selectivity and higher isomerization selectivity.And compare with the hydrotreating catalyst that aluminum oxide is made carrier, catalyzer provided by the invention has higher activity.For example, be reaction raw materials with the normal heptane, 350 ℃ of temperature of reaction, reaction pressure 2.5 MPas, liquid hourly space velocity 1 hour
-1Estimate fluorine-containing 3.5 heavy %, nickel oxide 2.7 heavy %, Tungsten oxide 99.999 27.7 heavy % under the condition of hydrogen flowing quantity 400 ml/min, the catalytic performance that contains the catalyzer of zeolite about 9.6 heavy % in the carrier, when catalyzer is to press CN1,056, during the catalyzer of 514A preparation, the normal heptane transformation efficiency is 48 heavy %, and the isomerization selectivity has only 15%.When catalyzer is that aluminum oxide is made carrier, during the catalyzer of fluorine, nickel oxide, tungsten oxide content higher (fluorine 4.9 heavy %, nickel oxide 3.3 heavy %, Tungsten oxide 99.999 29 heavy %), the normal heptane transformation efficiency has only 12 heavy %.And when catalyzer was catalyzer provided by the invention, the normal heptane transformation efficiency can reach 36～45 heavy %, and the isomerization selectivity is then up to 69～86%.
Again for example, adopt fluorine-containing 3.5 heavy % provided by the invention, nickel oxide 2.7 heavy %, Tungsten oxide 99.999 27.7 heavy %, the catalyzer that contains zeolite 9.6 heavy % in the carrier is to sulphur content 0.11 heavy %, nitrogen content 668ppm, the lubricating oil distillate of viscosity index 62 carries out hydrofining, 370 ℃ of temperature of reaction, pressure 6 MPas, liquid hourly space velocity 0.5 hour
-1Condition under, the sulphur content of product oil is reduced to below the 10ppm, nitrogen content is reduced to below the 6ppm, yield of lubricating oil is 70～82 heavy %.And employing CN1,056,514A catalyzer disclosed and of the present invention is formed close catalyzer, under identical reaction conditions, identical stock oil is carried out hydrofining, though sulphur content also can be reduced to below the 10ppm, nitrogen content also can be reduced to below the 6ppm, but the lubricating oil distillate yield has only 53 heavy %.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Example 1
This example illustrates Catalysts and its preparation method provided by the invention.
(1) quantitatively takes by weighing NaY zeolite (sodium oxide content 13.5 heavy %, silica alumina ratio 4.8, Chang Ling refinery catalyst plant is produced) be that the aqueous ammonium chloride solution of 1M mixes by solvent and solute weight ratio at 5: 1 with concentration, carried out ion-exchange 1 hour at 90 ℃, filter, be not detected 120 ℃ of oven dry, 550 ℃ of roastings 4 hours to there being chlorion with the deionized water wash filter cake.Repeat aforesaid operations process twice, obtain the y-type zeolite of sodium oxide content 0.35 heavy %.Wherein sodium oxide content adopts aas determination.
(2) taking by weighing aluminum nitrate 47 grams is dissolved in 210 ml deionized water.Y-type zeolite 300 gram and the methylcellulose gum (trade mark M20 of the sodium oxide content 0.35 heavy % that the solution that obtains and (1) are obtained; Shanghai chemical reagent factory product) 6 grams mix; be extruded into the bar shaped of 3 millimeters of diameters; 120 ℃ of oven dry place activation furnace, feed the deionized water of 375 Grams Per Hours and 1.5 liters/hour air in activation furnace; be warming up to 650 ℃ simultaneously; constant temperature 2 hours cools off, and gets the composition of zeolite and aluminum oxide.Contain y-type zeolite 96.4 heavy % in the composition, aluminum oxide 3.6 heavy %.
(3) the composition porphyrize that 120 grams (2) are obtained, with 280 gram (in aluminum oxide) hydrated aluminum oxide (title dry glue powders, Chang Ling refinery catalyst plant is produced) and suitable quantity of water mix, be extruded into diameter and be 3 millimeters bar shaped, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours obtain support of the catalyst, contain zeolite 28.9 heavy % in the support of the catalyst, aluminum oxide 71.1 heavy %.
(4) take by weighing support of the catalyst 200 grams that (3) obtain, with 200 milliliters of ammonium fluoride aqueous solutions dippings of fluorinated ammonium 21.4 grams, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours.Contain 26 gram nickelous nitrate [Ni (NO with 200 milliliters again
3)
26H
2O], 113 gram ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] aqueous solution dipping.120 ℃ of oven dry, 470 ℃ of roastings 4 hours, catalyzer C
1Catalyzer C
1Middle nickel, tungsten and fluorine content are listed in the table 1.
Wherein, nickel and W content using plasma emission spectrographic determination are referring to " petrochemical complex analytical procedure (RIPP test method) " P360～361, Science Press, 1990.Fluorine Determination on content method is referring to the P185 that ibidems～187.
Example 2
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 1 prepares catalyzer, methylate Mierocrystalline cellulose not in the different just steps (2).The Neutral ammonium fluoride consumption is 24.2 grams in the step (4), and the nickelous nitrate consumption is 36.9 grams, and the ammonium metawolframate consumption is 99.7 grams.The catalyzer of preparing be numbered C
2Catalyzer C
2Middle nickel, tungsten and fluorine content are listed in the table 1.
Example 3
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 1 prepares catalyzer, and the consumption of aluminum nitrate is 100 grams in the different just steps (1), the composition mesolite content 92.6 heavy % that obtain behind the steam roasting, alumina content 7.4 heavy %.Support of the catalyst mesolite content 27.8 heavy %, aluminum oxide 72.2 heavy %.The catalyzer that makes is numbered C
3Catalyzer C
3Middle nickel, tungsten and fluorine content are listed in the table 1.
Example 4
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 1 prepares catalyzer, and the different just consumptions of hydrated aluminum oxide described in the step (3) are 300 grams, and the composition consumption is 33 to exempt from, and described maturing temperature is 650 ℃, contains zeolite 9.6 heavy % in the support of the catalyst that obtains, aluminum oxide 90.4 heavy %.The catalyzer that makes is numbered C
4Catalyzer C
4Middle nickel, tungsten and fluorine content are listed in the table 1.
Example 5
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 1 prepares catalyzer, and the different just consumptions of hydrated aluminum oxide described in the step (3) are 300 grams, and the composition consumption is 33 grams, and maturing temperature is 650 ℃.Contain zeolite 9.6 heavy % in the support of the catalyst that obtains, aluminum oxide 90.4 heavy %.The Neutral ammonium fluoride consumption is 12.6 grams in the step (4), nickelous nitrate consumption 19.3 grams, ammonium metawolframate consumption 87.4 grams.The catalyzer that makes is numbered C
5Catalyzer C
5Middle nickel, tungsten and fluorine content are listed in the table 1.
Example 6
This example illustrates Catalysts and its preparation method provided by the invention.
(1) quantitatively taking by weighing NaY zeolite (specification is with example 1) and concentration is that the aqueous ammonium chloride solution of 1M mixes by solvent and solute weight ratio at 5: 1, carried out ion-exchange 1 hour at 90 ℃, filter, be not detected to there being chlorion with the deionized water wash filter cake, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Repeat the aforesaid operations process once, obtain the y-type zeolite of sodium oxide content 0.35 heavy %.Quantitatively take by weighing the y-type zeolite of sodium oxide content 0.35 heavy % and aluminum sulfate aqueous solution that concentration is 15.4 heavy % in liquid-solid ratio 10, carry out ion-exchange 1 hour under the condition that temperature is 90 ℃, filter, with the deionized water wash solid product to there not being acid ion, 120 ℃ of oven dry obtain the heavily AlY zeolite (mixture of zeolite and aluminum compound) of % of alumina content 1.4 heavy %, sodium oxide content 0.5.
(2) take by weighing AlY zeolite 300 grams that obtain, methylcellulose gum 6 grams mix with suitable quantity of water, be extruded into the bar shaped of 3 millimeters of diameters, the strip that obtains is placed activation furnace, in activation furnace, feed the deionized water of 375 Grams Per Hours and 1.5 liters/hour air, be warming up to 650 ℃ simultaneously, constant temperature 2 hours, cool off, get the composition of zeolite and aluminum oxide, composition mesolite and alumina content are respectively 98.6 heavy % and 1.4 heavy %.
(3) take by weighing the above-mentioned composition that obtains 29.2 grams and example 1 described hydrated aluminum oxide 270.8 grams (in aluminum oxide) and suitable quantity of water and mix, press method moulding, the roasting of example 1 step (3), get support of the catalyst.The support of the catalyst mesolite content 9.6 heavy % that obtain, alumina content 90.4 heavy %.
(4) press example 1 step (4) preparation catalyzer, obtain catalyzer C
6Catalyzer C
6Middle nickel, tungsten and fluorine content are listed in the table 1.
Example 7
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 6 prepares catalyzer, different is that the composition consumption that the middle hydrated aluminum oxide consumption (in aluminum oxide) of step (3) is 87.9 grams, zeolite and aluminum oxide is 212.1 grams, support of the catalyst mesolite content 28.9 heavy %, alumina content 71.1 heavy %.Make support of the catalyst C
7Catalyzer C
7Middle nickel, tungsten and fluorine content are listed in the table 1.
Example 8
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 6 prepares catalyzer, and hydrated aluminum oxide changes 100 grams into by EP435 in the step (3) that different is, the silicon gel (water-solid ratio is 5.0) and 251.2 of example 3 described methods preparations restrains hydrated aluminum oxides (specification is with example 1, in aluminum oxide) in 513.Support of the catalyst mesolite content 9.6 heavy %, alumina content 80.4 heavy %, silica content 10.0 heavy %.Make catalyzer C
8Table 1 has provided C
8The content of middle nickel, tungsten and fluorine.
Example 9
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 6 prepares catalyzer, and different is that deionized water feeding amount is 75 Grams Per Hours in the step (2), and the feeding amount of air is 20 liters/hour, 4 hours steam roasting time, makes catalyzer C
9Table 1 has provided C
9The content of middle nickel, tungsten and fluorine.
Example 10
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 6 prepares catalyzer, and different is to replace water vapor and Air mixing gas in the step (2) with 100% water vapor, and the feeding amount is 375 Grams Per Hours.The steam-treated temperature is 600 ℃ in the step (2), 6 hours treatment times.The catalyzer that makes is numbered C
10Table 1 has provided C
10The content of middle nickel, tungsten and fluorine.
Example 11
This example illustrates Catalysts and its preparation method provided by the invention.
Y-type zeolite 33 grams and 310.8 gram (in aluminum oxide) examples, 1 described hydrated aluminum oxide that step (1) in the example 1 is obtained mix, adding methylcellulose gum 6 grams and suitable quantity of water mixes, be extruded into the bar shaped of 3 millimeters of diameters, 120 ℃ of oven dry, forming composition is placed activation furnace, feed the deionized water of 375 Grams Per Hours and 1.5 liters/hour air, be warming up to 650 ℃ simultaneously, constant temperature 2 hours, cooling, get the composition of zeolite and aluminum oxide, composition mesolite 9.6 heavy %, aluminum oxide 90.4 heavy %.
Said composition directly as support of the catalyst, is flooded this carrier by the described material consumption of step (4) in the example 1, and drying and roasting under identical condition, catalyzer C got
11Table 1 has been listed C
11Middle nickel, tungsten and fluorine content.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference catalyst.
Method by example 11 prepares catalyzer, does not just soak fluorine, gets reference catalyst B
1B
1Middle nickel, W content are listed in the table 1.
Comparative Examples 2
The preparation of this Comparative Examples explanation reference catalyst.
Press CN1,056, the 514A disclosed method, y-type zeolite 33 grams of step (1) preparation in the example 1 and hydrated aluminum oxide (trade(brand)name SB, German Condea company produces) 310.8 grams (in aluminum oxide) are mixed, add methylcellulose gum 6 grams and suitable quantity of water and mix, be extruded into the bar shaped of 3 millimeters of diameters, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours, support of the catalyst.Contain zeolite 9.6 heavy % in the support of the catalyst, aluminum oxide 90.4 heavy %.
Press the described material consumption of step in the example 1 (4) impregnated carrier, and drying and roasting under the same conditions, comparative catalyst B got
2
Comparative Examples 3
The preparation of this Comparative Examples explanation reference catalyst.
Reference catalyst B
3Be commercial catalysts, industrial trade mark RL-1, the Chang Ling refinery is produced, and this catalyzer is made carrier with aluminum oxide, fluorine-containing 4.9 heavy %, nickel oxide 2.9 heavy %, Tungsten oxide 99.999 28.3 heavy %.
Example 12
This example illustrates Catalysts and its preparation method provided by the invention.
Y-type zeolite 5 grams with example 1 step (1) preparation, (sodium oxide content is 0.01 heavy % to h-mordenite, silica alumina ratio is 21, Fushun No.3 Petroleum Factory produces) 5 grams, example 1 described hydrated aluminum oxide 190 grams (in aluminum oxide) and suitable quantity of water mix, be extruded into the bar shaped of 3 millimeters of diameters, 120 ℃ of oven dry, the exsiccant forming composition is placed activation furnace, speed with 100 Grams Per Hours and 40 liters/hour feeds the deionization water and air respectively, be warming up to 650 ℃ simultaneously, constant temperature 3 hours, get zeolite and alumina composition, contain zeolite 5 heavy % in the composition, aluminum oxide 95 heavy %.
Directly as support of the catalyst, use the consumption of method dipping Neutral ammonium fluoride, nickelous nitrate and ammonium metawolframate, Neutral ammonium fluoride, nickelous nitrate and the ammonium metawolframate identical to be respectively 31.4 grams said composition with example 1 step (4), 31.9 grams, 120 grams make catalyzer C
12Table 1 has provided C
12The content of middle nickel, tungsten and fluorine.
Table 1
| Example number | The catalyzer numbering | Fluorine content, heavy % | Nickel oxide content, heavy % | Tungsten oxide content, heavy % |
| 1 | C 1 | 3.5 | 2.7 | 27.7 |
| 2 | C 2 | 4.0 | 4.0 | 25.2 |
| 3 | C 3 | 3.5 | 2.7 | 27.7 |
| 4 | C 4 | 3.5 | 2.7 | 27.7 |
| 5 | C 5 | 2.1 | 2.2 | 23.2 |
| 6 | C 6 | 3.5 | 2.7 | 27.7 |
| 7 | C 7 | 3.5 | 2.7 | 27.7 |
| 8 | C 8 | 3.5 | 2.7 | 27.7 |
| 9 | C 9 | 3.5 | 2.7 | 27.7 |
| 10 | C 10 | 3.5 | 2.7 | 27.7 |
| 11 | C 11 | 3.5 | 2.7 | 27.7 |
| Comparative Examples 1 | B 1 | 3.5 | 2.7 | 27.7 |
| Comparative Examples 2 | B 2 | 3.5 | 2.7 | 27.7 |
| Comparative Examples 3 | B 3 | 4.9 | 2.9 | 28.3 |
| 12 | C 12 | 4.9 | 3.3 | 29.0 |
Example 13～24
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Respectively with catalyzer C
1～C
12Be broken into the particle of 0.3～0.45 millimeter of diameter, mix with equigranular quartz sand respectively, on 2 milliliters micro-reactor, estimate its catalytic performance by 1: 1 volume ratio.2 milliliters of catalyzer and quartz sand mixture loading amounts, reaction raw materials is a normal heptane, elder generation's normal heptane with 3 heavy % dithiocarbonic anhydride under hydrogen atmosphere carried out prevulcanized 2 hours at 300 ℃ before the reaction, switch reaction raw materials, be warming up to 350 ℃, reaction is carried out under the following conditions: 350 ℃ of temperature of reaction, pressure 2.5 MPas, liquid hourly space velocity 1 hour
-1, hydrogen flowing quantity 400 ml/min.Evaluation result is listed in the table 2.Wherein,
Comparative Examples 4～6
The catalytic performance of following Comparative Examples explanation reference catalyst.
Press the method evaluation of catalyst activity of example 13～24, different is that catalyst system therefor is respectively reference catalyst B
1, B
2And B
3Evaluation result is listed in the table 2.
Table 2
| Example number | Catalyst system therefor | Transformation efficiency, heavy % | The isomerized products productive rate, heavy % | The isomery selectivity, % |
| 13 | C 1 | 58 | 35 | 60 |
| 14 | C 2 | 55 | 38 | 69 |
| 15 | C 3 | 51 | 37 | 73 |
| 16 | C 4 | 43 | 37 | 86 |
| 17 | C 5 | 45 | 36 | 80 |
| 18 | C 6 | 42 | 32 | 76 |
| 19 | C 7 | 53 | 28 | 53 |
| 20 | C 8 | 45 | 29 | 64 |
| 21 | C 9 | 45 | 33 | 73 |
| 22 | C 10 | 40 | 31 | 78 |
| 23 | C 11 | 36 | 25 | 69 |
| 24 | C 12 | 35 | 26 | 74 |
| Comparative Examples 4 | B 1 | 43 | 16 | 37 |
| Comparative Examples 5 | B 2 | 48 | 7 | 15 |
| Comparative Examples 6 | B 3 | 12 | 11 | 92 |
Example 25
Following example illustrates the catalytic performance of catalyzer provided by the invention.
The catalyzer C that the granular size of packing in 20 milliliters of small stationary bed bioreactors is 0.3～0.45 millimeter
420 milliliters, be warming up to 300 ℃ earlier, under hydrogen atmosphere, carried out prevulcanized 10 hours with the kerosene that contains 2 heavy % dithiocarbonic anhydride, switch reaction raw materials.Reaction raw materials is the kerosene(oil)fraction of 187～277 ℃ of boiling range scopes, and temperature of reaction is respectively 360 ℃, reaction pressure 4.0 MPas, liquid hourly space velocity 1.0 hours
-1, hydrogen volume is than 500.The boiling range scope of stock oil, sulphur, nitrogen and alkali nitrogen content are listed in the table 3, and evaluation result is listed in the table 4.
Comparative Examples 7～9
The catalytic performance of following contrast row explanation reference catalyst.
Press the catalytic performance of the method evaluate catalysts of example 25, just catalyst system therefor is respectively reference catalyst B
1, B
2And B
3Evaluation result is listed in the table 3.
Table 3
| The stock oil title | Kerosene |
| Boiling range, ℃ | 187～277℃ |
| Sulphur content, ppm | 500 |
| Nitrogen content, ppm | 77.5 |
| The alkali nitrogen content, ppm | 26.1 |
Table 4
| Example number | 25 | Comparative Examples 7 | Comparative Examples 8 | Comparative Examples 9 |
| Catalyzer | C 4 | B 1 | B 2 | B 3 |
| Temperature of reaction, ℃ | 360 | 360 | 360 | 360 |
| The treated oil yield, heavy % | 98.3 | 90.5 | 86 | 98.5 |
| Boiling range, ℃ | 185～280 | 185～280 | 185～280 | 185～280 |
| Sulphur content, ppm | 4 | 5 | 4 | 47 |
| Nitrogen content, ppm | 20 | 52 | 21 | 23 |
The result of table 4 shows that catalyzer provided by the invention has higher desulfuration and denitrification activity in the high purpose product yield of maintenance.
Example 26～33
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Press the method evaluate catalysts C of example 25
1, C
2, C
4, C
5, C
6, C
7, C
11, C
12Catalytic performance, just reaction raw materials is the three-way pressed oil of 362～507 ℃ subtract (lubricating oil distillate) for the boiling range scope, temperature of reaction is 370 ℃, reaction pressure 6.0 MPas, liquid hourly space velocity are 0.5, and hydrogen to oil volume ratio is 1000, reaction raw materials character is listed in the table 5, and evaluation result is listed in the table 6.
Comparative Examples 10
The catalytic performance of following contrast row explanation reference catalyst.
Press the catalytic performance of the method evaluate catalysts of example 26～33, just catalyst system therefor is reference catalyst B
2Evaluation result is listed in the table 6.
Table 5
| The stock oil title | Subtract three-way wax oil |
| Boiling range, ℃ | 362～507 |
| Viscosity index | 62 |
| Sulphur content, heavy % | 0.11 |
| Nitrogen content, ppm | 668 |
Table 6
| Example number | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | Comparative Examples 10 |
| Catalyzer | C 1 | C 2 | C 4 | C 5 | C 6 | C 7 | C 11 | C 12 | B 2 |
| ＞370 ℃ generate oily yield, heavy % | 65 | 68 | 82 | 78 | 79 | 60 | 70 | 82 | 53 |
| Viscosity index | 119 | 118 | 100 | 95 | 100 | 123 | 96 | 93 | 119 |
| Sulphur content, ppm | 2.5 | 4.0 | 6.5 | 3.2 | 3.6 | 2.7 | 7.8 | 8.2 | 8.2 |
| Nitrogen content, ppm | 4.3 | 3.4 | 5.4 | 5.5 | 3.2 | 4.5 | 5.0 | 4.9 | 5.0 |
Claims (30)
1. catalyst for hydrogenating hydrocarbon oil that contains zeolite, this catalyzer is by a kind of carrier and load on metal component of group VIB on this carrier and metal component of group VIII and auxiliary agent fluorine are formed, the content that it is characterized in that described auxiliary agent fluorine is 0.5～6 heavy %, in oxide compound, metal component of group VIB content is 10～35 heavy %, and metal component of group VIII content is 0.5～6 heavy %; Described carrier contains the composition of a kind of zeolite and aluminum oxide, said composition is the uniform mixture composition that roasting obtained more than 0.5 hour under 500～800 ℃ of water vapour atmospheres that sodium oxide content is not more than the compound of the zeolite of 1 heavy % and aluminium, content 1～99.95 heavy % of composition mesolite, the content of carrier mesolite is 1～80 heavy %, and described zeolite is selected from one or more in X type zeolite, y-type zeolite, mordenite and the Beta zeolite.
2. catalyzer according to claim 1, it is characterized in that the carrier of described catalyzer contains the composition of a kind of zeolite and aluminum oxide, said composition is that sodium oxide content is not more than the zeolite of 1 heavy % and the uniform mixture composition that roasting obtained more than 0.5 hour under 500～800 ℃ of water vapour atmospheres of aluminium hydroxide, the content of composition mesolite is 1～80 heavy %, also contain or do not contain a kind of heat-resistant inorganic oxide in the described carrier in addition, described carrier mesolite content is 1～80 heavy %.
3. catalyzer according to claim 2 is characterized in that described carrier mesolite content is 1～50 heavy %.
4. catalyzer according to claim 3 is characterized in that described carrier mesolite content is 1～35 heavy %.
5. catalyzer according to claim 1, it is characterized in that the carrier of described catalyzer contains the composition of a kind of zeolite and aluminum oxide, said composition is that sodium oxide content is not more than the zeolite of 1 heavy % and the uniform mixture composition that roasting obtained more than 0.5 hour under 500～800 ℃ of water vapour atmospheres of aluminum nitrate, content 80～99.5 heavy % of composition mesolite; Also contain a kind of heat-resistant inorganic oxide in the carrier, the content of heat-resistant inorganic oxide makes and contains zeolite 1～80 heavy % in the carrier.
6. catalyzer according to claim 5, the content that it is characterized in that described heat-resistant inorganic oxide make and contain zeolite 1～50 heavy % in the carrier.
7. catalyzer according to claim 6, the content that it is characterized in that described heat-resistant inorganic oxide make and contain zeolite 1～35 heavy % in the carrier.
8. catalyzer according to claim 1, it is characterized in that the carrier of described catalyzer contains the composition of a kind of zeolite and aluminum oxide, said composition is that sodium oxide content is not more than the aluminium type zeolite that the roasting under 500～800 ℃ of water vapour atmospheres of aluminum ions zeolite of containing of 1 heavy % obtained more than 0.5 hour, described aluminium type zeolite mesolite content 80～99.5 heavy %; Also contain a kind of heat-resistant inorganic oxide in the carrier, it is 1～80 heavy % that the content of heat-resistant inorganic oxide makes carrier mesolite content.
9. it is 1～50 heavy % that catalyzer according to claim 8, the content that it is characterized in that described heat-resistant inorganic oxide make carrier mesolite content.
10. it is 1～35 heavy % that catalyzer according to claim 9, the content that it is characterized in that described heat-resistant inorganic oxide make carrier mesolite content.
11., it is characterized in that described heat-resistant inorganic oxide is selected from one or more in silicon oxide, aluminum oxide, amorphous aluminosilicate, zirconium white, titanium oxide, magnesium oxide, Thorotrast, beryllium oxide, boron oxide, the Cadmium oxide according to any described catalyzer in claim 2 and 5～10.
12. catalyzer according to claim 11 is characterized in that described heat-resistant inorganic oxide is selected from one or more in silicon oxide, aluminum oxide, the amorphous aluminosilicate.
13. according to any described catalyzer in the claim 1,2,5 and 8, it is characterized in that described in moisture vapor atmosphere the temperature of the uniform mixture of roasting zeolite and aluminum compound be 550～750 ℃, roasting time is 0.5～8 hour.
14. catalyzer according to claim 13 is characterized in that described roasting time is 2～6 hours.
15. catalyzer according to claim 13 is characterized in that the atmosphere of described moisture vapor refers to water vapor and Air mixing gas or 100% water vapor.
16., it is characterized in that described zeolite is selected from one or more the mixture in y-type zeolite or y-type zeolite and X type zeolite, mordenite, the Beta zeolite according to any described catalyzer in the claim 1～10.
17. catalyzer according to claim 1 is characterized in that described metal component of group VIB is selected from one or more in the simple substance of tungsten, oxide compound, the sulfide; In oxide compound, the content of tungsten is 10～30 heavy %.
18. catalyzer according to claim 1 is characterized in that described metal component of group VIII is selected from one or more in the simple substance of cobalt, nickel, palladium, platinum, oxide compound and the sulfide.
19. catalyzer according to claim 18 is characterized in that described metal component of group VIII is selected from one or more in the simple substance of cobalt or nickel, oxide compound and the sulfide; In oxide compound, metal component of group VIII content is 2～5 heavy %.
20. catalyzer according to claim 1, the content that it is characterized in that described auxiliary agent fluorine are 1～5 heavy %.
21. claim 1 Preparation of catalysts method comprises successively with the solution of fluorochemicals and contains the solution impregnating carrier of group VIB, group VIII metal compound, carry out drying and roasting behind each dipping, wherein, described carrier contains the composition of a kind of zeolite and aluminum oxide, the preparation method of said composition comprises and sodium oxide content is not more than the uniform mixture of the zeolite of 1 heavy % and aluminum compound roasting is more than 0.5 hour under 500～800 ℃ of water vapour atmospheres that the consumption of zeolite and aluminum compound makes and contains zeolite 1～99.95 heavy % in the described composition.
22. method according to claim 21 is characterized in that the uniform mixture of described zeolite and aluminum compound refers to the uniform mixture of zeolite and aluminium hydroxide and/or aluminum nitrate or goes up aluminum ions aluminium type zeolite through the ion exchange method exchange.
23. method according to claim 21 is characterized in that can also containing extrusion aid and/or tackiness agent commonly used in a kind of hydrogenation catalyst preparation process in the uniform mixture of described zeolite and aluminum compound.
24. method according to claim 21, it is characterized in that the composition of described zeolite and aluminum oxide can directly be used alone as the carrier of catalyzer, also said composition can be mixed carrier as catalyzer with a kind of heat-resistant inorganic oxide, or mix with a kind of precursor of heat-resistant inorganic oxide, moulding or not moulding, be re-used as the carrier of catalyzer after drying, the roasting, the consumption of described heat-resistant inorganic oxide or its precursor makes and contains zeolite 1～80 heavy % in the support of the catalyst.
25. making, method according to claim 24, the consumption that it is characterized in that described heat-resistant inorganic oxide or its precursor contain zeolite 1～50 heavy % in the support of the catalyst.
26. making, method according to claim 25, the consumption that it is characterized in that described heat-resistant inorganic oxide or its precursor contain zeolite 1～35 heavy % in the support of the catalyst.
27., it is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous aluminosilicate, boron oxide, magnesium oxide, zirconium white, titanium oxide, Thorotrast, beryllium oxide, the Cadmium oxide according to any described method in the claim 24～27; The precursor of heat-resistant inorganic oxide can be selected from corresponding oxyhydroxide of above-mentioned oxide compound and colloidal sol thereof in one or more.
28. method according to claim 27 is characterized in that described heat-resistant inorganic oxide is selected from silicon oxide, aluminum oxide or their mixture; The precursor of described heat-resistant inorganic oxide is selected from one or more in hydrated aluminum oxide, silicon sol, silicon gel, the water glass.
29. method according to claim 21 is characterized in that described fluorine cpd are selected from Neutral ammonium fluoride and/or hydrogen fluoride; Described group VIB metallic compound is selected from one or more in ammonium metawolframate, metatungstic acid nickel, the ethyl ammonium metawolframate; Described group VIII metal compound is selected from muriate, nitrate, the muriate of nickel, the nitrate of cobalt, one or more in carbonate, acetate, the metatungstate.
30. method according to claim 21, it is characterized in that described in moisture vapor atmosphere the temperature of the uniform mixture of roasting zeolite and aluminum compound be 550～750 ℃, roasting time is 2～6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98120382A CN1069685C (en) | 1998-10-13 | 1998-10-13 | Zeolite-contained catalyst for hydrogenating hydrocarbon oil and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98120382A CN1069685C (en) | 1998-10-13 | 1998-10-13 | Zeolite-contained catalyst for hydrogenating hydrocarbon oil and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1250800A CN1250800A (en) | 2000-04-19 |
| CN1069685C true CN1069685C (en) | 2001-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98120382A Expired - Lifetime CN1069685C (en) | 1998-10-13 | 1998-10-13 | Zeolite-contained catalyst for hydrogenating hydrocarbon oil and its preparing process |
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| CN115957805B (en) * | 2021-10-13 | 2026-01-02 | 中国石油化工股份有限公司 | A chemical-grade hydrocracking catalyst, its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4401556A (en) * | 1979-11-13 | 1983-08-30 | Union Carbide Corporation | Midbarrel hydrocracking |
| CN1056514A (en) * | 1990-05-11 | 1991-11-27 | 中国石油化工总公司化工科学研究院 | Catalyst for hydrogenation treatment of heavy fraction oil |
| US5288396A (en) * | 1979-10-15 | 1994-02-22 | Union Oil Company Of California | Hydrocracking process using a catalyst selective for making middle distillates |
-
1998
- 1998-10-13 CN CN98120382A patent/CN1069685C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288396A (en) * | 1979-10-15 | 1994-02-22 | Union Oil Company Of California | Hydrocracking process using a catalyst selective for making middle distillates |
| US4401556A (en) * | 1979-11-13 | 1983-08-30 | Union Carbide Corporation | Midbarrel hydrocracking |
| CN1056514A (en) * | 1990-05-11 | 1991-11-27 | 中国石油化工总公司化工科学研究院 | Catalyst for hydrogenation treatment of heavy fraction oil |
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| CN1250800A (en) | 2000-04-19 |
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