CN1317368C - Method for preparing lubricating oil base oil - Google Patents
Method for preparing lubricating oil base oil Download PDFInfo
- Publication number
- CN1317368C CN1317368C CNB2004100298695A CN200410029869A CN1317368C CN 1317368 C CN1317368 C CN 1317368C CN B2004100298695 A CNB2004100298695 A CN B2004100298695A CN 200410029869 A CN200410029869 A CN 200410029869A CN 1317368 C CN1317368 C CN 1317368C
- Authority
- CN
- China
- Prior art keywords
- oil
- silica
- alumina
- hydrotreatment
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002199 base oil Substances 0.000 title abstract description 11
- 239000010687 lubricating oil Substances 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 239000003921 oil Substances 0.000 claims abstract description 53
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 32
- 239000000314 lubricant Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 210000004243 sweat Anatomy 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 30
- 239000010457 zeolite Substances 0.000 description 24
- 229910021536 Zeolite Inorganic materials 0.000 description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 239000002585 base Substances 0.000 description 16
- 150000002431 hydrogen Chemical class 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 241000640882 Condea Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052717 sulfur Chemical group 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 102000007641 Trefoil Factors Human genes 0.000 description 2
- 235000015724 Trifolium pratense Nutrition 0.000 description 2
- YIFVJYNWLCNYGB-UHFFFAOYSA-N [Si]=O.[Zr] Chemical compound [Si]=O.[Zr] YIFVJYNWLCNYGB-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- -1 Fluoride Anions Chemical group 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- CNGGOAOYPQGTLH-UHFFFAOYSA-N [O-2].[O-2].[Mg+2].[Al+3] Chemical compound [O-2].[O-2].[Mg+2].[Al+3] CNGGOAOYPQGTLH-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- OTUXRAAQAFDEQT-UHFFFAOYSA-N magnesium oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Mg+2].[Si+2]=O.[O-2] OTUXRAAQAFDEQT-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FMLYSTGQBVZCGN-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Si+2]=O.[O-2].[O-2] FMLYSTGQBVZCGN-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for preparing lubricating oil base oil, which comprises: (a): a hydrocarbon oil material contacts with a hydrotreating catalyst at the temperature of 320 to 430DEG C under the hydrogen partial pressure of greater than 11 to 30 megapascals in a hydrotreating reaction area; (b): the hydrotreated oil contacts with a dewaxing catalyst at the temperature of 310 to 430DEG C under the hydrogen partial pressure of greater than 11 to 30 megapascals in a dewaxing reaction area; (c): the dewaxed oil contacts with a hydrogenating catalyst with silicon oxide / aluminium oxide, platinum and palladium at the temperature of 170 to 320DEG C under the hydrogen partial pressure of greater than 11 to 30 megapascals in a hydrofining area so as to prepare the lubricating oil base oil.
Description
Technical field
The invention relates to a kind of preparation method of lubricant base.The method of more specifically saying so and adopting multistep hydrogenation preparing lubricant base about a kind of.
Background technology
Adopt the method for multistep hydrogenation preparing lubricant base to know in the art.In these class methods, the first step is to be purpose with hydrogenating desulfurization, nitrogen mostly, simultaneously with the saturated unifining process of part aromatic hydrogenation.Catalyst system therefor generally includes group VIII non-noble metal components and the VI family metal component on a kind of carrier and this carrier of load.The carrier that is fit to is aluminum oxide, silica-alumina or fluoro-containing alumina, and suitable hydrogenation active metals component is nickel-molybdenum, nickel-tungsten or cobalt-molybdenum.Thereafter hydrogenation step is looked stock oil, technical process and to generating different and different that oil quality requires.
CN 1225662A discloses a kind of method for preparing lubricant base, this method comprises: a) at a hydrotreatment reaction zone, the hydrogen dividing potential drop is lower than 11 MPas and temperature is under 260 ℃ of-427 ℃ of conditions, the petroleum of boiling point in 316 ℃ of-677 ℃ of scopes contacted with a kind of hydrotreating catalyst, prepare a kind of hydrotreatment oil, its viscosity index exceeds about 5,100 ℃ of viscosity than the viscosity index of petroleum at least and is at least about 2cSt; B) at a dewaxing reaction zone, under the Hydrodewaxing condition, with hydrotreatment oil contact with a kind of molecular sieve catalyst of intermediate pore size, prepare a kind of pour point be lower than this hydrotreatment the pressed oil of pour point of oil; And c) in the hydrofining district, under the hydroconversion condition pressed oil is contacted with a kind of hydrogenation catalyst that contains platinum/palldium alloy, the platinum in platinum/palldium alloy wherein/palladium mol ratio is between about 2.5: 1 to 1: 2.
The aromatic hydrogenation saturated activity of the hydrogenation catalyst that this method adopted is low, take off fragrant weak effect.In order to produce II, III class lubricating oil base oil, this method must be selected stock oil, and preferably before entering the hydrotreatment district stock oil is carried out solvent treatment.The viscosity index of the stock oil that is fit to should be greater than 75.
Summary of the invention
The objective of the invention is shortcoming, the method for the effective production high-quality lubricant base of a kind of new hydrogenation dearomatization is provided at prior art hydrogenation dearomatization weak effect.
Method provided by the invention comprises: a) at a hydrotreatment reaction zone, a kind of hydrocarbon oil feed is contacted the oil after separation obtains a kind of hydrotreatment with a kind of hydrotreating catalyst; B) one the dewaxing reaction zone, the oil after the hydrotreatment is contacted with a kind of dewaxing catalyst, prepare a kind of depression of pour point pressed oil; C) in a hydrofining district, pressed oil is contacted with a kind of hydrogenation catalyst that contains silica, platinum and metallic palladium, with the preparation lubricant base, it is characterized in that, described reaction conditions comprises the hydrogen dividing potential drop of hydrotreatment reaction zone greater than the 11-30 MPa, and temperature is 320-430 ℃; The hydrogen dividing potential drop of dewaxing reaction zone is greater than the 11-30 MPa, and temperature is 310-430 ℃; The hydrogen dividing potential drop in hydrofining district is greater than the 11-30 MPa, and temperature is 170-320 ℃, and sulphur content is less than 50 μ g/g in the oil after the described hydrotreatment, and nitrogen content is less than 10 μ g/g.
Compare with existing method, method hydrogenation aromatic hydrocarbons effect provided by the invention obviously improves.In addition, adopt the inventive method can directly be used for processing various stock oils, the pour point of the lubricant base of generation is low, yield is high.
For example, employing the invention provides method and processes a kind of content of wax lubricating oil distillate, and the hydrogen dividing potential drop is 12MPa, and the aromaticity content in the lubricant base that obtains is 1.8 weight %, and pour point is-15, and yield is 58 weight %; And adopt identical catalyzer, and when just the hydrogen dividing potential drop was 8MPa, the aromaticity content of the lubricant base that obtains was 7.2 weight %, and pour point is-9, and yield is 56 weight %.Employing the invention provides method and processes a kind of naphthenic lube oil distillate, aromaticity content in the lubricant base that obtains is 5.4 weight %, and adopt identical processing condition be hydrogenation catalyst not simultaneously, the aromaticity content in the lubricant base that obtains is still up to 12.5 weight %.
Description of drawings
Fig. 1 is the schematic flow sheet that the invention provides method.
Embodiment
According to method provided by the invention, the preferred k value of contained silica-alumina is 0.6-15A (cm in the described hydrogenation catalyst
2G)
-1Silica-alumina, further preferred k value is 1-13A (cm
2G)
-1Silica-alumina, be benchmark with the silica-alumina, the content of silicon oxide is preferably 1-60 weight % in the described silica-alumina, is preferably 5-45 weight %.Described k=B/M
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.
B adopts Bio-Rad IFS-3000 type determination of infrared spectroscopy.Concrete grammar is: be pressed into about 10mg/cm behind sample self porphyrize
2The self-supporting sheet, place the original position pond of infrared spectrometer, in 350 ℃, 10
-3Pa vacuum tightness lower surface purifying treatment 2 hours is reduced to room temperature and is introduced the pyridine saturated vapo(u)r, after the adsorption equilibrium 15 minutes, vacuumizes desorption 30 minutes under 200 ℃, reduces to room temperature and surveys absorption and decide the pyridine vibrational spectrum.Sweep limit is 1400cm
-1-1700cm
-1, with 1540 ± 5cm
-1[the infrared Absorption value of unit surface, unit mass sample is expressed as its protonic acid amount of ratio value defined of the infrared Absorption value of bands of a spectrum and sample strip weight and area: A (cm
2G)
-1].M
SiO2Calculate after adopting X fluorescent method [Yang Cuiding etc., petrochemical complex analytical procedure (RIPP test method), Science Press, 1990, P380] working sample to form.
The preparation of described silica-alumina can be containing si molecular sieves or containing the composition that disordering contains si molecular sieves and mix the hydrate of aluminum oxide and at least a disordering, in 350～850 ℃, best 450～650 ℃ of roastings 2～8 hours, best 3～6 hours; Can also be: will be selected from containing si molecular sieves or contain the composition that disordering contains si molecular sieves and directly mixing of the aluminum oxide of one or more crystal formations among γ, η, θ, δ and the χ and at least a disordering.
Wherein, the hydrate of said aluminum oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the unformed aluminium hydroxide.The hydrate of said aluminum oxide also can be the modifier of this hydrate, as add the modifier of silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth etc., the modifier of wherein preferred silicon, they can adopt prior art, are prepared as the method for USP5045519.
Said disordering molecular sieve comprises any one siliceous molecular sieve of disordering, for example silicon metal-the aluminate of disordering, silicon-phosphorus-aluminate, faujusite, ZSM series zeolite etc., the faujusite of preferred disordering or the ZSM series zeolite of disordering (as among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and the ZSM-38 one or more) are preferably in the ZSM series zeolite of the faujusite of disordering and disordering one or more.
The condition that the disordering molecular sieve should satisfy is: when adopting XRD to characterize, be that 100% characteristic peak is a benchmark with original molecule sieve relative intensity, the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 15%.
Containing si molecular sieves or containing the composition blended ratio that disordering contains si molecular sieves of the hydrate of said aluminum oxide and disordering should be 1-60 weight % with the silica content in the poriness silicon oxide-aluminum oxide that finally makes, and is preferably 5-45 weight %.
Containing si molecular sieves or containing the composition that disordering contains si molecular sieves of disordering can be in the hydrated alumina preparation process be directly introduced, also can be by itself and commercially available one or more hydrated alumina mechanically mixing are introduced.When introducing in the hydrated alumina preparation process, the control of alkali metal content can be finished in the hydrated alumina water washing process synchronously; When directly mixing with the commercial alumina hydrate, disordering contains si molecular sieves and preferably carries out ion-exchange individually and remove basic metal.
Described disordering contains si molecular sieves and can obtain by following two kinds of approach:
Article one, approach is to prepare the partially-crystallized si molecular sieves that contains.This partially-crystallized method can adopt in the prior art incomplete crystallization to prepare the method for low-crystallinity molecular sieve, for example C.P.Nicolaides is at ANovel Family of Solid Acid Catalysts:Substantially Amorphous orPartially Crystalline Zeolitic Materials, Applied Catalysis A:General 185,1999, reported among the 211-217.
The second approach is that the si molecular sieves that contains with complete crystallization carries out disordering and handles.For example to X type and Y zeolite, in exsiccant atmosphere (as steam partial pressure less than 0.0069 MPa, preferably less than 0.00138 MPa) roasting down; And for example, at high temperature and V
2O
5Or MoO
3Make the Y zeolite disordering under existing, this disordering trend increases (J.Thoret with the rising of temperature and/or the increase of metal oxide content, etc.Solid-State Interaction Between NaY Zeolite andVanadium Pentoxide, Molybdenum Trioxide, or Tungsten Trioxide, Zeolites, 13,1993,269-275); For another example, in the presence of water vapor, use V
2O
5Make Y zeolite disordering (Carlos A.Trujillo, etc.The Mechnism of Zeolite YDestruction by Steam in the Presence of Vanadium, Journal ofCatalysis 168,1-15,1997); Under certain condition, adopt halogenide to handle Y zeolite and can cause disordering (Kurt A.Becker equally, Catalytic Properties of SyntheticFaujasites Modified with Fluoride Anions, J, Chem.Soc., FaradayTrans.I, 1987,83,535-545), (Kurt A.Becker, etc., Modificationof HY-Zeolite with Trifluoromethane, React.Kinet.Catal.Lett., Vol.29, No.1,1-7,1985).
Described hydrogenization catalyst preparation method comprises described silica-alumina, its precursor, be after the containing si molecular sieves or contain mixture forming that disordering contains the composition of si molecular sieves, roasting of the hydrate of aluminum oxide and disordering, platinum and palladium are introduced described silica, the method of platinum and palladium being introduced described carrier can be any known technology, and for example Chang Yong method is to introduce with the method for the described carrier of solution impregnation of platiniferous, palladium compound.In element and with the catalyzer is benchmark, and the introducing method of described platinum and palladium should make final catalyzer contain platinum and the palladium of 0.1-5 weight %, is preferably 0.2-1.5 weight %, and to satisfy Pd/ (Pt+Pd) weight ratio be 0.3～1.0, is preferably 0.5～0.8.
Described moulding is carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.For example when extrusion, hydrated alumina can be mixed and add an amount of extrusion aid and/or tackiness agent, extrusion moulding then with the mixture of disordering molecular sieve with suitable quantity of water.The kind of described extrusion aid, peptizing agent and consumption all can be this area routines.
Described roasting condition comprises that temperature is 350～850 ℃, is preferably 500～650 ℃, roasting time is 2～84, the time, be preferably 3～6 hours.
Described hydrogenation catalyst reduces down in 150-500 ℃ in the presence of hydrogen before use usually, is translated into and goes back ortho states.This method of reducing is an ordinary method, and reduction can be carried out outside reactor, also can original position carry out in reactor.
According to method provided by the invention, described hydrotreating catalyst is the hydrotreating catalyst of knowing in this area.Usually by heat-resistant inorganic oxide carrier (containing or do not contain molecular sieve) with load on cobalt on this carrier and/or nickel, molybdenum and/or tungsten and fluorine or phosphorus are formed.Wherein, described each components contents is a conventional content, is benchmark in oxide compound and with the catalyzer, the cobalt and/or the nickel that preferably contain 1-8 weight %, molybdenum and/or the tungsten of 10-35 weight % are in element, one or more adjuvant components in fluorine, phosphorus and the boron of 0-6 weight %, the carrier of equal amount.
Heat-resistant inorganic oxide described in the hydrotreating catalyst is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay.Be preferably aluminum oxide and/or silicon oxide.
When containing molecular sieve in the described hydrotreating catalyst, described molecular screening one or more in zeolite or non-zeolitic molecular sieves, preferred bore dia is the molecular sieve of 0.6-0.8 nanometer, as be selected among L zeolite, y-type zeolite, X type zeolite, Beta zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, the SAPO-5 one or more, Y zeolite more preferably, more preferred Y zeolite through the hydrothermal method super stabilizing.
According to the ordinary method in this area, described hydrotreating catalyst is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
According to the invention provides method, described dewaxing catalyst is the catalytic dewaxing catalyzer of knowing in this area, normally contains at least a mesoporous molecular sieve that is selected from nickel, platinum and/or the metallic palladium component of group VIII.Described mesoporous molecular sieve is well known in the art, can be to be selected among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and the SAPO-41 one or more.In metal and with the catalyzer is benchmark, and the content of described group VIII metal is preferably 0.1-10 weight %, more is preferably 0.1-5 weight %.
According to method provided by the invention, the preferred hydrogen dividing potential drop of described hydrotreatment reaction zone is the 11.5-20 MPa, and temperature is 360-420 ℃; The preferred hydrogen dividing potential drop of wax reaction zone is the 11.5-20 MPa, and temperature is 330-390 ℃; The preferred hydrogen dividing potential drop in hydrofining district is the 11.5-20 MPa, and temperature is 190-290 ℃.
According to method provided by the invention, the feeding rate of each reaction zone can be the same or different, and usually, feeding rate can be 0.1-15h
-1(LHSV), be preferably 0.1-5h
-1, 0.2-2h more preferably
-1
According to method provided by the invention, the described known technology that is separated into this area is as the isolating method of high-pressure gas-liquid.Hydrotreatment after gas-liquid separation oil in sulphur content less than 50 μ g/g, preferably less than 20 μ g/g, nitrogen content is less than 10 μ g/g, preferably less than 5 μ g/g.Gas stream uses as recycle hydrogen after removing impurity such as hydrogen sulfide, ammonia.
According to method provided by the invention, by the generation oil that the hydrofining district obtains, can adopt the distillatory method to separate, to produce one or more different oils base oils that satisfy the lubricant base classificating requirement.Described distillatory method is known in this field, can comprise the operating unit of one or more flash distillations, air distillation and underpressure distillation usually, to finish desirable separation.
Method provided by the invention can realize by flow process shown in Figure 1.
To introduce hydrotreatment reaction zone 1 from the hydrogen of pipeline 6 with from the stock oil of pipeline 7, contact with a kind of hydrotreating catalyst, its reaction effluent enters through pipeline 8 and carries out gas-liquid separation in the disengaging zone 5, hydrogen rich stream is drawn through pipeline 11, oil after the hydrotreatment is introduced dewaxing reaction zone 2 through pipeline 9 with from the hydrogen of pipeline 15, contact with a kind of dewaxing catalyst, its reaction effluent is introduced hydrofining district 3 through pipeline 10, with a kind of silica that contains, the hydrogenation catalyst of platinum and metallic palladium contacts, its reaction effluent is introduced distillation zone 4 through pipeline 11 and is separated, obtain hydrogen rich stream and draw through pipeline 12, solvent oil is drawn through pipeline 13, lubricant base is drawn through pipeline 14.
Employing the invention provides method can directly process the various heavy distillates that boiling range is higher than the lubricant base boiling range at least in part that have, to produce various high-quality lubricant bases.Described heavy distillate can be one or more in each line vacuum distillate, solvent treatment vacuum distillate, hydrocracking tail oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, dewaxing vacuum distillate, frivolous asphalt oil, the heavy deasphalted oil.
The following examples will the present invention is described further.
Employed hydrotreating catalyst, dewaxing catalyst and hydrogenation catalyst and preparation method thereof are as follows in the embodiment of the invention:
1. hydrotreating catalyst
Employed hydrotreating catalyst is auxiliary agent with the fluorine for what prepare according to the example among the CN 1057021C 6 in the embodiment of the invention, nickel-tungsten is the catalyzer of active constituent loading on alumina supporter, be benchmark wherein with the catalyzer total amount, in oxide compound, the content of nickel is 2.3 weight %, and the content of tungsten is 22 weight %, in element, the content of fluorine is 4 weight %, and all the other are aluminum oxide.
2. dewaxing catalyst a
Employed dewaxing catalyst a is the catalyzer of active constituent loading on high-Si zeolite containing rare-earth five-membered ring structure/alumina supporter with nickel for what prepare according to the example among the CN 1448484A 3 in the embodiment of the invention, be benchmark wherein with the catalyzer total amount, in oxide compound, the content of nickel is 1 weight %, all the other are carrier, with the carrier is benchmark, and the content of high-Si zeolite containing rare-earth five-membered ring structure is 45 weight % in this carrier, and all the other are aluminum oxide.
2. dewaxing catalyst b
Employed dewaxing catalyst b is the catalyzer of active constituent loading on SAPO-11 molecular sieve/alumina supporter with platinum for what prepare according to the example among the CN 1382526A 6 in the embodiment of the invention, be benchmark wherein with the catalyzer total amount, the content of platinum is 0.3 weight %, all the other are carrier, with the carrier is benchmark, the content of SAPO-11 molecular sieve is 75 weight % in this carrier, and all the other are aluminum oxide.
3. hydrogenation catalyst a
Employed hydrogenation catalyst prepares according to following steps in the embodiment of the invention:
With 800 gram NaY type molecular sieve (SiO2/Al2O3=4.8, degree of crystallinity is defined as 100%, Chang Ling refinery product) placing 4000 milliliters, concentration is ammonium chloride (Beijing Chemical Plant's product of 1.0 moles, analytical pure) in the aqueous solution, exchange is 1 hour under 90 ℃ of stirrings, filters, and does not detect to there being chlorion with deionized water wash, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Repeat the Y zeolite A that said process obtains the heavy % of sodium content (in sodium oxide)＜0.35 (flame atomic absorption spectrometry mensuration) for twice, recording sample degree of crystallinity with x-ray diffraction method is 76%.
Getting Y zeolite A 200 gram, to place 1000 milliliters, concentration be in 0.2 mole Neutral ammonium fluoride (Beijing Chemical Plant's product, the analytical pure) aqueous solution, at 1 hour after-filtration of stirring at normal temperature, and 120 ℃ of oven dry, 700 ℃ of roastings 4 hours obtain Y zeolite disordering sample B.
Get disordering sample B 80 grams and a diaspore thorough mixing that is prepared into according to Chinese patent CN1250746A example 6, trefoil hole orifice plate extrusion with φ 1.8, the strip of gained is filtered back 120 ℃ of oven dry, 550 ℃ of roastings 4 hours, promptly get poriness silicon oxide-aluminum oxide Z1, with the carrier is benchmark, and its silica content is 32.5 weight %, and the k value is 10.4.
The dissolving in deionized water of 1204 milligrams of 437 milligrams in nitric acid four ammonia platinum [Pt (NH3) 4 (NO3) 2] and nitric acid four ammonia palladiums [Pd (NH3) 4 (NO3) 2] is formulated as steeping fluid, immerse 100 gram carrier Z2 in the steeping fluid fully, flood 10 hours after-filtration, through 120 ℃ of oven dry, obtained hydrogenation catalyst b in 4 hours 530 ℃ of roastings, be benchmark wherein with the catalyzer total amount, the content of platinum is 0.22 weight %, the content of metallic palladium is 0.43 weight %, all the other are carrier, and Pd/ wherein (Pt+Pd) weight ratio is 0.66.
3. hydrogenation catalyst b
Get 8 gram Y zeolite disordering sample B and a diaspore 111 grams, Siral-40 powder (production of Condea company) 149 gram thorough mixing, trefoil hole orifice plate extrusion with φ 1.8,120 ℃ of oven dry of strip with gained, 500 ℃ of roastings 6 hours, promptly get poriness silicon oxide-aluminum oxide Z2, with the carrier is benchmark, and its silica content is 25 weight %, and the k value is 2.1.
The dissolving in deionized water of 294 milligrams of 893 milligrams in nitric acid four ammonia platinum [Pt (NH3) 4 (NO3) 2] and nitric acid four ammonia palladiums [Pd (NH3) 4 (NO3) 2] is formulated as steeping fluid, immerse 100 gram carrier Z1 in the steeping fluid fully, flood 10 hours after-filtration, through 120 ℃ of oven dry, obtained hydrogenation catalyst a in 4 hours 530 ℃ of roastings, be benchmark wherein with the catalyzer total amount, the content of platinum is 0.45 weight %, the content of metallic palladium is 1.05 weight %, all the other are carrier, and Pd/ wherein (Pt+Pd) weight ratio is 0.7.
4. Comparative Examples spent hydroprocessing catalyst
Get Siral 40 (Condea company commodity) 163 gram (butt) and monohydrate alumina (SB powder, Condea company commodity) 37 grams (butt), mix and with φ 1.8 3 leaf orifice plate extrusions, dried 4 hours for 120 ℃, 600 ℃ of roastings obtained poriness silicon oxide-aluminum oxide N in 4 hours.With the carrier is benchmark, and its silica content is 32.5 weight %, and the k value is 0.47.
The dissolving in deionized water of 1204 milligrams of 437 milligrams in nitric acid four ammonia platinum [Pt (NH3) 4 (NO3) 2] and nitric acid four ammonia palladiums [Pd (NH3) 4 (NO3) 2] is formulated as steeping fluid, immerse 100 gram carrier N in the steeping fluid fully, flood 10 hours after-filtration, through 120 ℃ of oven dry, obtained contrasting hydrogenation catalyst a in 4 hours 530 ℃ of roastings, be benchmark wherein with the catalyzer total amount, the content of platinum is 0.22 weight %, the content of metallic palladium is 0.43 weight %, all the other are carrier, and Pd/ wherein (Pt+Pd) weight ratio is 0.66.
Embodiment 1
This example is a raw material with a kind of content of wax lubricating oil distillate, and its character sees Table 1.
Process this stock oil according to Fig. 1 technical process.Catalyzer wherein is: hydrotreating catalyst a, and dewaxing catalyst b, hydrogenation catalyst b, operational condition sees Table 2, generates oil nature and sees Table 3.
Table 1
| Stock oil | |
| Kinematic viscosity/mm 2s -1100 ℃ of wax content/m% aromatic hydrocarbons/m% S/m% N/ μ g/g boiling range/m% 5% 50% 95% | 11.5 15.4 18.5 1.3 1500 415 493 604 |
Table 2
| Processing condition | Hydrotreatment | Hydroisomerization | Hydrofining |
| Hydrogen dividing potential drop/MPa temperature of reaction/℃ volume space velocity/h -1 | 12.0 375 0.6 | 12.0 365 0.7 | 12.0 220 1.2 |
Table 3
| Base oil yield | 58% (hydrotreated feedstock relatively) |
| Base oil character | |
| Kinematic viscosity/mm 2s -1100 ℃ of 40 ℃ of viscosity index (VI) pour points/℃ S/ μ g/g N/ μ g/g aromatic hydrocarbons/m% | 9.63 70.13 117 -15 ＜10 ＜1 1.8 |
Comparative Examples 1
This Comparative Examples is used the stock oil identical with embodiment 1, identical catalyzer, the conditional operation that different is according to table 4, and the generation oil nature sees Table 5.
Table 4
| Processing condition | Hydrotreatment | Hydroisomerization | Hydrofining |
| Hydrogen dividing potential drop/MPa temperature of reaction/℃ volume space velocity/h -1 | 8.0 375 0.6 | 8.0 365 0.7 | 8.0 220 1.2 |
Table 5
| Base oil yield | 56% (hydrotreated feedstock relatively) |
| Base oil character | |
| Kinematic viscosity/mm 2s -1100 ℃ of 40 ℃ of viscosity index (VI) pour points/℃ S/ μ g/g N/ μ g/g aromatic hydrocarbons/m% | 9.85 71.23 119 -9 20 4.8 7.2 |
Embodiment 2
This example is a raw material with a kind of naphthenic lube oil distillate, and its character sees Table 6.
Process this stock oil according to Fig. 1 technical process.Catalyzer wherein is: hydrotreating catalyst a, and dewaxing catalyst a, hydrogenation catalyst a, operational condition sees Table 7, generates oil nature and sees Table 8.
Table 6
| Stock oil | |
| Kinematic viscosity/mm 2s -1100 ℃ of 40 ℃ of viscosity index (VI) pour points ℃ saturated hydrocarbons/m% aromatic hydrocarbons/m% colloid/m% S/ μ g/g N/ μ g/g | 72.69 3448 50 -3 66 24.7 9.3 1500 1800 |
Table 7
| Processing condition | Hydrotreatment | The hydrogenation pour point depression | Hydrofining |
| Hydrogen dividing potential drop/MPa temperature of reaction/℃ volume space velocity/h -1 | 15.0 385 0.4 | 15.0 320 1.0 | 15.0 220 1.0 |
Table 8
| Base oil yield m% | 65％ |
| Kinematic viscosity/mm 2s -1100 ℃ of 40 ℃ of viscosity index (VI) pour points/℃ S/ μ g/g N/ μ g/g aromatic hydrocarbons/m% | 28.5 486 82 -16 ＜10 ＜1 5.4 |
Comparative Examples 2
This Comparative Examples is used the stock oil identical with embodiment 2, identical technical process and operational condition, identical hydrotreating catalyst and identical dewaxing catalyst, and different is that hydrogenation catalyst is the contrast hydrogenation catalyst, and the generation oil nature sees Table 9.
Table 9
| Base oil yield m% | 65％ |
| Kinematic viscosity/mm 2s -1100 ℃ of 40 ℃ of viscosity index (VI) pour points/℃ S/ μ g/g N/ μ g/g aromatic hydrocarbons/m% | 28.5 486 82 -16 ＜10 ＜1 12.5 |
Claims (7)
1, a kind of preparation method of lubricant base, this method comprises: a) at a hydrotreatment reaction zone, a kind of hydrocarbon oil feed is contacted the oil after separation obtains a kind of hydrotreatment with a kind of hydrotreating catalyst; B) one the dewaxing reaction zone, the oil after the hydrotreatment is contacted with a kind of dewaxing catalyst, prepare a kind of depression of pour point pressed oil; C) in a hydrofining district, pressed oil is contacted with a kind of hydrogenation catalyst that contains silica, platinum and metallic palladium, described hydrogenation catalyst contains platinum and the palladium of 0.1-5 weight %, Pd/ wherein (Pt+Pd) weight ratio is 0.3～1.0, with the preparation lubricant base, it is characterized in that described reaction conditions comprises the hydrogen dividing potential drop of hydrotreatment reaction zone greater than the 11-30 MPa, temperature is 320-430 ℃; The hydrogen dividing potential drop of dewaxing reaction zone is greater than the 11-30 MPa, and temperature is 310-430 ℃; The hydrogen dividing potential drop in hydrofining district is greater than the 11-30 MPa, and temperature is 170-320 ℃, and sulphur content is less than 50 μ g/g in the oil after the described hydrotreatment, and nitrogen content is less than 10 μ g/g.
2, method according to claim 1 is characterized in that, the k value of the silica-alumina in the described hydrogenation catalyst is 0.6-15A (cm
2G)
-1, be benchmark with the silica-alumina, the content of silicon oxide is 1-60 weight %; Said k=B/M
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.
3, method according to claim 2 is characterized in that, the k value of described silica-alumina is 1-13A (cm
2G)
-1, be benchmark with the silica-alumina, the content of silicon oxide is 5-45 weight %.
4, method according to claim 1 is characterized in that, described hydrogenation catalyst contains platinum and the palladium of 0.2-1.5 weight %, and Pd/ wherein (Pt+Pd) weight ratio is 0.5～0.8.
5, method according to claim 1 is characterized in that, described reaction conditions comprises that the hydrogen dividing potential drop of hydrotreatment reaction zone is the 11.5-20 MPa, and temperature is 360-420 ℃; The hydrogen dividing potential drop of dewaxing reaction zone is the 11.5-20 MPa, and temperature is 330-390 ℃; The hydrogen dividing potential drop in hydrofining district is the 11.5-20 MPa, and temperature is 190-290 ℃.
6, method according to claim 1 is characterized in that, sulphur content is less than 20 μ g/g in the oil after the described hydrotreatment, and nitrogen content is less than 5 μ g/g.
7, method according to claim 1, it is characterized in that described hydrocarbon ils is selected from one or more in vacuum distillate, solvent treatment vacuum distillate, hydrocracking tail oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, dewaxing vacuum distillate, frivolous asphalt oil, the heavy deasphalted oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100298695A CN1317368C (en) | 2004-03-31 | 2004-03-31 | Method for preparing lubricating oil base oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100298695A CN1317368C (en) | 2004-03-31 | 2004-03-31 | Method for preparing lubricating oil base oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1676585A CN1676585A (en) | 2005-10-05 |
| CN1317368C true CN1317368C (en) | 2007-05-23 |
Family
ID=35049338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100298695A Expired - Lifetime CN1317368C (en) | 2004-03-31 | 2004-03-31 | Method for preparing lubricating oil base oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1317368C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978035A (en) * | 2008-03-25 | 2011-02-16 | 吉坤日矿日石能源株式会社 | Lubricant base oil, method for production thereof, and lubricant oil composition |
| CN101978036A (en) * | 2008-03-25 | 2011-02-16 | 吉坤日矿日石能源株式会社 | Lubricant oil composition for internal combustion engine |
| US8563486B2 (en) | 2008-10-07 | 2013-10-22 | Jx Nippon Oil & Energy Corporation | Lubricant composition and method for producing same |
| US8703663B2 (en) | 2008-10-07 | 2014-04-22 | Jx Nippon Oil & Energy Corporation | Lubricant base oil and a process for producing the same, and lubricating oil composition |
| US8785359B2 (en) | 2009-06-04 | 2014-07-22 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition |
| US8796194B2 (en) | 2009-09-01 | 2014-08-05 | Jx Nippon Oil & Energy Corporation | Lubricant composition |
| US8999904B2 (en) | 2009-06-04 | 2015-04-07 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition and method for making the same |
| US9029303B2 (en) | 2009-06-04 | 2015-05-12 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition |
| CN105209580A (en) * | 2013-05-02 | 2015-12-30 | 国际壳牌研究有限公司 | Process for preparing a heavy base oil |
| US9404062B2 (en) | 2009-06-04 | 2016-08-02 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition |
| US9447359B2 (en) | 2008-01-15 | 2016-09-20 | Jx Nippon Oil & Energy Corporation | Lubricant composition |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070062847A1 (en) * | 2005-09-16 | 2007-03-22 | Hyde Evan P | Integrated lubricant upgrading process using once-through, hydrogen-containing treat gas |
| CN100371422C (en) * | 2005-12-12 | 2008-02-27 | 中国石油化工集团公司 | Method for preparing base oil of heat transfer oil |
| CN101343564B (en) * | 2007-07-09 | 2011-12-21 | 中国石油化工股份有限公司 | Method for producing lubricating oil basic oil |
| CN101768470B (en) * | 2008-12-26 | 2013-03-06 | 中国石油化工股份有限公司 | Method for preparing bright stock |
| CN102242001B (en) * | 2010-05-13 | 2014-04-30 | 中国石油化工股份有限公司 | Method for producing lubricant base oil from foots oil |
| CN101862670B (en) * | 2010-06-11 | 2013-03-27 | 中国海洋石油总公司 | Carrier dry powder impregnation preparation method and application of lubricating oil hydrogenation catalyst |
| CN102732300B (en) * | 2011-04-14 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method of producing base oil of high viscosity index lubricant |
| CN102911720B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Hydrogenation method for producing lubricating base oil |
| CN103789019B (en) * | 2012-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce transformer oil base oil |
| CN103897728B (en) * | 2012-12-28 | 2016-04-06 | 中国石油天然气股份有限公司 | A kind of method of lubricant base deep hydrogenation post-refining |
| CN104611023B (en) * | 2013-11-05 | 2017-02-08 | 中国石油化工股份有限公司 | Method for producing special lubricating oil base oil |
| CN104629795B (en) * | 2013-11-08 | 2016-09-07 | 中国石油天然气股份有限公司 | Environment-friendly metal processing base oil and preparation method thereof |
| CN105778993B (en) * | 2014-12-23 | 2018-07-17 | 神华集团有限责任公司 | The lube base oil product that the system and method for production lube base oil and production obtain |
| CN106590743B (en) * | 2015-10-20 | 2018-07-31 | 中国石油化工股份有限公司 | A method of producing lube base oil |
| CN107760375B (en) * | 2016-08-17 | 2020-01-10 | 中国石油化工股份有限公司 | Conversion method of heavy Fischer-Tropsch wax |
| CN107746740A (en) * | 2017-09-06 | 2018-03-02 | 吴江华威特种油有限公司 | A kind of quickly cooling graphene lubricating oil preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664775A (en) * | 1982-07-31 | 1987-05-12 | Toa Nenryo Kogyo Kabushiki Kaisha | Method for manufacturing low pour point petroleum product with zeolite TSZ |
| CN1104678A (en) * | 1993-10-01 | 1995-07-05 | 巴西石油公司 | Process for producing lube base oils of high viscosity index and diesel oil of high cetane number |
| CN1225662A (en) * | 1996-07-15 | 1999-08-11 | 切夫里昂美国公司 | Lubricating base oil mfg. process |
-
2004
- 2004-03-31 CN CNB2004100298695A patent/CN1317368C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664775A (en) * | 1982-07-31 | 1987-05-12 | Toa Nenryo Kogyo Kabushiki Kaisha | Method for manufacturing low pour point petroleum product with zeolite TSZ |
| CN1104678A (en) * | 1993-10-01 | 1995-07-05 | 巴西石油公司 | Process for producing lube base oils of high viscosity index and diesel oil of high cetane number |
| CN1225662A (en) * | 1996-07-15 | 1999-08-11 | 切夫里昂美国公司 | Lubricating base oil mfg. process |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9447359B2 (en) | 2008-01-15 | 2016-09-20 | Jx Nippon Oil & Energy Corporation | Lubricant composition |
| CN101978035B (en) * | 2008-03-25 | 2015-11-25 | 吉坤日矿日石能源株式会社 | Lubricant base and manufacture method thereof and lubricating oil composition |
| CN101978036A (en) * | 2008-03-25 | 2011-02-16 | 吉坤日矿日石能源株式会社 | Lubricant oil composition for internal combustion engine |
| US8546312B2 (en) | 2008-03-25 | 2013-10-01 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition for internal combustion engine |
| CN101978035A (en) * | 2008-03-25 | 2011-02-16 | 吉坤日矿日石能源株式会社 | Lubricant base oil, method for production thereof, and lubricant oil composition |
| CN101978036B (en) * | 2008-03-25 | 2016-04-13 | 吉坤日矿日石能源株式会社 | Lubricant composition for internal combustion engine |
| US8563486B2 (en) | 2008-10-07 | 2013-10-22 | Jx Nippon Oil & Energy Corporation | Lubricant composition and method for producing same |
| US8703663B2 (en) | 2008-10-07 | 2014-04-22 | Jx Nippon Oil & Energy Corporation | Lubricant base oil and a process for producing the same, and lubricating oil composition |
| US8999904B2 (en) | 2009-06-04 | 2015-04-07 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition and method for making the same |
| US9029303B2 (en) | 2009-06-04 | 2015-05-12 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition |
| US8785359B2 (en) | 2009-06-04 | 2014-07-22 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition |
| US9404062B2 (en) | 2009-06-04 | 2016-08-02 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition |
| US8796194B2 (en) | 2009-09-01 | 2014-08-05 | Jx Nippon Oil & Energy Corporation | Lubricant composition |
| CN105209580A (en) * | 2013-05-02 | 2015-12-30 | 国际壳牌研究有限公司 | Process for preparing a heavy base oil |
| CN105209580B (en) * | 2013-05-02 | 2018-06-08 | 国际壳牌研究有限公司 | The method for preparing weight base oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1676585A (en) | 2005-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1317368C (en) | Method for preparing lubricating oil base oil | |
| US10669491B2 (en) | Base metal dewaxing catalyst | |
| TWI491725B (en) | Integrated hydrocracking and dewaxing of hydrocarbons | |
| TWI466995B (en) | Integrated hydrocracking and dewaxing of hydrocarbons | |
| EP3393657B1 (en) | Trim dewaxing of distillate fuel | |
| JP4806897B2 (en) | Catalyst comprising at least one zeolite selected from ZBM-30, ZSM-48, EU-2 and EU-11 and at least one Y zeolite and hydrogenation of hydrocarbon feeds using such a catalyst Conversion method | |
| CN1103636C (en) | Process for the preparation of catalyst composition | |
| EP2155840B1 (en) | Integrated hydroprocessing with high productivity catalysts | |
| US20170136448A1 (en) | Hydrocracking catalyst and process for producing lube base stocks | |
| US20180362860A1 (en) | Trim dewaxing of distillate fuel | |
| CN1854262A (en) | Hydrogenation cracking catalyst composition containing zeolite | |
| CN101035618A (en) | Hydroprocessing catalyst with zeolite and high mesoporosity | |
| KR101810827B1 (en) | Process for producing lube base oil, and lube base oil | |
| CN1723264A (en) | Extremely low acidity ultrastable Y zeolite catalyst composition and process | |
| CN1046544C (en) | Lubricating oil production with VI-selective catalyst | |
| WO2015088602A1 (en) | Method for making a middle distillate | |
| CN1926221A (en) | Process to continuously prepare two or more base oil grades and middle distillates | |
| US10888850B2 (en) | Noble metal and base metal dewaxing catalyst | |
| CN1888024A (en) | Hydrocarbon oil processing method | |
| RU2346977C2 (en) | Method for improvement of loss of mobility temperature of hydrocarbon material obtained by fischer-tropsch synthesis using zeolite mixture catalyst | |
| US10632453B2 (en) | Trimetallic base metal dewaxing catalyst | |
| CN112237947B (en) | Carrier and preparation method thereof, catalyst and preparation method thereof, and dewaxing method | |
| KR101671545B1 (en) | Integrated hydrocracking and dewaxing of hydrocarbons | |
| CN112023960A (en) | Catalyst composition and method for producing high viscosity lubricant base oil from propane deasphalted oil | |
| CN1715259A (en) | Hydrocarbon hydrogenation conversion catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20070523 |
|
| CX01 | Expiry of patent term |