CN102498193B - 包含低聚烯烃的基础油组合物 - Google Patents
包含低聚烯烃的基础油组合物 Download PDFInfo
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- CN102498193B CN102498193B CN2010800409780A CN201080040978A CN102498193B CN 102498193 B CN102498193 B CN 102498193B CN 2010800409780 A CN2010800409780 A CN 2010800409780A CN 201080040978 A CN201080040978 A CN 201080040978A CN 102498193 B CN102498193 B CN 102498193B
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- China
- Prior art keywords
- base oil
- oil
- propylene
- oligomeric
- ionic
- 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.)
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- 239000002199 base oil Substances 0.000 title claims abstract description 96
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 61
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 239000003921 oil Substances 0.000 claims description 34
- 238000006384 oligomerization reaction Methods 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003606 oligomerizing effect Effects 0.000 abstract description 3
- 230000029936 alkylation Effects 0.000 description 31
- 238000005804 alkylation reaction Methods 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- -1 olefin hydrocarbon Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004231 fluid catalytic cracking Methods 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007848 Bronsted acid Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000005649 metathesis reaction Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- RKMOGOGTQIHYMN-UHFFFAOYSA-N 4-(2-methylphenyl)-2h-benzotriazole Chemical compound CC1=CC=CC=C1C1=CC=CC2=NNN=C12 RKMOGOGTQIHYMN-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000005493 condensed matter Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical compound [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
- C10M107/06—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
- C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
- C10M105/28—Carboxylic acids or their salts having only one carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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Abstract
提供了一种基础油，其包含一种或多种低聚烯烃，其中该基础油具有：a.在100℃下大于2.9mm2/s的运动粘度；b.25-90的粘度指数；和c.小于-55℃的浊点。提供了一种通过在离子液体催化剂中使丙烯低聚制得的基础油，其中该基础油具有25-90的粘度指数并且该基础油为无色。还提供了一种通过在酸性烷基-吡啶鎓氯铝酸盐离子液体中使包含丙烯的烯烃进料低聚制得的基础油，其中该基础油具有在100℃下大于2.9mm2/s的粘度指数、25-90的粘度指数和小于-55℃的浊点。
Description
本申请涉及共同提交的题为“Oligomerization of Propylene toProduce Base Oil Products Using Ionic Liquids-Based Catalysis”和“Tuning an Oligomerizing Step to Produce a Base Oil with SelectedProperties”的专利申请；将它们全文并入本文。
发明领域
本发明涉及粘度指数为25-90的基础油组合物。
发明概述
提供了一种基础油，其包含一种或多种低聚烯烃，其中该基础油具有：
a.在100℃下大于2.9mm2/s的运动粘度；
b.25-90的粘度指数；和
c.小于-55℃的浊点。
提供了一种通过在离子液体催化剂中使丙烯低聚制得的基础油，其中该基础油具有25-90的粘度指数并且该基础油为无色。
还提供了一种通过在酸性烷基-吡啶鎓氯铝酸盐离子液体中使包含丙烯的烯烃进料低聚制得的基础油，其中该基础油具有在100℃下大于2.9mm2/s的粘度指数、25-90的粘度指数和小于-55℃的浊点。
发明详述
在本申请中术语基础油用于表示可用于生产成品润滑剂的润滑剂组分。
烯烃进料包含至少一种烯烃。烯烃是不饱和脂族烃。丙烯是具有化学式C3H6的不饱和有机化合物。丙烯具有一个双键。
丙烯可以来自许多来源，包括：作为副产品来自液体原料例如丙烷、丁烷、凝析油、石脑油和LPG的蒸汽裂解；来自炼厂中FCC单元内产生的废气；来自使用贵金属催化剂的丙烷脱氢；以及通过复分解产生。丙烯的供给逐渐增加并且存在将它们提升成有较高价值的产品例如基础油的需求。
FCC单元使用流化催化剂系统来促进催化剂以及在反应器和再生器之间的热传递。再生器中焦炭的燃烧提供了反应器所必需的热。FCC单元实例的很好的总述描述于“UOP Fluid Catalytic Cracking(FCC)and Related Processes”，UOP 4523-7，2008年6月；将其全文并入本文。
提高来自FCC单元的丙烯产量的新的催化剂和辛烷添加剂是可获得的。增加来自FCC单元的丙烯的辛烷添加剂的一个实例是ZSM-5。另外，可以将复分解与蒸汽裂解组合，或者将其增加到FCC单元，以增加丙烯产出。复分解单元需要使用(access)大量不含异丁烯和丁二烯的C4料流。
用于提高丙烯产量的其它工艺是Arco Chemical SuperflexTM工艺；Sinopec开发的深度催化裂解(DCC)；烯烃互变技术，其使用ZSM-5沸石催化剂采用流化(MOI)或固定的催化剂床将C4、轻裂解气(pygas)和轻石脑油转变成丙烯和乙烯。甲醇制烯烃(MTO)工艺具有足够的灵活性从而使丙烯产量提高到总产出量的45％。通过将烯烃裂解工艺(OCP)与MTO工艺整合可进一步增加丙烯产出。OCP工艺从MTO单元获得较重质的烯烃并且将它们转变成丙烯。丙烯还通过使用Lurgi和Statoil开发的MTP工艺使甲醇向丙烯转化来产生。
低聚
低聚是将两个或更多个有机分子化合。低聚步骤形成低聚物。烯烃进料中两个或更多个烯烃分子的低聚致使形成烯烃低聚物，该烯烃低聚物通常包含具有一个剩余双键的长支链分子。所述低聚在离子液体低聚区中使用离子液体催化剂来进行。低聚条件包括在离子液体催化剂的熔点和其分解温度之间的温度。在一个实施方案中，低聚条件包括为约0-约150℃，例如约0-约100℃，或约10-约100℃、约0-约50℃、约40℃-60℃，或者处于50℃左右的温度。
低聚在小于5小时内进行，在一些实施方案中可在小于2小时，或小于1小时内进行。在一个实施方案中低聚进行5分钟-60分钟、10分钟-45分钟、或15分钟-30分钟。
在一个实施方案中，低聚区不包含任何第8-10族过渡金属。
在一个实施方案中低聚在不存在任何异链烷烃的情况下进行。
在一个实施方案中低聚在一种或多种较长链的烯烃存在下进行。
烷基化
低聚物任选在异链烷烃存在下进行烷基化。所述异链烷烃是直链(正构)饱和烃的支链变型。异链烷烃的实例是异丁烷、异戊烷、异己烷、异庚烷和其它较高的异链烷烃。经济性和可获得性会是异链烷烃的选择的主要驱动因素。较轻质的异链烷烃由于它们低的汽油调合价值(归因于它们相对高的蒸气压)而倾向于成本不太高且更加可获得。还可使用异链烷烃的混合物。可使用混合物例如C4-C5异链烷烃并且因为减少的分离费用而可以使其处于有利地位。所述异链烷烃还可以包含稀释剂例如正链烷烃。这可通过减少将异链烷烃与沸点相近链烷烃分离的费用而节省费用。正链烷烃可倾向于成为烷基化步骤中不起反应的稀释剂。还可以将异链烷烃与戊烯进行混合。
在离子液体烷基化区使用离子液体催化剂进行烷基化。对烷基化条件的设定进行选择以形成烷基化的低聚产物。烷基化条件包括在离子液体催化剂的熔点和其分解温度之间的温度。在一个实施方案中烷基化条件包括约15-约200℃，例如约20-约150℃、约25-约100℃或约50-100℃的温度。
在一个实施方案中，将布朗斯台德酸例如HCl、金属卤化物、烷基卤化物、或者直接或间接供给质子的另一种组分或组分混合物加入到低聚区或烷基化区中的任一者或其二者中。虽然不希望受理论限制，但是认为布朗斯台德酸例如HCl或供给质子的其它组分的存在极大地增强了酸性，且因此增强了离子液体催化剂的活性。
基础油
基础油回收自来自低聚步骤的低聚物产物，来自烷基化步骤的烷基化低聚产物，或者回收自低聚步骤和烷基化步骤二者的产物。通过倾析容易地将基础油与离子液体催化剂相进行分离。基础油在100℃下的运动粘度可以为约1.5mm2/s-约70mm2/s。在一些实施方案中，基础油在100℃下的运动粘度为2.9mm2/s或更大、3mm2/s或更大、8mm2/s或更大、或者10mm2/s或更大。在一些实施方案中基础油在100℃下的运动粘度为小于50mm2/s或小于30mm2/s。在一个实施方案中基础油在100℃下的运动粘度为15-30mm2/s。
在一些实施方案中基础油具有包括以下在内的性能的组合：在100℃下为2.9mm2/s或更大的运动粘度，25-90的粘度指数(VI)，和小于-40℃的浊点。在其它实施方案中基础油具有包括以下在内的性能的组合：具有45-70wt％的沸点为900°F或更高的烃，25-90的粘度指数，和小于-25℃的浊点。
通过ASTM D 445-06测定运动粘度。通过ASTM D 2500-09测定浊点。通过ASTM D 2270-04测定粘度指数。通过ASTM D 5950-02(重新核准2007)测定倾点。通过引用将ASTM测试方法D 445-06、D 2500-09、D 2270-04和D 5950-02以它们的全文并入本文。
基础油的粘度指数通常小于120。在一些实施方案中粘度指数小于100，例如25-90，或35-80。在其它实施方案中粘度指数为50-90，或从大于50到85。
在一个实施方案中，当基础油在高温下具有低粘度(即低粘度指数)时，该基础油特别适合于调合成变压器油。通过将一种或多种添加剂调合到该基础油中制得变压器油。具有较低粘度指数的基础油有助于与其调合的变压器油吸收来自变压器部件例如绕组的热，并且将热较快速地带走。在过去为了有效移除热必须在变压器油中使用粘度指数为约45或更小的环烷属基础油。变压器工作温度可达到高达80℃、高达140℃或甚至更高，而由所述基础油制得的变压器油在这些高的工作温度下起到良好作用。
所述基础油具有低浊点。在一些实施方案中浊点可小于-25℃、小于-40℃、小于-45℃、小于-50℃、小于-55℃或甚至小于-60℃。所述基础油还具有低倾点，通常小于-10℃。在一些实施方案中倾点可以为-20℃至-50℃。
在一些实施方案中所述基础油是光亮油。之所谓光亮油是因为该基础油在210°F下的SUS粘度，该光亮油具有在40℃下高于180mm2/s，例如在40℃下高于250mm2/s，或在40℃下可能为500-1100mm2/s的运动粘度。
在一个实施方案中所述基础油具有宽沸程。所述基础油的沸程通过使用SIMDIST的模拟蒸馏来产生。SIMDIST涉及合宜地使用ASTM D 6352-04或ASTM D 2887-08。通过引用将ASTM D 6352-04和ASTM D 2887-08以它们的全文并入本文。
宽沸程是通过SIMDIST获得的T90沸点和T10沸点之差为至少225°F。在一些实施方案中基础油的T90沸点和T10沸点之差为至少225°F、250°F、275°F或300°F。因为所述宽沸程，该基础油可以包含两个或更多个粘度等级的基础油。一个粘度等级的基础油是与另一个粘度等级的基础油区别在于100℃下的运动粘度的差异为至少0.5mm2/s的基础油。回收自低聚步骤或烷基化步骤中之一或其二者的基础油中不同粘度等级的基础油可以通过真空蒸馏进行分离。不同粘度等级的基础油中的一种可以是蒸馏底部产物。
在一个实施方案中基础油包含显著wt％的沸点为900°F或更高的烃。该含量可以大于25wt％、大于35wt％或者为45-70wt％。期望较高含量的沸点为900°F或更高的烃，这是因为存在日益受限制量的具有这些性能的基础油，特别是因为I类基础油工厂正在被关停。
方法的调整(tuning)
有时存在对具有所选运动粘度的一种或多种基础油的提高的需求。在一个实施方案中将调整烷基化条件或低聚条件的设定以使具有所选运动粘度或所选粘度指数的基础油的产量最优化。例如，通过另外包括将一种或多种较长链的α烯烃与烯烃进料混合，提高基础油的粘度指数。较长链的α烯烃进料包含C6+烯烃。例如，较长链的α烯烃可包含C6、C7、C8、C9、C10、C11、C12或甚至更高碳数的α烯烃，或者它们的混合物。在一个实施方案中一种或多种较长链的α烯烃包含C6-C20α烯烃、C6-C12α烯烃或它们的混合物。
在一些实施方案中，与包含丙烯的烯烃进料混合的较长链的α烯烃的碳数越高，则以相同程度将该较长链的α烯烃纳入低聚物产物中所产生的基础油的粘度指数越高。在一些实施方案中，与包含丙烯的烯烃进料混合的较长链的α烯烃的碳数越高，则以相同程度将该较长链的α烯烃纳入低聚物产物中所产生的基础油在100℃下的运动粘度越低。
在一些实施方案中，在低聚期间升高温度，可产生较高粘度的基础油。
在一些实施方案中，对一组低聚条件或一组烷基化条件进行选择或调整，以使两个或更多个粘度等级的基础油之一的产量最优化。例如可将异链烷烃与烯烃的比率向上调节以有利于较大的烷基化和较少的低聚，从而提高较轻粘度等级的基础油的产量。或者，可以上下调节低聚区或烷基化区中的布朗斯台德酸或其它质子源的量以使具有所选运动粘度的基础油的产量最优化。
烷基化可任选在与低聚相同的条件下有效地进行。烷基化和低聚反应可有效地使用相同的离子液体催化剂系统和任选在类似或甚至相同的条件下进行的这种发现可用于获得高度整合的协同过程，从而产生具有所需性能的基础油。此外，在一个具体实施方案中烷基化和低聚可在相同条件下同时进行。
在一个实施方案中，离子液体低聚区或离子液体烷基化区包含酸性氯铝酸盐离子液体催化剂。
在一些实施方案中，离子液体低聚区和离子液体烷基化区均包含酸性氯铝酸盐离子液体催化剂。在一些实施方案中，在所述的两个区中使用相同的酸性氯铝酸盐离子液体催化剂。
低聚和烷基化可同时或分别进行。将低聚和烷基化组合的优点是较低的资金和操作费用。2步工艺(低聚后接着是在另外的区中的烷基化)的优点是可独立地使两个不同的反应区最优化。因此低聚条件可与烷基化条件不同。此外在不同区中离子液体催化剂可以不同。例如，可以优选的是使烷基化区比低聚区的酸性更大。这可能涉及在两个区中使用完全不同的离子液体催化剂或者所述区中之一可以例如通过将布朗斯台德酸加入到烷基化区中来进行更改。
在一个实施方案中，用于离子液体烷基化区和用于离子液体低聚区的离子液体催化剂是相同的。这有助于节省催化剂成本、免于潜在污染问题，并且在该过程中提供了协同机会。
离子液体催化剂
“离子液体”为这样的液体，该液体的组成由作为阳离子和阴离子的组合的离子组成。离子液体是一类完全由离子构成的化合物并且通常在环境温度和接近环境温度下为液体。离子液体倾向于在非常宽的温度范围内为液体，一些具有高达300℃或更高的液体范围。离子液体通常为非挥发性，有效地无蒸气压。许多对空气和水呈稳定性，并且对于许多无机材料、有机材料和聚合物材料可以是良好的溶剂。
最常见的离子液体是由有机基(organic-based)阳离子和无机或有机阴离子制备的那些。离子液体的性能可通过改变阳离子和阴离子对而进行设定(tailor)。离子液体和它们商业应用中一些描述于例如J.Chem.Tech.Biotechnol，68：351-356(1997)；J.Phys.CondensedMatter，5：(supp 34B)：B99-B106(1993)；Chemical and EngineeringNews，Mar.30，1998，32-37；J.Mater.Chem.，＊：2627-2636(1998)；和Chem.Rev.，99：2071-2084(1999)，在此通过引用将它们的内容并入本文。
许多离子液体是基于胺(amine-based)。属于最常见的离子液体是通过如下形成的那些：使含氮杂环(环胺)或含氮芳环(芳族胺)，与烷基化试剂(例如烷基卤)反应形成季铵盐，接着与路易斯酸或卤化物盐进行离子交换，或者通过与合适的阴离子源进行阴离子复分解反应以引入所需的反阴离子从而形成离子液体。
合适的杂芳环的实例包括吡啶和其衍生物、咪唑和其衍生物、吡咯和其衍生物。可用不同(varying)烷化剂将这些环状物(rings)烷基化以在氮上引入广泛范围的烷基，所述烷基包括直链、支链或环状C1-20烷基，但是优选C1-12烷基，这是因为比C1-12更大的烷基可以产生不期望的固体产物而不是离子液体。基于吡啶鎓和基于咪唑鎓的离子液体或许是最常用的离子液体。常使用包括环状和非环状季铵盐的其它基于胺的离子液体。还使用基于鏻或基于锍的离子液体。
离子液体中所使用的阴离子包括氯铝酸根、溴铝酸根、氯化镓(gallium chloride)、四氟硼酸根、四氯硼酸根、六氟磷酸根、硝酸根、三氟甲磺酸根、甲基磺酸根、对甲苯磺酸根、六氟锑酸根、六氟砷酸根、四氯铝酸根、四溴铝酸根、高氯酸根、氢氧根阴离子、二氯化铜阴离子、三氯化铁阴离子、六氟化锑、二氯化铜阴离子、三氯化锌阴离子，以及各种镧、钾、锂、镍、钴、锰和其它金属离子。
离子液体催化剂的阴离子组分的存在应该给予离子液体路易斯或富兰克林酸性特性。通常，阴离子组分与阳离子组分的摩尔比越大，则离子液体混合物的酸度也越大。
在一些实施方案中，离子液体催化剂是酸性卤铝酸盐，例如酸性氯铝酸盐离子液体催化剂。为了在烷基化时有效，离子液体催化剂为酸性。
在一个实施方案中，离子液体催化剂是具有通式RR’R”NH+Al2Cl7 -的季铵氯铝酸盐离子液体，其中RR’和R”是含有1-12个碳的烷基。季铵氯铝酸盐离子液体盐的实例是N-烷基-吡啶鎓氯铝酸盐、N-烷基-烷基吡啶鎓氯铝酸盐、吡啶鎓氢氯铝酸盐、烷基吡啶鎓氢氯铝酸盐、1-丁基-吡啶鎓氯铝酸盐、二烷基-咪唑鎓氯铝酸盐、四烷基-铵氯铝酸盐、三烷基-铵氢氯铝酸盐或它们的混合物。
在一个实施方案中，酸性氯铝酸盐离子液体催化剂是酸性吡啶鎓氯铝酸盐。实例是烷基-吡啶鎓氯铝酸盐。在一个实施方案中，酸性氯铝酸盐离子液体催化剂是具有长度为2-6个碳原子的单个线性烷基的烷基-吡啶鎓氯铝酸盐。经证明有效的一种特定酸性氯铝酸盐离子液体催化剂是1-丁基-吡啶鎓氯铝酸盐。
例如，制备正丁基吡啶鎓氯铝酸盐离子液体盐的典型反应混合物如下所示：
在任选的实施方案中，可将基础油进行加氢以降低该基础油中烯烃的浓度且因此减小溴值。在加氢之后，基础油具有小于0.8，例如小于0.5、小于0.3或小于0.2的溴值。
变压器油添加剂
将本文所述的基础油与一种或多种添加剂进行调合以提供变压器油。在使用时，一种或多种添加剂以有效量存在。用于变压器油的添加剂的有效量是赋予所需一种或多种性能的量。不希望包括超过所述有效量的添加剂量。添加剂的有效量相对小，通常小于变压器油的1.5重量％，优选小于1.0重量％，这是因为变压器油对少量添加剂反应非常灵敏。
可以用于变压器油的添加剂包含倾点抑制剂、抗氧化剂和金属减活剂(当它们使铜减活化时也称作金属钝化剂)。可以在Theo Mang和Wilfried Dresel编辑的“Lubricants and Lubrication”，85-114页中找到不同类别的润滑剂基础油添加剂的评论。
倾点抑制剂通过减少油中悬浮的蜡在该油中形成晶体或固体物质的倾向来降低该油的倾点，因此防止流动。有用的倾点抑制剂的实例是聚甲基丙烯酸酯；聚丙烯酸酯；聚丙烯酰胺；卤石蜡(haloparaffinwax)和芳族化合物的缩合产物；羧酸乙烯酯聚合物；以及富马酸二烷基酯、脂肪酸的乙烯基酯和烷基乙烯基醚的三聚物。倾点抑制剂公开于美国专利No.4,880,553和4,753,745中，通过引用将它们并入本文。所加入的倾点抑制剂的量优选为变压器油的约0.01-约1.0重量％。
对于变压器油而言优异的氧化稳定性是重要的性能。没有足够氧化稳定性的变压器油在过度的温度和氧的影响下，特别是在充当催化剂的小金属颗粒存在下被氧化。随着时间推移，油的氧化可产生油泥和沉积物。在料想的最坏情形中，设备中的油道变得被堵塞并且使设备过热，这进一步加剧了油氧化。油氧化可以产生带电(charged)副产物，例如酸和氢过氧化物，其倾向于降低变压器油的绝缘性能。本文所述的变压器油在不添加抗氧化剂的情况下通常具有优异的氧化稳定性。然而，当需要额外的氧化稳定性时，可以加入抗氧化剂。用于本发明的抗氧化剂的实例是酚类、芳胺、含硫和磷的化合物、有机硫化合物、有机磷化合物和它们的混合物。所加入的抗氧化剂的量优选为本发明变压器油的约0.001-约0.3重量％。
与抗氧化剂组合而使铜钝化的金属减活剂显示出强的协同效应，这是因为它们防止铜离子的形成，从而抑制它们作为氧化促进剂(pro-oxidant)的行为。用于变压器油的金属减活剂包含三唑、苯并三唑、甲苯基苯并三唑(tolyltriazole)和甲苯基苯并三唑衍生物。所加入的金属减活剂的量优选为所述变压器油的约0.005-约0.8重量％。
可以用于变压器油的添加剂系统的实例公开于美国专利No.6,083,889中，通过引用将其并入本文。
出于本说明书和所附权利要求的目的，除非另外标明，表达量、百分比或比例的所有数和说明书和权利要求所用的其它数都应理解为在所有情况下用术语“约”做修饰。此外，本文公开的所有范围是包含端点在内并可以独立组合。只要公开了具有下限和上限的数值范围，则落入该范围内的任何数字也被明确公开。
未定义的任何术语、缩写或简写按照提交本申请时本领域技术人员所使用普通含义来理解。单数形式的“一”、“一个”和“该”包括复数提及物，除非明确地和毫无疑义地限于一种的情形。
本申请中引用的所有出版物、专利和专利申请通过引用以它们的全文并入本文，并入的程度与好像将所公开的每个单独出版物、专利申请或专利明确地且单独地表明通过引用将其以全文并入本文相同。
所撰写的说明书使用实施例(包括最佳实施方式)来公开本发明，并且还能够使任何本领域技术人员实施和使用本发明。上文公开的本发明示例性实施方案的许多改变对于本领域技术人员而言是易于进行的。因此，本发明应理解为包括落入所附权利要求书范围内的所有结构和方法。
实施例
实施例1：纯丙烯的低聚
在手套箱内于氮气下，向300cc高压釜中装入20gm离子液体催化剂(正丁基吡啶鎓七氯铝酸盐)和20gm正己烷(作为稀释剂)。密封该高压釜，将其从手套箱移出并在干冰浴中冷却，通过允许丙烯流入反应器中的入口将其加接到丙烯罐(＞99％商业等级)，在所述入口将100gm丙烯转移到所述反应器(高压釜)中。将所述反应器加接到塔顶搅拌器。通过与温度控制设备连接的热电偶来控制反应温度。一旦一切就绪，通过在0℃下以分批型操作缓慢搅拌反应器中的装料开始反应。该反应呈放热并且温度的上升快速和突然。通过将该高压釜浸在冰浴中来控制温度的上升。将反应温度保持在约50℃。反应压力开始非常高并随着丙烯低聚而减小。让该反应进行15-30分钟。然后，停止该反应并让所述反应器冷却至室温。通过简单倾析出有机层(产物)对该反应进行后处理。用己烷洗涤剩余离子液相以从该离子液相移出所有剩余有机物，并将洗涤物(wash)加入到初始倾析物中。然后用水彻底洗涤该有机层并在无水MgSO4上将其干燥然后过滤。在旋转蒸发器上将滤液浓缩以移除己烷(用作从催化剂提取低聚物的溶剂)。然后分析该重质粘性无色油的沸程、粘度指数、在100℃和40℃下的运动粘度、倾点和浊点。无色是指基础油具有按照ASTM D1500-07的＜0.5ASTM颜色。对所述产物就它们的沸程通过模拟蒸馏进行分析。反应收率和丙烯转化率根据运行的持续时间而改变。所获得的低聚物取决于反应的长度而为60-＞90wt％。表1汇总了用纯丙烯时和在其它烯烃存在下的丙烯低聚产物的性能。
实施例2：炼厂丙烯的低聚
使用上述工序，按照实施例1的工序使含有77％丙烯和23％丙烷的炼厂丙烯进料低聚。产物和选择性与纯丙烯的低聚相同，其中粘度指数、粘度和低温性能(浊点和倾点)非常类似。该基础油也为无色。对于该低聚反应，没有迹象表明丙烷的存在导致任何问题。
实施例3：在1-己烯存在下丙烯的低聚
使用实施例1中所述的工序，在1-己烯(12gm)存在下使丙烯(90gm)进行低聚。一旦向高压釜中装入催化剂，则将其冷却至-30℃(干冰浴)并在加入丙烯之前向其加入1-己烯以使1-己烯的低聚最小化。然后还在该低温下加入丙烯并移走干冰浴。按实施例1中所述使反应进行。该反应提供72gm低聚物。参见关于低聚物性能的表1。
实施例4：在1-辛烯存在下丙烯的低聚
使用实施例3中所述的工序，在1-辛烯(15gm)存在下使丙烯(90gm)进行低聚。该反应获得75gm低聚物。在表1中显示了该油的性能。
实施例5：在1-癸烯存在下丙烯的低聚
使用实施例3中所述的工序，在1-癸烯(20gm)存在下使丙烯(90gm)进行低聚。该反应获得78gm低聚物。在表1中显示了该油的性能。
实施例6：在1-十二碳烯存在下丙烯的低聚
使用实施例3中所述的工序，在1-十二碳烯(20gm)存在下使丙烯(80gm)进行低聚。该反应获得66gm低聚物。在表1中显示了该油的性能。
实施例8：在C6-C12烯属混合物存在下丙烯的低聚
使用实施例3中所述的工序，在1-己烯(1.5gm)、1-辛烯(2gm)、1-癸烯(2.5gm)和1-十二碳烯(3gm)存在下使丙烯(90gm)进行低聚。该反应获得64gm低聚物。在表1中显示了该油的性能。
表1
实施例9
丙烯的低聚
在不存在异链烷烃或异烯烃的情况下，通过将丙烯与1-丁基-吡啶鎓氯铝酸盐离子液体催化剂和少量作为促进剂的HCl混合来进行丙烯的低聚。通过加入供给质子的组分即HCl，制得具有较高运动粘度的基础油。该反应所需的布朗斯台德酸的量非常小，并且可以为0.1gram-1gm的催化量。进料中ppm含量的水的存在足以产生所需的质子量。
制得具有表2中所汇总的性能的光亮油。
表2
| 在40℃下的运动粘度，mm2/s | 572 |
| 在100℃下的运动粘度，mm2/s | 25 |
| 粘度指数 | 36 |
| 倾点，℃ | -25 |
| 浊点，℃ | ＜-60 |
Claims (15)
1.一种基础油，其包含一种或多种低聚烯烃，其中所述基础油具有：
a.在100℃下15mm2/s或更大的运动粘度；
b.25-70的粘度指数；和
c.小于-55℃的浊点。
2.根据权利要求1的基础油，其还具有45-70wt%的沸点为900°F或更高的烃。
3.根据权利要求1的基础油，其还包含用以制备变压器油的一种或多种添加剂。
4.根据权利要求1的基础油，其中该基础油为无色。
5.根据权利要求1的基础油，其还具有-20至-50℃的倾点。
6.根据权利要求1的基础油，其中所述一种或多种低聚烯烃在包含离子液体催化剂的低聚区中制得。
7.根据权利要求6的基础油，其中所述离子液体催化剂选自基于胺、基于鏻、基于锍的离子液体和它们的混合物。
8.权利要求6的基础油，其中所述离子液体催化剂是酸性氯铝酸盐。
9.一种通过在离子液体催化剂中使丙烯低聚制得的基础油，其中该基础油具有在100℃下15mm2/s或更大的运动粘度、25-70的粘度指数并且该基础油为无色。
10.权利要求9的基础油，其中该基础油还具有在100℃下大于15-30mm2/s的运动粘度。
11.权利要求9的基础油，其中该基础油还具有小于-40℃的浊点。
12.根据权利要求9的基础油，其还包含用以制备变压器油的一种或多种添加剂。
13.一种通过在酸性烷基-吡啶鎓氯铝酸盐离子液体中使包含丙烯的烯烃进料低聚制得的基础油，其中该基础油具有在100℃下15mm2/s或更大的运动粘度、25-70的粘度指数和小于-55℃的浊点。
14.权利要求13的基础油，其中该基础油为无色。
15.根据权利要求13的基础油，其还包含用以制备变压器油的一种或多种添加剂。
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| Application Number | Priority Date | Filing Date | Title |
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| US12/538,752 US8101809B2 (en) | 2009-08-10 | 2009-08-10 | Base oil composition comprising oligomerized olefins |
| US12/538,752 | 2009-08-10 | ||
| PCT/US2010/044410 WO2011019564A2 (en) | 2009-08-10 | 2010-08-04 | Base oil composition comprising oligomerized olefins |
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| KR (1) | KR101712992B1 (zh) |
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| BR (1) | BR112012002908A2 (zh) |
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| MY (1) | MY158050A (zh) |
| SG (1) | SG178329A1 (zh) |
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| US8604258B2 (en) * | 2009-08-10 | 2013-12-10 | Chevron U.S.A. Inc. | Base oil having high kinematic viscosity and low pour point |
| US8524968B2 (en) * | 2010-12-13 | 2013-09-03 | Chevron U.S.A. Inc. | Process to make base oil by oligomerizing low boiling olefins |
| CA2880167C (en) | 2012-07-30 | 2016-12-06 | Reliance Industries Limited | Catalytic oligomerization of octenes |
| US9302199B2 (en) | 2012-07-31 | 2016-04-05 | Chevron U.S.A. Inc. | Alkylation process with recycle of hydrogen and recovery of hydrogen chloride |
| US9233316B2 (en) | 2012-07-31 | 2016-01-12 | Chevron U.S.A. Inc. | Hydrogen recycle and hydrogen chloride recovery in an alkylation process |
| US8704018B2 (en) | 2012-07-31 | 2014-04-22 | Chevron U.S.A. Inc. | Extracted conjunct polymer naphtha |
| CN104371773B (zh) * | 2013-08-13 | 2016-09-28 | 西安艾姆高分子材料有限公司 | 一种提高生物柴油低温流动性的方法 |
| US9108891B1 (en) | 2014-11-21 | 2015-08-18 | Chevron Phillips Chemical Company | Ethylene separation with pressure swing adsorption |
| US9732300B2 (en) | 2015-07-23 | 2017-08-15 | Chevron Phillipa Chemical Company LP | Liquid propylene oligomers and methods of making same |
| US10435491B2 (en) | 2015-08-19 | 2019-10-08 | Chevron Phillips Chemical Company Lp | Method for making polyalphaolefins using ionic liquid catalyzed oligomerization of olefins |
| CA3045636A1 (en) * | 2016-12-29 | 2018-07-05 | Exxonmobil Research And Engineering Company | Block processing with bulk catalysts for base stock production from deasphalted oil |
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| DE4205932A1 (de) * | 1992-02-27 | 1993-09-02 | Basf Ag | Verfahren zur herstellung von propenoligomeren |
| GB9402612D0 (en) * | 1994-02-10 | 1994-04-06 | British Petroleum Co Plc | Ionic liquids |
| US5766517A (en) * | 1995-12-21 | 1998-06-16 | Cooper Industries, Inc. | Dielectric fluid for use in power distribution equipment |
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| CN1906277A (zh) * | 2003-12-23 | 2007-01-31 | 切夫里昂美国公司 | 单环烷烃含量高和多环烷烃含量低的润滑基础油 |
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| KR20120061868A (ko) | 2012-06-13 |
| WO2011019564A3 (en) | 2011-06-16 |
| ZA201201030B (en) | 2013-05-29 |
| WO2011019564A4 (en) | 2011-09-01 |
| MY158050A (en) | 2016-08-30 |
| SG178329A1 (en) | 2012-03-29 |
| AU2010282772A1 (en) | 2012-03-01 |
| AU2010282772B2 (en) | 2014-05-22 |
| US20110034743A1 (en) | 2011-02-10 |
| US8101809B2 (en) | 2012-01-24 |
| IN2012DN01456A (zh) | 2015-06-05 |
| KR101712992B1 (ko) | 2017-03-10 |
| WO2011019564A2 (en) | 2011-02-17 |
| BR112012002908A2 (pt) | 2016-04-05 |
| CN102498193A (zh) | 2012-06-13 |
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