CN112725054B - Process method for directly synthesizing high-performance high-viscosity base oil by polymerization of low-carbon olefin - Google Patents
Process method for directly synthesizing high-performance high-viscosity base oil by polymerization of low-carbon olefin Download PDFInfo
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- CN112725054B CN112725054B CN201911032644.8A CN201911032644A CN112725054B CN 112725054 B CN112725054 B CN 112725054B CN 201911032644 A CN201911032644 A CN 201911032644A CN 112725054 B CN112725054 B CN 112725054B
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- Prior art keywords
- base oil
- hydrogenation
- polymerization
- group
- alkyl
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- 239000002199 base oil Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 90
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 94
- 239000002904 solvent Substances 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 38
- 239000003921 oil Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 230000000171 quenching effect Effects 0.000 claims description 15
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000002950 monocyclic group Chemical group 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 14
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- -1 C 1 -C 4 Alkyl Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000010687 lubricating oil Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000002619 bicyclic group Chemical group 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 229920013639 polyalphaolefin Polymers 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 125000001188 haloalkyl group Chemical group 0.000 description 10
- 239000004711 α-olefin Substances 0.000 description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 238000000199 molecular distillation Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004042 decolorization Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000006168 tricyclic group Chemical group 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 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
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000574 NaK Inorganic materials 0.000 description 1
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000013638 trimer 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
- C10M107/04—Polyethene
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
- C10M2205/0225—Ethene used as base material
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
- C10M2205/0245—Propene used as base material
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Lubricants (AREA)
Abstract
The application relates to a process method for directly synthesizing high-performance high-viscosity base oil through polymerization of low-carbon olefin. Specifically, the application discloses a method for directly synthesizing high-performance high-viscosity base oil through low-carbon olefin, which comprises a plurality of procedures such as polymerization, hydrogenation, rectification and the like. The method has the advantages of easily obtained raw materials, less three wastes, reduced pollution in the production process, good performance of the synthesized base oil and low production cost.
Description
Technical Field
The application relates to the technical field of synthetic base oil production, in particular to a method for preparing low-carbon olefin (C) 2 -C 4 ) A process method for directly synthesizing high-performance high-viscosity base oil through polymerization.
Background
The lubricating oil is an indispensable material in industry, and has important value for saving energy, reducing consumption, protecting and guaranteeing long-term high-efficiency operation of equipment. It is counted that 1/3-1/2 of the global industrial energy consumption is caused by friction, and 80% of the failed parts are caused by abrasion, so that the high-performance lubricating oil has great significance for reducing abrasion, reducing energy consumption and sustainable development of society. Since the lubricating oil is composed of 70 to 95% of base oil and 5 to 30% of additives, the properties of the base oil basically determine the quality of the lubricating oil. The internationally common base oil at present comprises mineral oil (API I-API III) and synthetic oil (API IV-V), wherein the total synthetic oil PAO (API IV) has the characteristics of wide operating temperature range, good viscosity temperature performance, high viscosity index, low pour point, small evaporation loss, good oxidation stability, environmental friendliness and the like, is a high-quality lubricating oil base oil, and is applied to a plurality of high-end fields.
The existing PAO production mainly comprises the following three production processes: 1) BF (BF) 3 +alcohol catalytic system: mainly comprises (1) polymerization, (2) BF 3 Recycling, (3) washing, (4) normal pressure distillation, (5) hydrogenation, (6) reduced pressure rectification, and (7) blending seven working procedures; 2) AlCl 3 +alcohol catalytic system: mainly comprises the main procedures of (1) polymerization, (2) sedimentation and slag cutting, (2)1 neutralization, (2)2 filtration, (2)3 normal pressure distillation, (2)4 hydrogenation, (2)5 reduced pressure rectification), (8) clay refining, and (9) tempering; 3) Metallocene catalytic system: mainly comprises (1) polymerization, (2)0 quenching-adsorption, (3) filtration, (4) normal pressure distillation, (5) hydrogenation, (6) reduced pressure rectification, and (7) tempering, wherein the main procedures are as follows. Wherein BF 3 The +alcohol catalytic system is mainly used for producing low viscosity PAO; alCl 3 +alcohols mainly produce medium to high viscosity PAO; metallocene catalytic systems mainly produce PAOs of high viscosity.
The polymerization raw materials for synthesizing PAO by the three processes are mainly C 8 、C 10 And C 12 Alpha-olefins of (C) 10 The quality of the (1-decene) synthesized PAO is best. The alpha-olefin is mostly sourced from ethylene oligomerization, the carbon number of the olefin obtained by oligomerization through SHOP process accords with Flory distribution, and C 8 、C 10 And C 12 The content is about 40%; the target alpha-olefin is obtained through oligomerization and separation and then is subjected to catalytic polymerization to obtain PAO, so that the total conversion rate of ethylene is lower, the whole process is very complex, the process flow is longer, and the production cost of the PAO is greatly increased.
Raw materials for producing PAO in China are all imported, and the goods sources are unstable. There are also related alternative processes: 1) The mixed alpha-olefin prepared by cracking is polymerized, but the olefin distribution of the mixed alpha-olefin obtained by cracking is wide, and contains a large amount of internal olefin and other impurities which cannot participate in polymerization, so that the quality difference between the PAO obtained by cracking and the PAO obtained by using foreign raw materials is obvious. 2) In patent CN201510439004.4, it is reported that the high temperature fischer-tropsch synthesis is performed for the α -olefin, and then the separation polymerization is performed, but the yield of the α -olefin obtained by this scheme is also low (45%), the carbon number of the olefin is continuously distributed (both containing odd carbon and even carbon), resulting in high cost for the early separation, and the purity of the α -olefin is low, especially the adjacent odd carbon and even carbon cannot be separated, which affects the stability and quality of the product performance. In addition, purification at the early stage of polymerization is costly and requires the use of potassium-sodium alloy and the like.
In addition to the above raw material problems, the existing catalytic systems have the following problems:
1)AlCl 3 the +alcohol catalytic reaction system has wide molecular weight distribution, unrecoverable catalyst, great corrosion to equipment due to the existence of great amount of chloride ion, clay neutralization in the early stage and clay refining in the later stage, so that great amount of waste residue is produced in the process (about 10% of the product).
2)BF 3 +alcohol catalytic System due to BF 3 The toxicity is high, the corrosiveness is high, the catalyst recovery is necessary, the recovery cost is very high, and a large amount of wastewater is generated in the post-treatment;
3) The metallocene catalyst systems are mainly very costly in terms of cocatalysts (MAO or perfluorophenyl boron) used.
4) In the above PAO production process, after the polymerization of the α -olefin, the poly α -olefin with different polymerization degrees needs to be first decompressed, rectified and cut to obtain different fractions (for example: dimer, trimer, tetramer, pentamer and other polymers), and then obtaining PAO products with different viscosity grades through subsequent blending steps.
In summary, the existing process flow has the defects of high production cost, complex process flow, more three wastes, shortage of raw material sources and the like, and becomes a main factor affecting the large-scale production and application of PAO. Thus, there is an urgent need in the art to develop new processes to achieve low cost, low pollution, synthesis of high performance base oils.
Disclosure of Invention
The application aims to provide a process route for producing fully synthetic lubricating base oil LPE by one-step polymerization of low-carbon olefin.
The first aspect of the application provides a process for directly preparing base oil by polymerization of low-carbon olefin, comprising the following steps:
(1) Polymerization: sequentially adding a first solvent and aluminum alkyl a into a tubular reactor or a kettle reactor at a set polymerization temperature, continuously introducing low-carbon olefin at the set polymerization pressure, and then adding a catalyst solution into the reactor in batches for polymerization reaction to form the base oil before hydrogenation; wherein,,
the polymerization temperature is 10-60 ℃;
the polymerization pressure is 0.7-2.0 MPa;
the time of the polymerization reaction is 1-24 hours;
the low-carbon olefin is selected from the following groups: ethylene, propylene, or a combination thereof;
the aluminum alkyl a is selected from the group consisting of: triethylaluminum, trimethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, or a combination thereof;
the first solvent is selected from the group consisting of: c (C) 6 ～C 12 Alkane, white oil, toluene, xylene, halogenated C 1 ～C 12 Is an alkane of (a);
the catalyst solution is a solution formed by a complex and aluminum alkyl b in a second solvent; wherein, the molar ratio of the aluminum alkyl b to the complex is as follows: 1 to 100/1;
the aluminum alkyl b is selected from the following group: triethylaluminum, triisobutylaluminum, diethylaluminum chloride, or a combination thereof;
the second solvent is selected from the group consisting of: toluene, halogenated C 1 ～C 12 Is an alkane of (a);
the complex is a combination of a ligand compound I and a divalent metal salt, or the complex is a complex shown as II:
in the method, in the process of the application,
Y 1 respectively is hydrogen, C 1 -C 8 Alkyl or C 1 -C 8 Haloalkyl, unsubstituted or substituted phenyl;
Y 2 CR respectively 4 R 5 、NR 6 O or S, R 4 、R 5 、R 6 Each independently H, C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group;
is an unsubstituted or substituted 5-7 membered monocyclic ring, or a bicyclic or tricyclic group (e.g., spiro structure) containing said 5-7 membered monocyclic ring, wherein said 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;
Y 3 is one or more optionally substituted groups located on the 5-7 membered monocyclic ring or a bicyclic or tricyclic group containing the 5-7 membered monocyclic ring, each Y 3 Independently hydrogen, C 1 -C 8 Alkyl, C 1 -C 8 Haloalkyl, C 5 -C 8 Cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;
z is C respectively 1 -C 8 Alkyl, C 1 -C 8 Haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl;
wherein the term "substituted" as defined in the above definitions means that the group has 1 to 5 substituents selected from the group consisting of: c (C) 1 -C 4 Alkyl and C 1 -C 4 Haloalkyl, halogen, nitro, cyano, CF 3 、-O-R 1 、-N(R 2 ) 2 、-Si(R 3 ) 3 、-CH 2 -O-R 8 、-SR 9 、-CH 2 -S-R 10 、-CH-(R 10 ) 2 Or phenyl which is unsubstituted or substituted by 1 to 5 substituents selected from the group consisting of: c (C) 1 -C 4 Alkyl and C 1 -C 4 Haloalkyl, wherein R 1 、R 2 、R 3 Each independently is C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group; and R is 8 、R 9 And R is 10 Respectively C 1 -C 8 Alkyl or phenyl.
The divalent metal salt is divalent nickel metal salt;
wherein X is independently halogen, C 1 -C 4 Alkyl, C 2 -C 6 Alkenyl, allyl-OAc、 - OTf or benzyl;
(2) Hydrogenation: the base oil before hydrogenation is subjected to hydrogenation reaction through a fixed bed or a kettle type hydrogenation reactor, so that hydrogenated base oil is obtained;
(3) And (3) rectifying: and carrying out molecular rectification on the hydrogenated base oil by negative pressure, thereby obtaining the base oil with high viscosity grade.
In another preferred embodiment, the halogen is preferably fluorine, chlorine or bromine.
In another preferred embodiment, the complex may be used after the ligand compound I is coordinated with the divalent metal salt and then purified, or may be used directly after the ligand compound I is mixed with the divalent metal salt in situ without purification.
In another preferred embodiment, the substituted phenyl has 1 to 3 substituents.
In another preferred embodiment, in the step (2), the solvent used for the fixed bed hydrogenation is an alkane or a mixture of alkanes.
In another preferred embodiment, in the step (2), the solvent used for the fixed bed hydrogenation is hexane; more preferably n-hexane, isohexane, cyclohexane or a mixture of hexane.
In another preferred embodiment, the tubular reactor is a loop.
In another preferred embodiment, the tank reactor is a reaction tank.
In another preferred embodiment, in the step (1), the aluminum alkyl a is selected from the group consisting of: triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride
In another preferred embodiment, in the step (1), the aluminum alkyl a is triethylaluminum.
In another preferred embodiment, in the step (1), the alkyl aluminum a is diethyl aluminum chloride, ethyl aluminum dichloride or ethyl aluminum sesquichloride.
In another preferred example, in the step (1), when ethylene is used as a single raw material, the polymerization temperature is 40-60 ℃, and the polymerization pressure is 1.5-2.0 MPa; when propylene is used as a single raw material, the polymerization temperature is 10-30 ℃, and the polymerization pressure is 0.7-1.2 MPa.
In another preferred embodiment, the method further comprises a solvent recovery and purification step.
In another preferred example, in the step (2), the hydrogenation reaction is performed by a fixed bed hydrogenation process, wherein the fixed bed hydrogenation reaction conditions are as follows:
hydrogenation temperature: 220-300 ℃;
hydrogenation pressure: 2.0 to 4.0MPa;
airspeed: 1.5 to 2.5 hours -1 ；
Hydrogen to oil ratio: 200-300 parts.
In another preferred embodiment, the fixed bed hydrogenation reaction conditions are as follows:
hydrogenation temperature: 220-250 ℃;
hydrogenation pressure: 3-4 MPa;
airspeed: 1.8 to 2.2 hours -1 ；
Hydrogen to oil ratio: 200-300 parts.
In another preferred example, in the step (2), the hydrogenation reaction is performed by a kettle type hydrogenation process, wherein the kettle type hydrogenation process is as follows:
hydrogenation temperature: 100-200 ℃;
hydrogenation pressure: 2.0 to 6.0MPa;
concentration of oil: 0.2-1.0 Kg/L.
In another preferred example, the kettle type processing technology is as follows:
hydrogenation temperature: 100-200 ℃;
hydrogenation pressure: 2.0 to 6.0MPa;
concentration of oil: 0.8-0.9Kg/L.
In another preferred embodiment, in the step (3), the process parameters of the negative pressure rectification are as follows: rectification temperature: 300-350 ℃; and (3) rectification absolute pressure: 1 to 700Pa.
In another preferred embodiment, in the step (3), the negative pressure distillation may use a molecular distillation apparatus, a short path distillation apparatus, or any other apparatus capable of achieving the distillation of the base oil.
In another preferred embodiment, the hydrogenation step and the rectification step may be performed in the same order.
In another preferred embodiment, the step (1) further comprises a post-treatment step after the polymerization reaction is completed: adding a quenching agent into the mixture after the polymerization reaction is completed, and filtering, recovering the solvent and decoloring to obtain clear and transparent pre-hydrogenation base oil; wherein the quencher is selected from the group consisting of: diatomaceous earth, alcohol, silica gel powder, water, or combinations thereof.
In another preferred embodiment, the quencher is an alcohol.
In another preferred example, the molar ratio of the quencher (e.g., alcohol) to the alkyl aluminum=2: 1 to 4:1.
in another preferred embodiment, the quenching agent is methanol, ethanol, isopropanol, t-butanol, n-butanol, isobutanol, or a combination thereof.
In another preferred embodiment, the quenching agent is water.
In another preferred embodiment, the quencher is wet diatomaceous earth.
In another preferred embodiment, the filtering device is a commercially available filtering device.
In another preferred embodiment, the filter screen used for the filtration has a pore size of 1 to 5 microns.
In another preferred embodiment, the liquid-liquid separation device used for recovering the solvent can be a simple atmospheric distillation or rectification device or a reduced pressure distillation or rectification device.
In another preferred embodiment, the apparatus used for the decolorization is a fixed bed decolorization column.
In another preferred example, the filler of the fixed bed can be activated clay, diatomite, silicon dioxide and activated carbon.
In another preferred embodiment, the filler of the fixed bed is activated clay.
In another preferred embodiment, the decolorization temperature is 20-50 ℃.
In another preferred embodiment, the high viscosity grade base oil has a kinematic viscosity of 100 to 300mm at 100 DEG C 2 /s。
In another preferred embodiment, the high viscosity base oil has a molecular weight distribution of less than 2.0, more preferably less than 1.8.
In another preferred embodiment, the high viscosity grade base oil has a kinematic viscosity of 100 to 300mm at 100 DEG C 2 And/s, an acid number of less than 0.01mg KOH/g, wherein the NOACK evaporation loss is less than 1%, the pour point is less than-20 ℃, and the viscosity index is higher than 170.
In a second aspect, the present application provides a high viscosity base oil having a kinematic viscosity of 100 to 300mm at 100 DEG C 2 /s。
In another preferred embodiment, the high viscosity grade base oil has a kinematic viscosity of 100 to 300mm at 100 DEG C 2 And/s, an acid number of less than 0.01mg KOH/g, wherein the NOACK evaporation loss is less than 1%, the pour point is less than-20 ℃, and the viscosity index is higher than 170.
In another preferred embodiment, the base oil is made by the process of the first aspect.
In a third aspect of the application, there is provided a process for the preparation of a mechanical lubricating oil, characterized in that a base oil is prepared by a process according to the first aspect of the application; and
mechanical lubricating oil is prepared from the base oil.
It is understood that within the scope of the present application, the above-described technical features of the present application and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Drawings
Figure 1 shows a process flow diagram for the direct polymerization of ethylene to make a base oil.
FIG. 2 shows the molecular weight and molecular weight distribution (GPC) of the high viscosity base oil LPE100 after molecular fractionation in example 1.
FIG. 3 shows the molecular weight and molecular weight distribution (GPC) of the high viscosity base oil LPE120 after molecular fractionation in example 2.
Detailed Description
The present inventors have conducted extensive and intensive studies and have found that a base oil of high viscosity grade can be obtained by controlling a polymerization process including a formation manner of a catalytic species, a temperature and a pressure of a polymerization reaction, and after further hydrogenation, by a simple rectification process. The method of the application can directly prepare the high-performance high-viscosity base oil from the low-carbon olefin without adopting a very complex or high-cost separation process and a blending process (of course, further, the method can be further blended with other high-performance base oils). On this basis, the inventors completed the present application.
Terminology
As used herein, the term "C 6 ～C 12 By "alkane" is meant a straight or branched chain alkane having from 6 to 12 carbon atoms, including, for example, but not limited to: hexane, heptane, octane, and the like.
As used herein, the term "C 1 ～C 12 By haloalkane "is meant a straight or branched haloalkane having 1 to 12 carbon atoms, including, for example, but not limited to: methylene chloride, 1, 2-dichloroethane, 1, 2-tetrachloroethane and the like;
as used herein, the term "C 1 -C 4 Alkyl "means a straight chain or having 1 to 4 carbon atomsBranched alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
As used herein, the term "C 1 -C 8 Alkyl "refers to straight or branched chain alkyl groups having 1 to 8 carbon atoms, including, for example, but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl. Tertiary butyl, pentyl, hexyl and the like.
As used herein, the term "C 5 -C 8 Cycloalkyl "refers to cycloalkyl groups having 5-8 carbon atoms, including, for example, but not limited to: cyclopentyl, cyclohexyl, cycloheptyl, and the like.
As used herein, the term "halogenated" or "halo" refers to substitution with a halogen (e.g., fluorine, chlorine, bromine, iodine).
Low-carbon olefin
The lower olefins used in the present application may be C 2 -C 4 Olefins, for example, ethylene, propylene, or combinations thereof.
Complex and preparation method thereof
The complexes used for the polymerization reaction herein can be prepared by complexing the ligand compound I with a divalent metal salt in an inert solvent.
The ligand compound I has the structure as follows:
in the method, in the process of the application,
Y 1 respectively is hydrogen, C 1 -C 8 Alkyl or C 1 -C 8 Haloalkyl, unsubstituted or substituted phenyl;
Y 2 CR respectively 4 R 5 、NR 6 O or S, R 4 、R 5 、R 6 Each independently H, C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group;
or Y 1 And Y is equal to 2 And the C-C bonds co-joined to each other form together an unsubstituted orSubstituted 5-12 membered rings; preferably, Y 1 And Y 2 C-C bonds which may be co-linked with both to form unsubstituted or substituted C 6 -C 8 An membered ring;
is an unsubstituted or substituted 5-7 membered monocyclic ring, or a bicyclic or tricyclic group containing said 5-7 membered monocyclic ring, wherein the 5-7 membered monocyclic ring contains 1-3N, O or S atoms and contains at least one N;
Y 3 is one or more optionally substituted groups located on the 5-7 membered monocyclic ring or a bicyclic or tricyclic group containing the 5-7 membered monocyclic ring, each Y 3 Independently hydrogen, C 1 -C 8 Alkyl or C 1 -C 8 Haloalkyl, C 5 -C 8 Cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl;
z is selected from the group consisting of: c (C) 1 -C 8 Alkyl, C 1 -C 8 Haloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl;
wherein the term "substituted" as defined in the above definitions means that the group has 1 to 5 substituents selected from the group consisting of: c (C) 1 -C 4 Alkyl and C 1 -C 4 Haloalkyl, halogen, nitro, cyano, CF 3 、-O-R 1 、-N(R 2 ) 2 、-Si(R 3 ) 3 、-CH 2 -O-R 8 、-SR 9 、-CH 2 -S-R 10 、-CH-(R 10 ) 2 Or phenyl which is unsubstituted or substituted by 1 to 5 substituents selected from the group consisting of: c (C) 1 -C 4 Alkyl and C 1 -C 4 Haloalkyl, wherein R 1 、R 2 、R 3 Each independently is C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group; and R is 8 、R 9 And R is 10 Respectively C 1 -C 8 Alkyl or phenyl.
The divalent metal salt may be a divalent nickel metal salt, for example, including but not limited toIn the following steps: niCl 2 、NiBr 2 、NiI 2 、(DME)NiBr 2 、(DME)NiCl 2 、(DME)NiI 2 Etc.
The inert solvent may be any conventionally used solvent which does not affect the progress of the reaction, including alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ethers, esters, nitrile solvents, preferably halogenated hydrocarbon solvents, among which preferred results are obtained in halogenated hydrocarbon and lipid solvents, preferably dichloromethane, 1, 2-dichloroethane, ethyl acetate, tetrahydrofuran.
For example, the complex suitable for the process or preparation method of the present application has a structure represented by the following formula (II):
wherein X is independently halogen, C 1 -C 4 Alkyl, C 2 -C 6 Alkenyl, allyl - OAc、 - OTf or benzyl; the C is 1 -C 4 Alkyl is preferably methyl; the halogen is preferably bromine, chlorine or iodine.
When X is a hydrocarbyl group, such as methyl or benzyl, this catalytic action is often achieved by reacting the corresponding chloride or bromide with a methyl Grignard reagent or a benzyl Grignard reagent under conventional reaction conditions similar to those of the reaction, and whether X in the nickel complex (II) is a halogen or a hydrocarbyl group or any other group which can coordinate to nickel, such as an oxygen-containing compound, as long as the complex can form a Ni-C bond or a Ni-H bond under the action of an aluminum alkyl, these compounds all have the same active center during the catalytic ethylene polymerization and thus exhibit the same or similar properties.
For a specific synthetic method of the complex, reference is made to CN201410555078X.
The complex can be used for catalyzing low carbon (C) after being separated and purified after being coordinated by a ligand compound I and a metal precursor 2 -C 4 ) Polymerization of olefins, or direct catalysis of low carbon (C) 2 -C 4 ) The polymerization of olefins, both modes have no significant effect on the polymerization results and product properties in the case of the same remaining polymerization processes.
Process for preparing base oils (lubricating base oils)
The preparation method or process of the base oil is that under the action of selecting one or a mixture of a plurality of the complexes, the base oil is prepared by low carbon (C 2 -C 4 ) The mixture of one or more of olefins (including ethylene and propylene) is used as a raw material, and the synthetic base oil LPE with high viscosity quality is obtained through the procedures of polymerization, hydrogenation, rectification and the like.
The preparation method comprises the following steps:
(1) Polymerization: sequentially adding a first solvent and an aluminum alkyl a to a tubular reactor or a tank reactor at a set polymerization temperature, and continuously introducing a low carbon (e.g., C 2 -C 4 ) Olefins (e.g., refined olefins) (e.g., ethylene, propylene, or mixtures thereof) are then polymerized in batches by adding the catalyst solution to the reactor to form the pre-hydrogenated base oil.
The catalyst solution may be added in two, three or more batches.
The catalyst solution is added in portions at fixed or non-fixed intervals throughout the polymerization reaction until the reaction is completed.
In the polymerization process, the polymerization temperature can be controlled between 10 ℃ and 60 ℃, the polymerization pressure is controlled between 0.7 MPa and 2.0MPa, the reaction is stopped after the polymerization is carried out for 1 to 24 hours, and the materials are put into the next process.
In the polymerization step, the aluminum alkyl a is selected from the group consisting of: triethylaluminum, trimethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, or a combination thereof; more preferred are triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride.
In the polymerization process, the first solvent is alkane (such as C 6 ～C 12 An alkane of toluene, xylene or halogenated alkane; preferably, the alkanes are hexane and white oil; the halogenated alkane may preferably be dichloromethane, 1, 2-dichloroethane or 1, 2-tetrachloroethane.
In the polymerization step, the catalyst solution is a solution of the complex and the aluminum alkyl b in a second solvent; wherein, the molar ratio of the aluminum alkyl b to the complex is as follows: 1 to 100/1; the aluminum alkyl b is selected from the following group: triethylaluminum, triisobutylaluminum, diethylaluminum chloride, or a combination thereof; the second solvent is selected from the group consisting of: toluene, halogenated C 6 ～C 12 Is an alkane of (a).
In the polymerization process, the structure of the reactor has a certain influence on the polymerization efficiency, but the property of a polymerization product is not influenced, namely, the structure of the kettle body possibly influences the yield, but qualified base oil can be obtained. The processes provided herein are applicable to both tank reactors and tubular reactors (e.g., loop). The kettle type reactor can be independently used, and a plurality of kettle type reactors can be used in series, depending on specific output requirements.
(2) Hydrogenation: and (3) carrying out hydrogenation reaction on the pre-hydrogenation base oil obtained in the polymerization step through a fixed bed or kettle type hydrogenation reactor, thereby obtaining the hydrogenation base oil.
Wherein, the fixed bed hydrogenation process can be as follows:
hydrogenation temperature: 220-300 ℃;
hydrogenation pressure: 2.0 to 4.0MPa;
airspeed: 1.5 to 2.5 hours -1 ；
Hydrogen to oil ratio: 200-300 parts.
Wherein, the kettle type processing technology can be as follows:
hydrogenation temperature: 100-200 ℃;
hydrogenation pressure: 2.0 to 6.0MPa;
concentration of oil: 0.2-1.0 Kg/L.
In the hydrogenation step, the catalyst used for hydrogenation is a conventional hydrogenation catalyst, preferably a supported hydrogenation catalyst used in petrochemical industry, such as DC series products, RIW series, supported raney nickel catalyst, alnico hydrogenation catalyst, palladium-carbon catalyst, etc., but not limited to the above-mentioned hydrogenation catalysts.
In the hydrogenation step, the solvent used in the hydrogenation reaction is common hydrogenation solvent, including alkane and alkane mixture, such as white oil, petroleum ether, hexane, etc.; hexane is preferred; the hexane may comprise n-hexane, isohexane, cyclohexane or a mixture of hexane.
(3) And (3) rectifying: adding carclazyte into the reaction mixture obtained in the previous step, filtering, and carrying out molecular rectification on the filtrate by negative pressure so as to obtain the base oil with high viscosity grade.
The negative pressure rectification can use a conventional rectifying tower, molecular distillation equipment or any device available in the market and capable of realizing liquid fractionation.
Preferred process parameters when using molecular rectification apparatus are as follows: rectification temperature: 300-350 ℃; and (3) rectification absolute pressure: 1 to 700Pa;
in order to ensure long-term stable operation of the process, after the process (1) is finished, the quenching reaction can be selected firstly and then the process (2) is carried out, the quenching mode can be selected according to factory environment, requirements and the like, a small amount of quenching agent is directly added into the materials finished in the process (1), or the liquid generated in the process (1) is transferred to another kettle and then is contacted with the quenching agent, conventional silica gel, diatomite, clay, water, steam and the like can be used as the quenching agent, the quenching agent can be used singly or in a mixture of a plurality of types, the dosage can be adjusted according to the requirements, the quenching catalyst can be used for stopping polymerization, and more quenching agents can be added without influencing the quenching effect, but the burden of the subsequent process is possibly increased, or more waste residues are caused;
in addition, in order to ensure the quality, chromaticity and process stability of the oil, some auxiliary processes such as solvent recovery process, product decolorization, filtration, etc. can be added. All of these auxiliary steps may be used, or one or more of them may be used as needed; the auxiliary procedures can be used in different process links according to the needs;
the hydrogenation of the oil product in the working procedure (2) can be carried out before the working procedure (3) or after the fractionation and cutting of the oil product are finished according to working conditions and product requirements, so that the quality of the product, including the performances of viscosity, viscosity index and the like, is not influenced, but the cost of the product is possibly influenced.
The process flow diagram for the direct polymerization of ethylene to make base oils is now described in connection with figure 1 as follows:
(i) Polymerization: sequentially adding a first solvent and aluminum alkyl a into a tubular reactor or a kettle reactor at a set polymerization temperature, continuously introducing refined ethylene at the set polymerization pressure, adding a catalyst solution into the reactor in batches for polymerization reaction, and thus forming the base oil before hydrogenation;
controlling the polymerization temperature at 10-60 ℃, the polymerization pressure at 0.7-2.0 MPa, the polymerization time at 1-24 hours, stopping the reaction, and putting the materials to the next working procedure.
The first solvent may be selected from the group consisting of: c (C) 6 ～C 12 Is an alkane of (a); toluene, xylene; halogenated C 1 ～C 12 Is an alkane of (a); preferably selected from the group consisting of: hexane, dichloromethane, 1, 2-dichloroethane, 1, 2-tetrachloroethane.
The amount of the first solvent used depends on the reaction vessel and the reaction yield, and it is generally preferable to achieve a final product concentration of not more than 70% (v/v).
The alkyl aluminum a is selected from the following group: triethylaluminum, trimethylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride; triethylaluminum is preferred.
The catalyst solution is a solution formed by a complex and aluminum alkyl b in a second solvent; the pre-reaction of the complex and the alkyl aluminum b at room temperature before being added into the reaction system is to control the concentration of the catalytic species and the stability of the polymerization reactionAnd an important step of product quality, in which the selection of the alkyl aluminum b and the second solvent is important to ensure that the complex forms a true active species while ensuring the stability of the active species in the absence of olefin, wherein the alkyl aluminum b in the catalyst solution may be the same as or different from the alkyl aluminum a added to the polymerization reactor, and is triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, or a mixture of two or more thereof; the molar ratio of the aluminum alkyl b to the complex is 1-100/1; the second solvent is selected from toluene or halogenated C 6 ～C 12 Is an alkane of (a); the concentration of the catalyst solution is preferably 0.01 to 0.5M.
The molar ratio of the total aluminum amount and the complex in the final polymerization reaction system is preferably 100 to 800/1.
The reaction temperature is preferably 40 to 60 ℃.
The reaction pressure is preferably 0.7 to 1.0MPa.
The reaction time is preferably 6 to 10 hours.
(ii) Post-treatment: adding a quenching agent into the mixture after the reaction in the steps, filtering, recovering the solvent, and decoloring to obtain clear and transparent pre-hydrogenation base oil.
The quenching agent comprises diatomite, alcohol, silica gel powder, water, preferably alcohol;
the molar ratio of the quencher (e.g. alcohol)/alkyl aluminum=2 to 4.
(iii) Hydrogenation: and (3) carrying out hydrogenation reaction on the pre-hydrogenation base oil obtained in the steps through a fixed bed or kettle type hydrogenation reactor to obtain hydrogenated base oil.
The fixed bed hydrogenation process can be as follows:
hydrogenation catalyst: the supported hydrogenation catalyst used in petrochemical industry can reach ideal hydrogenation effect, such as DC series products, RIW series, supported Raney nickel catalyst, aluminum nickel alloy hydrogenation catalyst, palladium carbon catalyst and the like.
Hydrogenation temperature: 220-300 ℃;
hydrogenation pressure: 2.0 to 4.0MPa;
airspeed: 1.5 to 2.5 hours -1 ；
Hydrogen to oil ratio: 200-300 parts.
The kettle type processing technology can be as follows:
hydrogenation catalyst: the supported hydrogenation catalyst used in petrochemical industry can reach ideal hydrogenation effect, such as DC series products, RIW series, supported Raney nickel catalyst, aluminum nickel alloy hydrogenation catalyst, palladium carbon catalyst and the like.
Hydrogenation temperature: 100-200 ℃;
hydrogenation pressure: 2.0 to 6.0MPa;
concentration of oil: 0.2-1.0 Kg/L.
Solvent: hexane
(iv) And (3) negative pressure rectification: and (3) carrying out molecular distillation on the hydrogenated base oil obtained in the step (iii) through negative pressure distillation equipment, thereby obtaining the base oil with high viscosity grade.
The technological parameters of the molecular distillation can be as follows: 300-350 ℃; and (3) rectification absolute pressure: 1 to 700Pa.
Base oil (lubricating base oil)
The application can prepare the material with the kinematic viscosity of 100-300 mm at 100 ℃ according to the method or the process 2 High viscosity base oils per second (ASTMD 445-15 a). Wherein the viscosity index (VI value) of the high-viscosity base oil is higher than 170, the NOACK evaporation loss is lower than 1%, and the pour point is lower than-20 ℃; the base oils prepared typically have sulfur and nitrogen contents of less than 5ppm, various metals of less than 5ppm, other impurities of less than 5ppm, acid number of less than 0.01mg KOH/g, water content of less than 50ppm, ASTM color<0.5。
The main advantages of the application include:
(1) Using low carbon (C) 2 -C 4 ) Olefins (including ethylene, propylene, or mixtures thereof) are used as feedstock to directly prepare the fully synthetic base oil. Because the raw materials are all polymer-grade olefin, the prepared total synthetic base oil is clean, the sulfur and nitrogen contents are generally lower than 5ppm, the contents of various metals are all lower than 5ppm, the contents of other impurities are lower than 5ppm, the acid value is lower than 0.01mg KOH/g, the viscosity index is higher than 170, the pour point is lower than-20 ℃, and the water content is lowAt 50ppm, ASTM color<0.5。
In addition, C is adopted in the process route 4 The internal olefin is used as a raw material, so that the raw material source is sufficient and low in cost; avoid the preparation and separation of C by oligomerization of ethylene 8 -C 12 Alpha-olefin process of (2), especially when ethylene is used as feedstock, the conversion of ethylene into oil is efficient>80 percent) can be higher than 95 percent under the process optimization condition, and greatly reduces the cost of the base oil.
(2) The process of the application is easy to prepare high viscosity synthetic oil through process adjustment.
(3) The application has safe process and small corrosion to equipment in the production process. Compared with the traditional AlCl 3 +alcohol, BF 3 The +alcohol cation polymerization production mode is different, the complex addition amount in the process is less (less than or equal to 0.01%), the activity is high, the cocatalyst is easy to remove, and the system does not contain chloride ions which are strong in corrosiveness and difficult to remove.
(4) The application has simple post-treatment process and less waste water and waste residue. The application has simple post-treatment process, does not need water washing or alkali washing or adding a large amount of clay for adsorption, and can obtain the oil with low acid value and low impurity content only through filtration and fixed bed adsorption.
(5) Gel Permeation Chromatography (GPC) analysis shows that the base oil obtained in step (1) of the present application is a high viscosity base oil, and that the molecular weight distribution of the high viscosity base oil is narrow, typically less than 1.8 (e.g., as shown in fig. 2, 3), and that whether hydrogenated or not does not alter the GPC results of the oil. The base oil produced by the method can be directly used as the base oil of synthetic lubricating oil, and is mixed with the required additive according to the required proportion (base oil/additive: 100-70/0-30) according to different purposes and then used as a final product; the high-viscosity base oil produced by the process of the application can be mixed with other base oils with different viscosities according to a specific proportion as required, and mixed with the required additives according to a required proportion and used as a final product; it may also be mixed with one or more of group II, group III, group IV and group V oils (according to the American Petroleum Institute (API) classification) and used as a final product in the desired proportions.
The application is further described below in conjunction with the specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated. The materials or instruments used in the examples of the present application are commercially available unless otherwise specified.
In the examples, complex A or complex B will be described as an example, but it is to be understood that the practice of the process of the application is not limited to the use of these two complexes as catalysts:
example 1
Into a 20L reaction kettle, 10L of methylene dichloride and 300mmol of triethylaluminum are added at the temperature of 40-50 ℃, ethylene is continuously introduced under the polymerization pressure of 1.0-1.2 MPa in the reaction kettle, and 100mL (Et 3 Al/Complex A:30/l (molar ratio), solvent: hexane, concentration of 0.01M) was added to the reaction vessel to start polymerization; after a polymerization time of 6 hours, the reaction was stopped and ethylene was consumed at 3.3Kg. 600mmol of ethanol is added into the obtained reaction solution, the reaction solution is filtered, decolored and the solvent is removed under negative pressure, so that 3.0Kg of clear and transparent base oil before hydrogenation is obtained, the yield is 91%, and the ethylene conversion rate is 98.5%.
The obtained base oil before hydrogenation is hydrogenated by a fixed bed, and the hydrogenation catalyst is as follows: supported catalyst RIW-2; hydrogenation temperature: 220 ℃; hydrogenation pressure: 4.0MPa; airspeed: 2.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Hydrogen to oil ratio: 300, obtaining hydrogenated base oil; and then carrying out molecular distillation on the hydrogenated base oil by negative pressure, wherein the absolute pressure of the system is 50Pa, the heating temperature is 300 ℃, and the clear and transparent base oil LPE100 with high viscosity grade is obtained, and the molecular weight distribution are shown in figure 2. The resulting high viscosityThe basic physicochemical properties of the grade base oil LPE100 are as follows:
example 2
In a 20L reaction kettle, 10L of methylene dichloride and 300mmol of triethylaluminum are added at 50-60 ℃, 300g of propylene and ethylene are introduced under the polymerization pressure of 0.8-1.0 MPa in the reaction kettle, and 100mL ((iBu) of catalyst solution is obtained 3 Al/Et 3 Al) (1/1)/complex B:40/l (molar ratio), solvent: hexane, concentration of 0.01M) was added to the reaction vessel to start polymerization, and after 10 hours of polymerization time, the reaction was stopped, and ethylene consumed 3.2Kg. 600mmol of ethanol is added to the obtained reaction solution, decolorization and solvent removal are carried out, so that 3.2Kg of clear and transparent base oil before hydrogenation is obtained, the yield is 91.5%, and the conversion rate is 99%.
The obtained base oil before hydrogenation is hydrogenated by a fixed bed, and the hydrogenation catalyst is as follows: supported catalyst RIW-2; hydrogenation temperature: 220 ℃; hydrogenation pressure: 4.0MPa; airspeed: 2.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Hydrogen to oil ratio: 300, obtaining hydrogenated base oil; and then carrying out molecular distillation on the hydrogenated base oil by negative pressure, wherein the absolute pressure of the system is 50Pa, the heating temperature is 300 ℃, and the clear and transparent base oil LPE120 with high viscosity grade is obtained, and the molecular weight distribution of the clear and transparent base oil LPE are shown in figure 3. The basic physicochemical properties of the resulting high viscosity grade base oil LPE120 are shown in the following table:
example 3
Adding 10L of 1, 2-tetrachloroethane and 300mmol of diethyl aluminum chloride into a 20L reaction kettle at 20-30 ℃, controlling polymerization pressure in the reaction kettle to be 0.7-0.8 MPa, and introducing propylene in batches100mL of the catalyst solution (Et 3 Al/Complex A:50/l (molar ratio), solvent: hexane, concentration of 0.01M) is added into the reaction kettle to start polymerization; after a polymerization time of 4 hours, the reaction was stopped and propylene was consumed at 3.2Kg. 600mmol of ethanol was added to the reaction mixture, followed by filtration, chromatography for decolorization and solvent removal to give 2.9Kg of clear and transparent base oil before hydrogenation in a yield of 91.2% and a propylene conversion of 98.6%.
The obtained base oil before hydrogenation is hydrogenated by a fixed bed, and the hydrogenation catalyst is as follows: supported catalyst RIW-2; hydrogenation temperature: 220 ℃; hydrogenation pressure: 4.0MPa; airspeed: 2.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Hydrogen to oil ratio: 300, obtaining hydrogenated base oil; and then carrying out molecular distillation on the hydrogenated base oil by negative pressure, wherein the absolute pressure of the system is 50Pa, and the heating temperature is 300 ℃, so as to obtain clear and transparent base oil LPE140 with high viscosity grade.
The basic physicochemical properties of the resulting high viscosity grade base oil LPE140 are shown in the following table:
example 4
Other conditions were the same as in example 1, except that the temperature was changed to 50 to 60℃to obtain 3.1Kg of high viscosity grade base oil LPE160. The basic physicochemical properties of the resulting high viscosity grade base oil LPE160 are shown in the following table:
example 5
Other conditions were the same as in example 1, except that the solvent was changed to heptane, to obtain 2.92Kg of high viscosity grade base oil LPE220. The basic physicochemical properties of the resulting high viscosity grade base oil LPE220 are shown in the following table:
/>
example 6
Other conditions were the same as in example 1, except that the pressure was changed to 1.6 to 1.7MPa, to obtain 2.9Kg of high viscosity grade base oil LPE240. The basic physicochemical properties of the resulting high viscosity grade base oil LPE240 are shown in the following table:
all documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. A process method for directly preparing base oil by polymerization of low-carbon olefin is characterized by comprising the following steps:
(1) Polymerization: sequentially adding a first solvent and aluminum alkyl a into a tubular reactor or a kettle reactor at a set polymerization temperature, continuously introducing low-carbon olefin at the set polymerization pressure, and then adding a catalyst solution into the reactor in batches for polymerization reaction to form the base oil before hydrogenation; wherein the low-carbon olefin is ethylene, the polymerization temperature is 40-60 ℃, and the polymerization pressure is 1.0-1.5 MPa;
the time of the polymerization reaction is 1-24 hours;
the aluminum alkyl a is selected from the group consisting of: triethylaluminum, trimethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, or a combination thereof;
the first solvent is selected from the group consisting of: c (C) 6 ～C 12 Alkane, white oil, toluene, xylene, halogenated C 1 ～C 12 Is an alkane of (a);
the catalyst solution is a solution formed by a complex and aluminum alkyl b in a second solvent; wherein, the molar ratio of the aluminum alkyl b to the complex is as follows: 1 to 100/1;
the aluminum alkyl b is selected from the following group: triethylaluminum, triisobutylaluminum, diethylaluminum chloride, or a combination thereof;
the second solvent is selected from the group consisting of: toluene, halogenated C 1 ～C 12 Is an alkane of (a);
the complex is prepared by coordination of a ligand compound I and divalent metal salt; wherein the complex is a combination of a ligand compound I and a divalent metal salt, or the complex is a complex shown as II:
in the method, in the process of the application,
Y 1 is unsubstituted or substituted phenyl, said substituents meaning groups having 1 to 5 substituents selected from the group consisting of: halogen, -O-R 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is a C1 alkyl group;
Y 2 is O;is an unsubstituted or substituted 5 membered monocyclic ring, or a bicyclic group containing said 5 membered monocyclic ring;
Y 3 is one or more optionally substituted groups located on the 5-membered monocyclic ring, or a bicyclic group containing the 5-membered monocyclic ring, Y 3 Is C 1 -C 8 An alkyl group;
z is unsubstituted or substituted phenyl; the substituent groups have 1 to 5 substituents selected from halogen or C 1 -C 4 Substituents of alkyl:
the divalent metal salt is divalent nickel metal salt;
wherein X is independently halogen, C 1 -C 4 Alkyl, C 2 -C 6 Alkenyl and allyl)、 - OAc、 - OTf or benzyl;
(2) Hydrogenation: the base oil before hydrogenation is subjected to hydrogenation reaction through a fixed bed hydrogenation reactor, so that hydrogenated base oil is obtained; wherein, the fixed bed hydrogenation reaction conditions are as follows:
hydrogenation temperature: 220-300 ℃;
hydrogenation pressure: 2.0 to 4.0MPa;
airspeed: 1.5 to 2.5. 2.5h -1 ；
Hydrogen to oil ratio: 200-300 parts;
(3) And (3) rectifying: molecular rectification is carried out on the hydrogenated base oil through negative pressure, so that base oil with high viscosity grade is obtained; wherein, the technological parameters of the negative pressure rectification are as follows: rectification temperature: 300-350 ℃; and (3) rectification absolute pressure: 1-700 and Pa.
2. The process of claim 1 wherein said complex is selected from the group consisting of:
。
3. the process of claim 1 wherein in step (1), said aluminum alkyl a is selected from the group consisting of: triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride.
4. The process of claim 1, further comprising a solvent recovery and purification step.
5. The process of claim 1 wherein the sequence of hydrogenation and rectification steps is interchangeable.
6. The process according to claim 1, wherein in the step (1), after the polymerization reaction is completed, the method further comprises a post-treatment step of: adding a quenching agent into the mixture after the polymerization reaction is completed, and filtering, recovering the solvent and decoloring to obtain clear and transparent pre-hydrogenation base oil; wherein the quencher is selected from the group consisting of: diatomaceous earth, alcohol, silica gel powder, water, or combinations thereof.
7. The process of claim 1 wherein said high viscosity grade base oil has a molecular weight distribution of less than 2.0.
8. The process of claim 1 wherein said high viscosity grade base oil has a molecular weight distribution of less than 1.8.
9. The process of claim 1 wherein said high viscosity grade base oil has a kinematic viscosity of 100 to 300mm at 100 ℃ 2 And/s, an acid number of less than 0.01mg KOH/g, wherein the NOACK evaporation loss is less than 1%, the pour point is less than-20 ℃, and the viscosity index is higher than 170.
10. Process according to the preceding claim, wherein the high viscosity grade base oil prepared is used in mechanical lubricating oils.
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