EP0413795A1 - Synthetic lube composition and process. - Google Patents
Synthetic lube composition and process.Info
- Publication number
- EP0413795A1 EP0413795A1 EP90904065A EP90904065A EP0413795A1 EP 0413795 A1 EP0413795 A1 EP 0413795A1 EP 90904065 A EP90904065 A EP 90904065A EP 90904065 A EP90904065 A EP 90904065A EP 0413795 A1 EP0413795 A1 EP 0413795A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant
- composition
- catalyst
- hydrocarbons
- oligomer
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 39
- 230000008569 process Effects 0.000 title claims description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000000314 lubricant Substances 0.000 claims abstract description 63
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 claims abstract description 36
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 36
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000029936 alkylation Effects 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000010687 lubricating oil Substances 0.000 claims abstract description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 5
- 239000000539 dimer Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 24
- 239000006227 byproduct Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000002168 alkylating agent Chemical class 0.000 claims description 10
- 229940100198 alkylating agent Drugs 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 230000002152 alkylating effect Effects 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 18
- 230000001050 lubricating effect Effects 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 50
- 239000000463 material Substances 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- -1 vinylidenyl structure Chemical group 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- UZEDIBTVIIJELN-UHFFFAOYSA-N chromium(2+) Chemical class [Cr+2] UZEDIBTVIIJELN-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003606 oligomerizing effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- UVLKUUBSZXVVDZ-HTXNQAPBSA-N (e)-icos-9-ene Chemical compound CCCCCCCCCC\C=C\CCCCCCCC UVLKUUBSZXVVDZ-HTXNQAPBSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- NEAFLGWVOVUKRO-UHFFFAOYSA-N 9-methylidenenonadecane Chemical compound CCCCCCCCCCC(=C)CCCCCCCC NEAFLGWVOVUKRO-UHFFFAOYSA-N 0.000 description 1
- VAEODIOQYMCRMF-UHFFFAOYSA-N 9-methylnonadec-9-ene Chemical compound CCCCCCCCCC=C(C)CCCCCCCC VAEODIOQYMCRMF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- WDNIVTZNAPEMHF-UHFFFAOYSA-N acetic acid;chromium Chemical compound [Cr].CC(O)=O.CC(O)=O WDNIVTZNAPEMHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910001683 gmelinite Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GHYZNGUAPGNBKZ-UHFFFAOYSA-N icos-8-ene Chemical compound CCCCCCCCCCCC=CCCCCCCC GHYZNGUAPGNBKZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
-
- 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
- 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
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
Definitions
- This invention relates to novel compositions prepared from synthetic lubricants by reaction with olefins and to the process for their production.
- the invention particularly pertains to the modification of a high viscosity index synthetic lubricant oligomer fraction employing low molecular weight by-product oligomer fractions as reactant.
- the modified synthetic lubricants are themselves useful, inter alia, as lubricants with improved thermal stability.
- One characteristic of the molecular structure of 1-alkene oligomers that has been found to correlate very well with improved lubricant properties in commercial synthetic lubricants is the ratio of methyl to methylene groups in the oligomer.
- the ratio is called the branch ratio and is calculated from infra red data as discussed in "Standard Hydrocarbons of High Molecular Weight", Analytical Chemistry, Vol.25, no.10, p.1466 (1953). Viscosity index has been found to increase with lower branch ratio.
- branch ratio is calculated from infra red data as discussed in "Standard Hydrocarbons of High Molecular Weight", Analytical Chemistry, Vol.25, no.10, p.1466 (1953). Viscosity index has been found to increase with lower branch ratio.
- oligomeric liquid lubricants exhibiting very low branch ratios have not been synthesized from 1-alkenes.
- oligomers prepared from 1-decene by either cationic polymerization or Ziegler catalyst polymerization have branch ratios of greater than 0.20.
- Shubkin, Ind. Eng.Chem. Prod. Res. Dev. 1980, 19, 15-19, provides an explanation for the apparently limiting value for branch ratio based on a cationic polymerization reaction mechanism involving rearrangement to produce branching.
- Other explanations suggest isomerization of the olefinic group in the one position to produce an internal olefin as the cause for branching.
- U.S.Patent 4,282,392 to Cupples et al. discloses an alpha-olefin oligomer synthetic lubricant having an improved viscosity-volatility relationship and containing a high proportion of tetramer and pentamer via a hydrogenation process that effects skeletal rearrangement and iso eric composition.
- the composition claimed is a trimer to tetramer ratio no higher than one to one. The branch ratio is not disclosed.
- HVI-PAO novel lubricant compositions
- the HVI-PAO lubricants are made by a process which comprises contacting C ⁇ -C ⁇ Q 1-alkene feedstock with reduced valence state chromium oxide catalyst on porous silica support under oligomerizing conditions in an oligomerization zone whereby high viscosity, high VI liquid hydrocarbon lubricant is produced having branch ratios less than 0.19 and pour point below -15°C
- the process is distinctive in that little isomerization of the olefinic bond occurs compared to known oligomerization methods to produce polyalpha-olefins using Lewis acid catalyst.
- Lubricants produced by the process cover the full range of lubricant viscosities and exhibit a remarkably high viscosity index (VI) and low pour point even at high viscosity.
- the as-synthesized HVI-PAO oligomer has a preponderance of terminal olefinic unsaturation.
- the HVI-PAO oligomer is hydrogenated to improve stability for lubricant applications. Those modifications to HVI-PAO oligoraers that result in improved thermal stability are particularly preferred.
- alpha-olefin dimer ⁇ containing olefinic unsaturation can be separated from the oligomerization reaction.
- the composition of the dimer mixture conforms to the unique specificity of the oligomerization reaction in that little double bond isomerization is found and shows a low branch ratio. Separation of the dimer, representing non-lube range molecular weight material, is necessitated to control product volatility and viscosity.
- the non-lube range dimer fraction by-product yield increases in proportion to that lowering in average molecular weight of the oligomerization product.
- the increase in dimer by-product yield represents a substantial economic burden on the overall process to produce useful lower viscosity lubricant.
- a method for improving the thermal stability of synthetic lube produced by the oligomerization of a 1-alkene comprises reacting the oligomer with an olefin.
- the reaction which is believed to proceed mainly by alkylation with some side reactions such as cracking, isomerization and polymerization, is carried out in the presence of an alkylation catalyst under conditions appropriate for alkylation.
- a preferred olefin for reaction with the lube oligomer is the lower molecular weight, non-lubricant olefin produced in the course of. the oligomerization of the alpha-olefin starting material.
- Using these lower molecular weight materials in this way not only improves the thermal stability of the final lube products but also increases the product yield and olefin utilization, thus avoiding the economic penalty attached to the production of the lower viscosity range lubricants.
- the lower molecular weight non-lubricant range olefinic hydrocarbons produced in the course of the oligomerization of 1-alkenes are used to upgrade the lube range oligomer.
- the reaction is carried out using acidic catalyst.
- Effective acidic catalysts comprise alkylation catalysts, preferably the open-pore catalyst such as those derived from fluorided alumina.
- the composition of the present invention is polymeric residue of linear C 6 -C 20 1-alkenes, which has at least one higher alkyl (C ⁇ -C ⁇ ) Drancn P er oligomer molecule.
- the hydrocarbon oligomer generally contains from 30 to 1300 carbon atoms per molecule.
- the novel composition has a methyl to methylene branch ratio of less than 0.19 and pour point below -15°C
- the preferred process for the conversion of the alpha-olefins to the desired thermally stable, high viscosity index lubricant product comprises: contacting - to C2 Q alpha-olefin feedstock, or mixtures thereof, under oligomerization conditions with a reduced valence state Group VIB metal catalyst on porous support whereby an oligomerization product mixture is produced containing oligomers comprising olefinic lubricant range hydrocarbons and olefinic non-lubricant range hydrocarbon by-product; separating the lubricant and non-lubricant hydrocarbons and hydrogenating the lubricant range hydrocarbons; contacting the hydrogenated hydrocarbons and the olefinic by-product hydrocarbons as alkylating agent in an alkylation zone under alkylating conditions with acidic catalyst whereby alkylated lubricant range hydrocarbons are produced.
- Figure 1 shows the relationship between degree of alkylation and viscosity loss for modified HVI-PAO.
- Figure 2 shows the relationship between viscosity and viscosity index for HVI-PAO oligomer and modified HVI-PAO oligomer.
- synthetic hydrocarbon lubricants are modified by reaction with alkenes including the unique olefin dimers produced as by-product in the oligomerization reaction that produces the synthetic lubricant.
- the alkenes which can be used to react with HVI-PAO oligomers as described herein include linear or branched alkenes but, in particular, 1-alkenes and the olefinic dimer by-product of the HVI-PAO oligomerization reaction.
- Preferred 1-alkenes for reaction with HVI-PAO oligomers include those olefins containing from 6 to 14 carbon atoms such as 1-hexene, 1-octene, 1-decene, 1-dodecene and
- 1-tetradecene and branched chain isomers such as 4-methyl-l-pentene.
- Particularly preferred 1-alkenes are the Cg to C,Q alpha-olefins, e.g., 1-octene, 1-decene and the olefin dimers produced in the oligomerization process for producing the initial lube range materials.
- the oligomerization reaction is carried out by the oligomerization of 1-alkenes in contact with reduced metal catalysts, preferably reduced chromium oxide on a silica support.
- a characteristic of the novel oligomerization reaction from which the by-product dimers used as alkylating agent in the present invention are produced is the production of mixtures of dialkyl vinylidenic and 1,2 dialkyl or trialkyl mono-olefin oligomers, or HVT-PA0 oligomers, as determined by infra-red and NMR analysis.
- the HVI-PAO oligomers have the following regular head-to-tail structure where n is preferably 0 to 17, terminating in olefinic unsaturation:
- the HVI-PAO process produces a surprisingly simpler and useful dimer compared to the dimer produced by 1-alkene oligomerization with BF, or AlCl, as commercially practiced.
- the by-product dimer from 1-decene oligomerization according to the
- HVI-PAO process which can be used as alkylating olefin in the present invention, has been found to contain three major components, as determined by gas chromatography (GC). Based on -13 NMR analysis, the unhydrogenated components were found to be 8-eicosene,
- Olefins suitable for use as starting material in the preparation of olefinic HVI-PAO oligomers and the by-product dimer used as starting material in the present invention include those olefins containing from 6 to 14 carbon atoms such as 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene and branched chain isomers such as 4-methyl-l-pentene.
- a preferred 1-alkene is 1-decene.
- olefin-containing refinery feedstocks or effluents are also suitable for use. However, the olefins used in this invention are preferably alpha olefinic as for example 1-octene to 1-dodecene and more preferably 1-decene, or mixtures of such olefins.
- the lube range HVI-PAO oligomers of alpha-olefins used in this invention have a low branch ratio of less than 0.19 and superior lubricating properties compared to the alpha-olefin oligomers with a high branch ratio, as produced in all known commercial methods.
- This class of unsaturated HVI-PAO alpha-olefin oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alpha-olefins are not isomerized. These reactions include alpha-olefin oligomerization by supported metal oxide catalysts, such as Cr compounds on silica or other supported IUPAC Periodic Table Group VIB compounds.
- the catalyst most preferred is a lower valence Group VIB metal oxide on an inert support.
- Preferred supports include silica, alumina, titania, silica alumina, magnesia and the like.
- the support material binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 angstroms are preferred.
- the support material usually has high surface area and
- the support should have large average pore openings of at least 40 x 10 mm, with an average pore opening of
- the supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for example, ethanol,methanol, or acetic acid.
- the solid catalyst precursor is then dried and calcined at 200 to 900°C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, CO, H 2 , NH 3 , H 2 S, CS 2 , CH 3 SCH 3 , CHjSSCH j ,metal alkyl containing compounds such as R ⁇ Al, R,B,R 2 Mg, RLi, R 2 Zn, where R is alkyl, alkoxy, aryl and the like.
- the resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to 250°C at a pressure of 10.1 kPa (0.1 atmosphere) to 34580 kPa (5000 psi).
- oligomerization temperature is preferably between 90-250°C at a feedstock to catalyst weight ratio between 10:1 and 30;1.
- Contact time of both the olefin and the catalyst can vary from one second to 24 hours.
- the catalyst can be used in a batch type reactor or in a fixed bed, continuous-f1ow reactor.
- the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is then mixed and dried at room temperature.
- the dry solid gel is purged at successively higher temperatures to 600°C for a period of 16 to 20 hours.
- the catalyst is cooled down under an inert atmosphere to a temperature of 250 to 450°C and a stream of pure reducing agent is contacted therewith for a period when enough CO has passed through to reduce the catalyst as indicated by a distinct color change from bright orange to pale blue.
- the catalyst is treated with an amount of CO equivalent to a two-fold stoichiometric excess to reduce the catalyst to a lower valence CrII state.Finally the catalyst is cooled to room temperature and is ready for use.
- the product oligomers have a very wide range of viscosities with high viscosity indices suitable for high performance lubrication use.
- the product oligomers also have atactic molecular structure of mostly uniform head-to-tail connections with some head-to-head type connections in the structure.
- low branch ratio oligomers have high viscosity indices at least 15 to 20 units and typically 30-40 units higher than equivalent viscosity prior art oligomers, which regularly have higher branch ratios and correspondingly lower viscosity indices. These low branch oligomers maintain better or comparable pour points.
- the branch ratios defined as the ratios of CH, groups to
- CH 2 groups in the reaction products and by-products are calculated from the weight fractions of methyl groups obtained by infrared methods, published in Analytical Chemistry, Vol. 25, No. 10, p. 1466 (1953).
- Branch ratio wt fraction of methyl group l-(wt fraction of methyl group)
- the unique olefinic dimers used as alkylating agent in the present invention are produced as by-product of the HVI-PAO oligomerization reaction.
- the oligomerization reaction mixture is separated from the catalyst and separated by vacuum distillation to remove unreacted alpha-olefin and lower boiling by-products of the oligomerization reaction, such as alpha-olefin dimer.
- This provides a lubricant basestock of suitably high volatility and viscosity. While other methods known to those skilled in the art, such as solvent extraction, may be used to separate the alpha-olefin dimer by-product, distillation is preferred.
- the reaction provides as a by-product the olefinic dimer used as alkylating agent or reactant in the present invention.
- the dimer is separated by distillation from the oligomerization reaction mixture.
- Example 1 Catalyst Preparation and Activation Procedure 1.9 grams of chromium (II) acetate (Cr 2 (OCOCH 3 ) 4 2H 2 0) (5.58 mmole) (commercially obtained) is dissolved in 50 ml of hot acetic acid. Then 50 grams of a silica gel of 8-1.2 mesh size, a surface area of 300 m /g, and a pore volume of lml/g, also is added. Most of the solution is absorbed by the silica gel. The final mixture is mixed for half an hour on a rotavap at room temperature and dried in an open-dish at room temperature.
- the dry solid (20 g) is purged with N 2 at 250°C in a tube furnace.
- the furnace temperature is then raised to 400°C for 2 hours.
- the temperature is then set at 600°C with dry air purging for 16 hours.
- the catalyst is cooled under N 2 to a temperature of 300°C.
- a stream of pure CO (99.991 from Matheson) is introduced for one hour.
- the catalyst is cooled to room temperature under N 2 and ready for use.
- Example 2 The catalyst prepared in Example 1 (3.2 g ) is packed in a 9.5 m (3/8") stainless steel tubular reactor inside an N 2 blanketed dry box. The reactor under N 2 atmosphere is then heated to 150°C by a single-zone Lindberg furnace. Pre-purified 1-hexene is pumped into the reactor at 1069 kPa (140 psi) and 20 ml/hr. The liquid effluent is collected and stripped of the unreacted starting material and the low boiling material at 6.7 kPa (0.05 mm Hg). The residual clear, colorless liquid has viscosities and VI's suitable as a lubricant base stock.
- Example 3 A commercial chrome/silica catalyst which contains 1% Cr on a large-pore volume synthetic silica gel is used.
- the catalyst is first calcined with air at 800°C for 16 hours and reduced with CO at 300°C for 1.5 hours. Then 3.5 g of the catalyst is packed into a tubular reactor and heated to 100°C under the N 2 atmosphere. 1-Hexene is pumped through at 28 ml per hour at 101 kPa (1 atmosphere). The products are collected and analyzed as follows: Sample C D E F
- lubricants prepared by the methods described above contain olefinic unsaturation they are typically hydrogenated to stabilize them for lubricant use.
- very high molecular weight oligomers may not need to be hydrogenated since the number of olefin bonds in such oligomers is comparatively small.
- Lower molecular weight oligomers of particular interest in the present invention to provide low viscosity lubricants are hydrogenated by means well known to those skilled in the lubricant arts.
- the thermal stability of the hydrogenated lubricant range oligomers is improved by reaction with an olefin, preferably the non-lube range olefins produced as a by-product in the oligomerization reaction.
- an olefin preferably the non-lube range olefins produced as a by-product in the oligomerization reaction.
- the reaction employed herein to modify HVI-PAO oligomer is described as an alkylation reaction and the reactant alkene as an alkylating agent.
- alkylation is a significant reaction occurring in the instant invention carried out under alkylation conditions, other reactions are occurring as well, e.g., cracking, isomerization and polymerization. Accordingly, the term alkylation as used herein includes all those reactions occurring that result in the beneficial modification of HVI-PAO oligomers as herein described.
- the catalyst used in the alkylation reaction of the present invention is preferably a porous, solid acidic catalyst containing large pore openings.
- a preferred catalyst is a fluorided alumina, prepared as described hereinafter.
- Other useful solid catalysts include acidic zeolites. Zeolites useful as catalysts in the present invention include all natural or synthetic acidic large pore
- _7 size zeolites typically with a pore size of 6.4 x 10 mm to.7.5 x
- particularly useful catalysts include the acidic form of ZSM-4, ZSM-12, ZSM-20,
- alkylation catalysts which are also useful in the process of the present invention include conventional alkylation catalysts known to those skilled in the art including HF, AlC , BF-, and BF-, complexes, SbCl 5 , SnCl 4 , TiCl 4 , P 2 0 5 , H 2 S0 4 , ZnCl 2 and acidic clays.
- the alkylation reaction of the present invention produces alkylated synthetic lube containing large alkyl branches.
- the alkyl branches preferably contain between 12 and 40 carbon atoms, or mixtures thereof, depending on the olefin used in the alkylation reaction, e.g. the dimer of the C 6 -C 2Q alpha-olefin.
- Branches containing between 2 and 40 carbon atoms can be produced when monomeric olefins, e.g. ethylene, propylene, 1-decene, are used as alkylating agent.
- branching introduced by the olefin can be controlled by the mole ratio of alkene such as dimer olefin to synthetic lube in the alkylation reaction.
- the molar ratio of olefin to the lube range material will be between 40 to 1 and 1 to 1, preferably between 5 to l and 1 to 1 molar ratio.
- the product characteristics can range from synthetic lube containing at least one large alkyl group per mole to a reaction product containing a mixture of alkylated synthetic lube and synthetic lube.
- alkylation with alkene dimer produces an alkylated product that maintains the high VI and low pour point of the unalkylated HVI-PAO oligomer and shows an increase in thermal stability.
- the following Examples illustrate the preparation of a preferred alkylation catalyst of the present invention and further illustrate the novel alkylation reaction.
- alumina Harshaw Catapal-S, 0.8 ram (1/32 inch) extrudate
- 25 grams of alumina Harshaw Catapal-S, 0.8 ram (1/32 inch) extrudate
- alumina Harshaw Catapal-S, 0.8 ram (1/32 inch) extrudate
- excess water is removed under reduced pressure at 80°C.
- the aluminum nitrate impregnated alumina is then contacted with 8.17 grams ammonium fluoride in 50ml water to form aluminum fluoride in the alumina.
- the aluminum fluoride/alumina catalyst is dried under vacuum at 115°C for 18 hours and then calcined at 538°C for 12 hours.
- Synthetic lube is prepared according to the process for HVI-PAO reacting 1-decene over chromium supported silica as previously described herein.
- the unsaturated decene dimer is separated by distillation as a by-product to remove unreacted decene and lubricant product hydrogenated.
- the lube product viscosity was 9.2 mm 2 /s (9.2cS), measured at 100°C.
- Example 6 Alkylation of HVI-PAO Lube Alkylation reactions are performed in a fixed-bed reactor. The unit is maintained at 2861 kPa (400 psig) and the liquid hourly space velocity (IHSV) is 0.5. The feed is a mixture of 315 grams of 1-decene HVI-PAO lube and 140 grams of 1-decene dimer representing 30.8 weight percent. Alkylation reactions are carried out at reaction temperatures of 167, 204 and 250°C, Examples 7-1, 7-2 ⁇ 7-3. The results of these alkylation reactions are presented in Table 1 Table 1
- HVI-PAO fed Based upon the initial percent of HVI-PAO present in the feed, the amount of HVI-PAO fed can be calculated and is found in Table 1 for each example. After alkylation, a weight increase is expected and is noted in the table. Weight increases vary between 8.4 and 15.9 percent and appear to be a function of reaction temperature.
- the overall yield of final product is increased by the addition by alkylation of dimer by-product to the synthetic HVI-PAO lubricant.
- the alkylated product has an increased viscosity compared to the starting HVI-PAO lubricant and maintains the high VI characteristic of these oligomers.
- Example 7 Catalyst Preparation 25 grams of alumina is contacted with a solution comprised of 5.3 grams of alumina nitrate (nona-hydrate) in 30ml of water for one hour. Excess water is removed by vacuum. The dried alumina nitrate impregnated alumina is then contacted with another solution containing 2.7 grams of ammonium fluoride in 50ml of water. After five minutes the excess water is decanted and the resulting fluorided alumina is dried in vacuum at 95°C for three days. This catalyst contains 5% aluminum fluoride.
- HVI-PAO increases. At 30.6% alkylation the viscosity loss is reduced to 10.1% ( ⁇ 100°C).
- HVI-PAO is alkylated as described above using the same fluorided alumina catalyst, except 1-decene alone was mixed with the HVI-PAO for reaction instead of HVI-PAO dimer.
- Table 4 presents the thermal stability test results on the product of Example 9.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
On améliore la stabilité thermique de lubrifiants synthétiques composés d'oligomères d'alpha-oléfines par réaction avec une oléfine telle que la décène ou les oléfines de faible masse moléculaire de la gamme non lubrifiante, produites au cours de l'oligomérisation de 1-alcènes. On procède à l'alcoylation de l'oligomère de la gamme lubrifiante à l'aide d'un catalyseur d'alcoylation acide tel qu'un catalyseur solide à pores ouverts, par exemple de l'oxyde d'aluminum fluoré. Les compositions lubrifiantes améliorées de l'invention comprennent une composition d'oligomère lubrifiant liquide d'indice de viscosité élevé, contenant des hydrocarbures C30-C1300 comportant au moins une ramification d'alcoyle inférieur contenant entre 12 et 40 atomes de carbone. Dans un mode de réalisation préféré, la nouvelle composition lubrifiante alcoylée a un rapport de ramification entre le méthyle et le méthylène inférieur à 0,19, ainsi qu'un point d'écoulement inférieur à -15°C.The thermal stability of synthetic lubricants composed of alpha-olefin oligomers is improved by reaction with an olefin such as decene or low molecular weight olefins from the non-lubricating range produced during the oligomerization of 1-alkenes. . The oligomer of the lubricating range is alkylated using an acidic alkylation catalyst such as a solid catalyst with open pores, for example fluorinated aluminum oxide. The improved lubricant compositions of the invention comprise a liquid lubricant oligomer composition of high viscosity index, containing C30-C1300 hydrocarbons having at least one branch of lower alkyl containing between 12 and 40 carbon atoms. In a preferred embodiment, the new alkylated lubricant composition has a branching ratio between methyl and methylene of less than 0.19, as well as a pour point of less than -15 ° C.
Description
Claims
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AT90904065T ATE88493T1 (en) | 1989-02-21 | 1990-02-15 | SYNTHETIC LUBRICATION OIL COMPOSITION AND PROCESS. |
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US31357689A | 1989-02-21 | 1989-02-21 | |
US313576 | 1989-02-21 |
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EP (1) | EP0413795B1 (en) |
JP (1) | JP2945134B2 (en) |
AU (1) | AU629618B2 (en) |
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US4990709A (en) * | 1989-04-28 | 1991-02-05 | Mobil Oil Corporation | C2-C5 olefin oligomerization by reduced chromium catalysis |
US4967032A (en) * | 1989-09-05 | 1990-10-30 | Mobil Oil Corporation | Process for improving thermal stability of synthetic lubes |
US5902849A (en) * | 1991-11-07 | 1999-05-11 | Henkel Kommanditgesellschaft Auf Aktien | Filling compound |
DE4136617C2 (en) | 1991-11-07 | 1997-08-14 | Henkel Kgaa | Filling compound and its use |
US7572943B2 (en) * | 2005-12-20 | 2009-08-11 | Chevron U.S.A. Inc. | Alkylation of oligomers to make superior lubricant or fuel blendstock |
US8168838B2 (en) | 2009-01-21 | 2012-05-01 | Shell Oil Company | Hydrocarbon compositions useful as lubricants |
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GB636372A (en) * | 1947-03-07 | 1950-04-26 | Standard Oil Dev Co | Production of synthetic lubricating oil |
US4827064A (en) * | 1986-12-24 | 1989-05-02 | Mobil Oil Corporation | High viscosity index synthetic lubricant compositions |
US4827073A (en) * | 1988-01-22 | 1989-05-02 | Mobil Oil Corporation | Process for manufacturing olefinic oligomers having lubricating properties |
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1990
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- 1990-02-15 WO PCT/US1990/000863 patent/WO1990010050A1/en active IP Right Grant
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JP2945134B2 (en) | 1999-09-06 |
AU5171490A (en) | 1990-09-26 |
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EP0413795B1 (en) | 1993-04-21 |
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