CN1867653A - Lubricant base oils with optimized branching - Google Patents
Lubricant base oils with optimized branching Download PDFInfo
- Publication number
- CN1867653A CN1867653A CNA2004800303032A CN200480030303A CN1867653A CN 1867653 A CN1867653 A CN 1867653A CN A2004800303032 A CNA2004800303032 A CN A2004800303032A CN 200480030303 A CN200480030303 A CN 200480030303A CN 1867653 A CN1867653 A CN 1867653A
- Authority
- CN
- China
- Prior art keywords
- lubricant base
- oil
- branch
- less
- base
- 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
- 239000000314 lubricant Substances 0.000 title claims abstract description 196
- 239000002199 base oil Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 65
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 100
- 239000003921 oil Substances 0.000 claims description 86
- 229910052799 carbon Inorganic materials 0.000 claims description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 239000000203 mixture Chemical class 0.000 claims description 30
- 238000006317 isomerization reaction Methods 0.000 claims description 25
- -1 methyl hydrocarbon Chemical class 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 239000010687 lubricating oil Substances 0.000 claims description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000012169 petroleum derived wax Substances 0.000 claims description 7
- 235000019381 petroleum wax Nutrition 0.000 claims description 7
- 229920013639 polyalphaolefin Polymers 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 42
- 239000002585 base Substances 0.000 description 145
- 239000001993 wax Substances 0.000 description 67
- 239000000047 product Substances 0.000 description 42
- 239000002904 solvent Substances 0.000 description 40
- 238000009835 boiling Methods 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 24
- 239000002808 molecular sieve Substances 0.000 description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 23
- 239000002994 raw material Substances 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 230000009466 transformation Effects 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002050 diffraction method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012188 paraffin wax Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004088 simulation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 230000002152 alkylating effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 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 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 238000002397 field ionisation mass spectrometry Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
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- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin 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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
-
- 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
-
- 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
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
-
- 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
- C10N2020/02—Viscosity; Viscosity index
-
- 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
- C10N2020/071—Branched chain compounds
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to lubricant base oils comprising paraffinic hydrocarbon components having optimized branching. These lubricant base oils comprising paraffinic hydrocarbon components with optimized branching have low amounts of branching overall with the branching concentrated toward the center of the lubricant base oil molecules. The present invention also relates to processes of producing these lubricant base oils from waxy feeds and commercial finished lubricants comprising these lubricant base oils.
Description
Invention field
The present invention relates to contain the lubricant base of alkane component with optimized branching.The described lubricant base that contains the alkane component with optimized branching contains a spot of branch, and branch concentrates to the middle part of lube base oil molecule.The described lubricant base that contains the alkane component with optimized branching has low pour point and high viscosity index.The invention still further relates to by waxy feed and produce the described method that contains the lubricant base of alkane component with optimized branching.Described lubricant base is applicable to finished commercial prod's lubricating oil.
Background of invention
High-quality lubricating oil with regard to character should be and normally alkane belong to because alkane has high viscosity index.But particularly normal paraffin is a wax, makes oil product that high pour point be arranged.Therefore, can produce the dewaxing of ramose hydroisomerization and make the alkane feedstock conversion of wax become lubricant base by making on the alkane molecule.The hydroisomerization dewaxing is produced usually has higher ramose lubricant base.Produce branch pour point is descended though belong on the molecule at wax alkane, it also makes viscosity index (VI) descend.Reach target pour point and cloud point with full hydroisomerization method, need a large amount of branches.Therefore, because a large amount of relatively branches, the product that is obtained by the hydroisomerization method has the optimum viscosity of being lower than exponential viscosity index usually.The lube base oil production of producing with the hydroisomerization method may have the US of being similar to patent Nos.6, branch's characteristic of those disclosed product in 096,940,6,090,989 and 6,059,955.
In lubricant base, low pour point is wished.Low pour point shows that lubricant base can flow and lubricate at low temperatures.Pour point is that of temperature measures, and sample will begin to flow under this temperature under the condition of careful control.Pour point can be by measuring of describing among the ASTM D 5950.Many commercial lubricant bases have the technical specification about pour point.When lubricant base had low pour point, they also may have other good low-temperature performance, for example low cloud point, low cold filter clogging temperature and cold-starting viscosity.
Pour point-cloud point scope (pour-cloud point spreads) is lower than about 30 ℃ lubricant base also wishes.In order to meet the technical specification of cloud point, higher pour point-cloud point area requirement is worked into very low pour point with lubricant base.
Also wish to obtain the lubricant base of high viscosity index (HVI).Viscosity index (VI) is the empirical no units of expression temperature variation to the influence of oil product kinematic viscosity.The viscosity with temperature of liquid changes, and viscosity diminishes when being heated; The VI of oil product is high more, and the tendency that viscosity with temperature changes is low more.The lubricating oil of high VI is needs under any occasion that needs relative constant viscosity under the wide transformation temperature.For example, in automobile, the essential enough unrestricted flow of engine oil is so that can cold-starting, but must be later on enough heavy-gravity at warming-up, so that provide lubricated fully.VI can be by measuring of describing among the ASTM D 2270-93.
Branch on the alkane molecule of pour point and VI and lubricant base can be connected.Producing branch on straight-chain paraffin makes pour point decline usually and viscosity index (VI) is descended.If the number that equal length replaces doubles, VI usually obviously descends, but may be less to the influence of pour point.The data of No. 42 projects of API (by No. 42 research projects of American Petroleum Institute (API) in the University of Pennsylvania July 1 nineteen forty-three to the research of finishing between July 1 nineteen forty-six) show, for the butyl on the straight-chain paraffin, phenyl and cyclohexyl branch, VI descends with the middle part that branch moves to molecule.
Wax hydro carbons by the Fischer-Tropsch process preparation is the good potential raw material of preparation high quality lubricating oil.Advantageously, fischer-tropsch synthesis product contains seldom (if any) typical petroleum pollution, for example aromatic substance, sulfocompound and nitrogenous compound.But initial f-t synthetic wax matter alkane is generally straight waxes.Therefore, fischer-tropsch synthesis product need further be processed or upgrading, so that obtain high-quality lubricant base raw material.
Many investigators studied with various waxy feed particularly the waxy feed that obtains of Fischer-Tropsch synthesis change into the method for lubricant base raw material.For example, producing enough branches so that pour point is descended but in the trial that inexcessive branch so that VI obviously descend, the method of prior art has used hydroisomerization to combine with solvent dewaxing, and hydroisomerisation step is used the zeolite catalyst (for example β zeolite) of unbodied or macropore.Yet in the method for the prior art of using this technology, still produce considerable branch.
For example, U.S. patent No.6,090,989 discloses a kind of Hydrodewaxing method of producing the lubricant base raw material.Wherein disclosed lubricant base raw material contains alkane component, wherein branch degree of being measured by the percentage ratio of methyl hydrogen (BI) and the proximity (CH of branch that is measured by the percentage ratio that repeats mesomethylene carbon (they have 4 or 4 above carbon apart from end group or branch)
2＞4) be such: (a) BI-0.5 (CH
2＞4) greater than 15 and (b) BI+0.85 (CH
2＞4)＜45.This calculating means that for the molecule that contains 24 carbon, each molecule should have at least 2.5 branches, or for per 100 carbon, has greater than about 9 branches.
US patent No.6,008,164 discloses a kind of method of producing the lubricant base raw material by f-t synthetic wax, and wherein the lubricant base raw material has the oxidative stability of preliminary election.Disclosed lubricant base contains the mixture of branch's alkane, wherein branch's alkane contain up to 4 alkyl branches and wherein the uncombined carbon index (FCI) of branch's alkane be at least about 3.The embodiment of ' 164 patents proves that each molecule of described lubricant base has 3.46,3.14,4.19 and 3.59 branches.
WO 99/45085 discloses a kind of integrated processes for preparing the lubricant base raw material, comprising isomerization steps, follows by the solvent dewaxing step.In this method, incite somebody to action wherein disclosed waxy feed, waxy feed isomerization on the molecular sieve of selecting is carried out solvent dewaxing to isomerized oil then to middle pour point.The viscosity index of the lubricant base raw material that makes is greater than about 140.The viscosity index that the embodiment of ' 085 open text proves the lubricant base raw material is up to 156 at 140 these orders of magnitude.
EP 0776959A2 discloses and has a kind ofly produced the method that VI is at least 150 lubricant base by the f-t synthetic wax charging, and described method comprises the f-t synthetic wax charging is contacted under the hydrocracking condition with hydrogenation conversion catalyst; The hydrocracking effluent that makes is separated at least a light ends and a kind of heavy ends; And heavy ends dewaxing obtained base oil.The charging of sending into described method only limits to congelation point at least 50 ℃ f-t synthetic wax and following boiling range is arranged, and wherein the difference between 90 weight % boiling points and the 10 weight % boiling points is in 40-150 ℃ of scope.Disclosed hydrogenation conversion catalyst is an amorphous catalyst.
U.S. patent No.6,096,940 discloses a kind of method of producing biodegradable hydro carbons lubricant base.Described method comprises: 700 +f-t synthetic wax charging is contacted on difunctional group VIII non-precious metal catalyst with hydrogen carry out hydroisomerization, and hydrocracking reaction, weight by 700 that are converted into 700 -material+charging, 700 of one way benchmark+transformation efficiency is about 20 to about 50%, produces C
5The thick cut of-1050 .The methyl that contained isoparaffin has in thick cut branches into per 100 carbon to be had less than about 7.5 methyl branches.From C
5It is the residual fractions of about 650 to about 750 that-1050 cuts reclaim initial boiling range.Residual fraction reclaims pressed oil then through dewaxing.Reclaim biodegradable hydrocarbon base oils from pressed oil.In an embodiment, the VI of the lubricant base of recovery is 130 and 140 these orders of magnitude.
US patent No.5,059,299 disclose that a kind of to make pour point by following steps be that approximately-21 ℃ or lower and viscosity index are about 130 or the maximized method of productive rate of higher lubricant base raw material: 1) with wax isomerization on isomerization catalyst, so that about 15 to 30% unconverted waxes are still stayed in the oil distillate of the isomerization product of boiling point in the lubricating oil boiling range, 2) with described product fractionation, 3) be 9 ℃ or littler with the cut solvent dewaxing of boiling point in the lubricating oil boiling range to pour point/strainer δ T (pour point of pressed oil and the temperature head between the filter temperature), and 4) reclaim the lube product of dewaxing.The dewaxing catalyst that is applicable to this invention is broadly defined and is comprised various catalyzer, for example fluorizated aluminum oxide.
Also studied composition how to analyze lubricant base with and form the character that how to influence lubricant base.For example, Kramer, D.C., Deng, be 1999 AIChE SpringNational Meeting in Houston, the report that March 16,1999 prepares " II and III class base oil are formed the influence to VI and oxidative stability " is pointed out, in measuring alkane and the distribution of naphthenic hydrocarbon in II and III class base oil, field ionization mass spectrum (FIMS) is valuable especially.Be lower than under 1% aromatic hydrocarbons, the effective way that the author finds further to improve oxidative stability is to improve VI.Generally speaking, the author finds that the concentration of polycyclic naphthene hydrocarbon is low more in the oil product, and its VI and oxidative stability are high more.
Still a kind of method of efficient and cost-effective that becomes the high quality lubricant base particularly to have the lubricant base of good low temperature properties and high viscosity index (HVI) wax alkane feedstock conversion there is demand.
Summary of the invention
The present invention relates to a kind of lubricant base, it comprises branch degree is that per 100 carbon are less than 8 alkyl branches and at 2 described alkyl ramose alkane components that have less than 20 weight %.The pour point of this lubricant base is less than-8 ℃; Kinematic viscosity under 100 ℃ is about 3.2cSt or bigger; And viscosity index is greater than the target viscosities index that calculates in order to following equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132.
On the other hand, the present invention relates to a kind of lubricant base, it comprises the pour point less than-8 ℃; Under 100 ℃ greater than the kinematic viscosity of 3.2cSt; And greater than the target viscosities exponential viscosity index of calculating in order to following equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132.
On the other hand, the present invention relates to a kind of finished lube.This finished lube contains lubricant base described here and one or more lubricating oil additives.
On the other hand, the present invention relates to a kind of middle isomerized oil (intermediate oilisomerate).It is that per 100 carbon have less than 7 alkyl ramose alkane components that this centre isomerized oil contains by the synthetic branch degree that obtains of fischer-tropsch.
The accompanying drawing summary
Viscosity under 100 ℃ of the description of drawings is mapped to viscosity index, obtains calculating target viscosities exponential equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132 wherein ln (kinematic viscosity under 100 ℃) is the natural logarithm of the kinematic viscosity under 100 ℃.
The detailed description of illustrative embodiment
The present invention relates to lubricant base, it comprises the mixture of alkane component, and the mixture of wherein said alkane component has optimized branching.These lubricant bases that comprise the mixture of the alkane component with optimized branching have a spot of branch generally, and described branch concentrates to the middle part of lube base oil molecule.The invention still further relates to finished commercial prod's lubricating oil of producing the method for these lubricant bases and contain these lubricant bases by waxy feed.
Find that surprisingly in the lubricant base of the kinematic viscosity under 100 ℃ greater than about 3.2cSt, best branch can provide low especially pour point and high viscosity index, it is greater than the target viscosities index that defines here.Best branch of the present invention is meant that the lube base oil molecule comprises a spot of ramose alkane component is arranged generally, and described branch concentrates to the middle part of molecule.
The kinematic viscosity that comprises under alkane component with optimized branching and 100 ℃ can be produced by the combination of demulcent hydroisomerization solvent dewaxing subsequently greater than the lubricant base of about 3.2cSt.According to the present invention, make waxy feed under such condition, carry out the mild hydrogenation isomerization process, so that obtain comprising the middle isomerized oil of alkane component with specific branch character.Then middle isomerized oil is carried out solvent dewaxing under such condition, obtain comprising kinematic viscosity under alkane component with optimized branching and 100 ℃ greater than the lubricant base of about 3.2cSt.Method of the present invention obtains comprising the lubricant base of the alkane component with optimized branching, so that a spot of branch is arranged generally, and described branch concentrates to the middle part of molecule.Branch degree and branch location can be analyzed with NMR and measure.
Find surprisingly, overall branch is minimized make simultaneously branch's maximization, the lubricant base with the low pour point of ultra-high viscidity exponential sum can be provided towards the central authorities of lube base oil molecule.Therefore, make the high quality lubricant base of the low pour point of ultra-high viscidity exponential sum.
Definition
Unless add explanation in addition, following term is used for whole specification sheets and following implication is arranged.
" by fischer-tropsch synthetic or method obtains " is meant that described cut, logistics or product come from Fischer-Tropsch synthesis or produced by Fischer-Tropsch process in a certain stage.
" wax hydrocarbon raw material " is C for a kind of carbon number that comprises
20+Molecule and boiling point usually greater than the charging or the logistics of about 600 (316 ℃).The wax hydrocarbon raw material that is applicable to method disclosed herein can be the synthetic wax raw material, f-t synthetic wax matter hydro carbons for example, or can by natural origin for example petroleum wax make.
" lubricant base " is meant a kind of cut or product that meets the lubricant base technical specification.The method according to this invention makes lubricant base oil fraction with hydroisomerization/solvent dewaxing process, and they have optimized branching character.Other character of the lubricant base that the present invention obtains comprise the initial boiling point of 600-950 , the final boiling point of 800-1200 , the viscosity of 3.2-20cSt (100 ℃), 158-240, preferred 163-220, the more preferably viscosity index of 165-200.Lubricant base further have less than-8 ℃, preferably less than-9 ℃, more preferably≤-15 ℃ even be more preferably less than-15 ℃, and preferred-8 to-35 ℃ pour point.Lubricant base can also have+5 to-20 ℃ cloud point.
" hydro carbons or hydrocarbon-containifirst " is meant a kind of compound or material of hydrogeneous and carbon atom, and it also can contain heteroatoms, for example oxygen, sulphur or nitrogen.
" target viscosities index " is an experience number that is obtained by kinematic viscosity and viscosity index.The target viscosities index calculates in order to following equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132 wherein ln (kinematic viscosity under 100 ℃) is the natural logarithm of the kinematic viscosity under 100 ℃.Target viscosities exponential mensuration has been described in the accompanying drawings.
" alkyl " is meant the straight chain saturated mono valency alkyl of a kind of 1-6 carbon atom or the saturated univalence hydrocarbyl of side chain of 3-8 carbon atom.Preferably, alkyl is a methyl.The example of alkyl includes but not limited to such group, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl etc.
" uncombined carbon index " is to be positioned in the isoparaffin apart from least 5 carbon of terminal carbon and measuring from the number of the carbon atom of 4 carbon of side chain (FCI).
Find that surprisingly the kinematic viscosity that comprises under the alkane component, 100 ℃ of the branch's character (optimized branching) with some hope has high viscosity index and fabulous low pour point greater than the lubricant base of about 3.2cSt.The viscosity index of lubricant base of the present invention is greater than the target viscosities index of oil product.Preferably, the viscosity index of lubricant base of the present invention adds 5 greater than the target viscosities index of oil product.As defined above, the target viscosities index is that viscosity is dependent, and calculates in order to following equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132.
These lubricant bases comprise the mixture of alkane component, and wherein the total mixture of alkane component has optimized branching.These lubricant bases that comprise the alkane component with optimized branching are produced by waxy feed.The invention still further relates to the middle isomerized oil that makes in the method for production lubricant base of the present invention.Isomerized oil comprises the alkane component with specific branch character in the middle of of the present invention.Therefore, when middle isomerized oil changed into lubricant base, lubricant base comprised the alkane component with optimized branching character.Middle isomerized oil is made up of alkane component, and wherein said alkane component has a spot of overall branch.
Middle isomerized oil is changed into the lubricant base of forming by alkane component with optimized branching character.Best branch character of the present invention is meant that described alkane component has a spot of overall branch, and described branch concentrates to the middle part of molecule.Therefore, the branch near molecular end is minimized.
Branch into alkyl branch on the alkane component of lubricant base and middle isomerized oil.In lubricant base and middle isomerized oil, alkyl branch is mainly the (CH of methyl branch
3).According to the present invention, in lubricant base, branch's character is optimised.Branch's character comprises branch degree and branch location.Branch degree can be measured by the alkyl number of branches of each fixed number order carbon of alkane component.Preferably, branch degree is measured with the alkyl number of branches of per 100 carbon.Come the position of measurement branches with respect to the end of alkane hydrocarbon chain, end carbon is 1, and next adjacent carbons is 2, and next again carbon is 3 or the like, when reaching hydrocarbon chain central till.Position on the hydrocarbon chain can be described as follows:
CH
3-CH
2-CH
2-CH
2-CH
2-(CH
2)
10-CH
2-CH
2-CH
2-CH
2-CH
3
1 2 3 4 5 5 4 3 2 1
Middle isomerized oil is the intermediate product of the method for production lubricant base of the present invention.Middle isomerized oil is produced by with the particular type shape-selective catalyst waxy feed being carried out the mild hydrogenation isomerization process, and described catalyzer produces pour point decline significantly and minimum branch degree.With middle isomerized oil solvent dewaxing, obtain lubricant base of the present invention.
According to the present invention, middle isomerized oil comprises the alkane component with specific branch character.Middle isomerized oil is formed by having a small amount of overall ramose alkane component.Particularly, middle isomerized oil comprises per 100 carbon has less than 7.0 alkyl branches, preferred per 100 carbon and has less than 6.5 alkyl ramose alkane components.
With middle isomerized oil solvent dewaxing, make lubricant base of the present invention.According to the present invention, described lubricant base comprises the wherein optimised alkane component of branch.Lubricant base comprises the alkane component with optimized branching, because the alkane component of isomerized oil has a spot of overall branch, described branch concentrates to the middle part of molecule.
Particularly, described lubricant base comprise per 100 carbon have less than 8 alkyl branches, preferred per 100 carbon have less than 7 alkyl branches, more preferably per 100 carbon have less than 6.5 alkyl ramose alkane components.In addition, lubricant base is included in 2 has less than 20 weight % branches, preferably has less than 15% ramose alkane component at 2.Lubricant base 2 add 3 also have a small amount of branch, preferably less than 25 weight %, be more preferably less than 20 weight %.In addition, lubricant base has 5 or bigger position greater than 45 weight %, more preferably greater than the branch of 50 weight %.
Generally believing to have higher motion viscosity and also have the lubricant base of desired pour point to compare with production in the art, easier production has harmonic motion viscosity (under 100 ℃ usually less than about 3.2cSt) and has the lubricant base of low pour point.The harmonic motion viscosity lubricant base that contains alkane molecule has short relatively alkane chain, and normal length is less than about 25 carbon atoms.Because the lubricant base that has than harmonic motion viscosity has short relatively alkane chain, so in order to reach low pour point, these lubricant bases need branch still less usually.
On the contrary, the lubricant base of viscosity higher comprises the longer alkane molecule of long-chain.In these longer alkane molecules of the lubricant base of viscosity higher, more be difficult to isomerization and obtain a small amount of branch and obtain low pour point.
In addition, verified in the past, for butyl, phenyl and cyclohexyl branch, when branch when the middle part of straight-chain paraffin is mobile, VI descends.So, do not contain and think and wish to produce the lubricant base of branch part, but very it is shocking towards the alkane molecule middle part, done like this and combined with a small amount of branch, can obtain having the lubricant base of high VI and low pour point.
The method according to this invention, waxy feed is processed in such a way, so that reaches this required numbers of branches and position (being optimized branching).So, produce the lubricant base of high viscosity, low pour point and high VI.The kinematic viscosity of lubricant base of the present invention under 100 ℃ is greater than about 3.2cSt, preferably about 3.2cSt is to about 20cSt.In addition, the average carbon number that comprises of lubricant base of the present invention greater than about 27, be preferably greater than about 30, more preferably greater than about 27 but less than about 70.
Branch degree and branch location can be analyzed with NMR and measure.
NMR branch analyzes
Branch's character of lubricant base of the present invention and middle isomerized oil is measured by analyzing oil sample with C-13NMR by 8 following footworks.The reference that is drawn in method is described provides the detailed content of method steps.Step 1 and 2 is only carried out the initial material from novel method.
1.) determine that with DEPT Pulse sequence CH divides branch center and CH
3Branch's terminating point (Doddrell, D.T.; D.T.Pegg; M.R.Bendall, Journal of MagneticResonance 1982,48,323ff.).
2.) confirm to lack to cause a plurality of ramose carbon (quaternary carbon) (Patt, S.L. with APT pulse sequence; J.N.Shoolery, Journal of Magnetic Resonance1982,46,535ff.).
3.) various branches carbon resonance is distributed to specific branch location and length (Lindeman, L.P., Journal of Qualitative AnalyticalChemistry 43,1971 1245ff with tabulated value and calculated value; Netzel, D.A., et.al., Fuel, 60,1981,307ff.).
Example:
Branch's nmr chemical displacement (ppm)
2-methyl 22.5
3-methyl 19.1 or 11.4
4-methyl 14.0
4+ methyl 19.6
Interior ethyl 10.8
Propyl group 14.4
Adjacent methyl 16.7
4.) comprehensive strength by its terminal methyl group carbon comes the quantitative relative frequency that occurs in different carbon locations place branch with the comparison (total mark/number of the carbon of each molecule in the=mixture) of single carbon intensity.
For this unique situation of 2-methyl branch, wherein terminal methyl group occurs at identical resonant position with the branch methyl, occurs before the frequency computation part intensity divided by two carrying out branch.
If 4-methyl component is calculated and is tabulated, for fear of dual calculating, essential contribution of deducting it to the 4+ methyl.
5., analyze the result who obtains with sample average carbon number that calculates and C-13 NMR and calculate the uncombined carbon index) as described in the EP 1062305.Uncombined carbon index (FCI) is to be positioned in the isoparaffin apart from least 5 carbon of end carbon and measuring from the number of the carbon atom of 4 carbon of side chain.For the lubricating oil material, can by with the molecular weight of sample divided by 14 (CH
2Chemical formula weight) measure average carbon number with enough accuracy.Molecular weight can be measured with ASTM D2502, ASTM D2503 or other method that is fit to.According to the present invention, molecular weight is preferably measured with ASTM D2503-02.
6.) with U.S. patent No.6, disclosed method of calculation are come Branch Computed index (BI) and branch's degree of approach (BP) in 090,989.Branch's index is the per-cent of total non-benzyl aliphatic series hydrogen in interior non-benzyl methyl hydrogen of 0.5-1.05ppm scope and the 0.5-2.1ppm scope.Branch's degree of approach is the % that is equal to the mesomethylene carbon of reproduction, and these mesomethylene carbon have 5 or more a plurality of carbon (ε carbon) apart from end group or branch.
7.) number of branches of each molecule be the ramose that obtains in the step 4 and.
8.) (step 7) multiply by the alkyl ramose number that 100 carbon numbers divided by each molecule calculate per 100 carbon atoms by the number of branches of each molecule.
Available any fourier transformation NMR spectrometer is measured.Preferably, with there being the spectrometer of 7.0T or bigger magnet to measure.In all cases, with mass spectroscopy, UV or NMR measure confirm not have aromatics carbon after, spectrum width is limited to the saturated carbon scope, about 0-80ppm vs.TMS (tetramethylsilane).It then is 0.8 second detection time that 15-25 weight % solution among chloroform-dl excites by 45 ° of pulses.For non-homogeneous intensity data is minimized, remove gate (gated off) in 10 seconds deferring procedures of proton-decoupled device before excitation pulse, gate in detection process (gated on).Total experimental period is 11-80 minute.DEPT and APT sequence are undertaken by document description, and the fine difference of describing in Varian or the Bruker operational manual is arranged.
DEPT is the undistorted enhancing of polarization transfer.DEPT does not show quaternary carbon.DEPT 45 sequences provide binding all carbon signals to the proton.90 expressions of DEPT CH carbon.DEPT 135 expression CH and CH upwards
3CH with 180 degree (downwards) of phasic difference mutually
2APT connects hydrogen number test (Attached Proton Test).As seen it make all carbon, if but CH and CH
3Make progress, so quaternary carbon and CH
2Downwards.Described sequence is suitable for, because each branch's methyl should have corresponding C H.Clearly determined methyl with chemical shift and phase place.The both describes in the reference that is drawn.
Measure branch's character of each sample with C-13 NMR, use following hypothesis in calculating: whole lubricant base or middle isomerized oil sample are isoparaffin.Do not do correction for normal paraffin or naphthenic hydrocarbon, they may exist with different quantity in oil sample.Owing in preparation, use mild hydrogenation isomerization dewaxing method, the whole naphthenic hydrocarbon % in the lubricant base normally low or do not have.The content of naphthenic hydrocarbon can be measured with field ionization mass spectroscopy (FIMS).
Raw material
According to the present invention, the charging of producing the method for the lubricant base that optimized branching is arranged is a kind of wax hydrocarbon feed.The wax hydrocarbon raw material that is applicable to method disclosed herein can be the synthetic wax raw material, f-t synthetic wax matter hydro carbons for example, perhaps can by natural origin for example petroleum wax make.Therefore, the waxy feed of described method can comprise the synthetic waxy feed that obtains of fischer-tropsch, petroleum wax, waxy fraction oil raw material for example gas oil, lube stock, high pour point poly-alpha olefins, foots oil, positive alpha-olefin wax, gatch, dewaxed oil and Microcrystalline Wax and composition thereof.Preferably, waxy feed is made by the charging of f-t synthetic wax matter.It is C that the major portion of waxy feed comprises carbon number
20+Molecule and also boiling point usually greater than about 600 (316 ℃).Most of molecules in the waxy feed are the normal paraffin and the ramose alkane slightly of higher molecular weight that helps the waxy nature of charging.
If desired, the method that can here describe of wax hydrocarbon raw material was carried out hydrotreatment in the past.
Fischer-tropsch is synthetic
Preferably, waxy feed of the present invention is made by the charging of f-t synthetic wax matter.In the fischer-tropsch synthetic chemistry, synthetic gas is changed into liquid hydrocarbon by under reaction conditions, contacting with Fischer-Tropsch catalyst.Usually, can be with methane and randomly will send into traditional synthetic gas generator than heavy hydrocarbons (ethane and more heavy hydrocarbons), so that obtain synthetic gas.Usually, synthetic gas contains hydrogen and carbon monoxide, and can contain amounts of carbon dioxide and/or water.The existence of sulphur, nitrogen, halogen, selenium, phosphorus and arsenic impurities is undesirable in synthetic gas.Owing to this reason and relevant with the quality of synthetic gas, removing desulfuration before carrying out the fischer-tropsch synthetic chemistry from charging is preferred with other impurity.For those skilled in the art, the equipment of removing these impurity is that everybody is familiar with.For example, in order to remove sulphur impurity, ZnO protection bed is preferred.For those skilled in the art, the equipment of removing other impurity also is that everybody is familiar with.For any other sulphur compound of removing the carbonic acid gas that generates and also do not remove in the synthesis gas reaction process, the purifying synthetic gas also may be wished before the F-T synthesis reaction device.This for example can contact in packed tower with medium basic solution (for example wet chemical) by synthetic gas and finish.
In the fischer-tropsch building-up process, contain H
2Under the temperature and pressure reaction conditions that is fit to, contact with Fischer-Tropsch catalyst with the synthetic gas of the mixture of CO, generate liquid hydrocarbon and gas hydro carbons.F-T synthesis reaction is usually in about 300 to 700 (149-371 ℃), the preferred temperature of about 400-550 (204-228 ℃); About 10-600psia (0.7-41 crust), the preferred pressure of about 30-300psia (2-21 crust); About 100-10,000cc/g/hr, preferred about 300-3 carry out under the catalyzer air speed of 000cc/g/hr.For those skilled in the art, the example that carries out the condition of fischer-tropsch synthesis type reaction is that everybody is familiar with.
The product of Fischer-Tropsch synthesis can be at C
1-C
200+Change in the scope, wherein most of at C
5-C
100+In the scope.Reaction can be carried out in various types of reactors, for example with the combination of fixed-bed reactor, slurry-phase reactor, fluidized-bed reactor or the dissimilar reactors of one or more beds.Such reaction method and reactor are that everybody is familiar with, and on the books in the literature.
The slurries Fischer-Tropsch synthesis is preferred in enforcement of the present invention, and it utilizes heat transfer (and mass transfer) characteristic superior for strong exothermic reaction, and when using cobalt catalyst, it can produce relative high-molecular weight alkane.In slurry method, the synthetic gas that will contain hydrogen and carbon monoxide mixtures makes progress bubbling by contain the fischer-tropsch synthesis type hydrocarbon synthesis catalyst particulate slurries that disperse and suspend in slurries liquid as third phase, and it is the hydrocarbon product of the building-up reactions of liquid that described slurries liquid contains under reaction conditions.The mol ratio of hydrogen and carbon monoxide can broadly be about 0.5 to about 4, but is more typically about 0.7 to about 2.75, preferred about 0.7 to about 2.5.Particularly preferred Fischer-Tropsch synthesis is open in EP 0609079, incorporates this paper under all occasions as a reference fully into.
In general, Fischer-Tropsch catalyst contains group VIII transition metal on metal oxide carrier.Catalyzer also can contain noble metal promoted agent and/or crystalline molecular sieve.The Fischer-Tropsch catalyst that is fit to contains one or more among Fe, Ni, Co, Ru and the Re, and cobalt is preferred.Preferred Fischer-Tropsch catalyst contains the cobalt of effective quantity and among Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and the La one or more on the inorganic carrier material that is fit to, the preferred inorganic support material is the material that contains one or more infusible metal oxides.Usually, in the catalyzer content of cobalt be whole catalyst composition about 1 to about 50 weight %.Catalyzer also can contain basic oxide promotor, for example ThO
2, La
2O
3, MgO and TiO
2, other promotor, for example ZrO
2, precious metal (Pt, Pd, Ru, Rh, Os, Ir), coinage metals (Cu, Ag, Au) and other transition metal, for example Fe, Mn, Ni and Re.The solid support material that is fit to comprises aluminum oxide, silicon oxide, magnesium oxide and titanium oxide or its mixture.For the catalyzer that contains cobalt, preferred carrier comprises titanium oxide.The Catalysts and its preparation method that is suitable for is known, and explanation in U.S. patent 4,568,663, and it only is used for explanation, rather than the restriction that catalyzer is selected.
Known some catalyzer can provide and be low to moderate medium chainpropagation probability relatively, and reaction product comprises a high proportion of relatively lower molecular weight (C
2-8) alkene and the relative high molecular (C that hangs down ratio
30+) wax.Known some other catalyzer can provide high relatively chainpropagation probability, and reaction product comprises the lower molecular weight (C of low relatively ratio
2-8) alkene and relative a high proportion of high molecular (C
30+) wax.For those skilled in the art, such catalyzer is that everybody is familiar with, and can be easy to obtain and/or prepare.
The product that Fischer-Tropsch synthesis obtains mainly contains alkane.The product that F-T synthesis reaction obtains comprises lightweight reaction product and wax reaction product usually.Lightweight reaction product (condensate fraction just) comprises the hydro carbons (for example tail gas is to midbarrel fuel) that boiling point is lower than about 700 , and is most of at C
5-C
20Scope is a small amount of high to about C
30Wax reaction product (wax slop just) comprises the hydro carbons (for example vacuum gas oil is to heavy paraffin) that boiling point is higher than about 600 , and is most of at C
20+Scope is low to moderate C on a small quantity
10
Lightweight reaction product and waxy product both are mainly alkane.Waxy product contains usually greater than 70 weight % normal paraffins, usually greater than 80 weight % normal paraffins.The lightweight reaction product contains the alcohols and the alkene of alkane product and remarkable ratio.In some cases, the lightweight reaction product can contain nearly 50 weight % and even more alcohols and alkene.The raw material that can be used as the inventive method is wax reaction product (wax slop just).
Hydroisomerization
According to the present invention, the wax hydrocarbon raw material is carried out hydroisomerization in the hydroisomerization section, isomerized oil in the middle of generating.
Hydroisomerization is intended to by branch's selectivity being added to the cold flow characteristics of improving lubricant base in the molecular structure.The hydroisomerization dewaxing will realize the high level of conversion of waxy feed to non-wax isoparaffin in theory, minimize and cracking is transformed.
According to the present invention, carry out hydroisomerization with selecting the shape mesoporous molecular sieve.Be applicable to that hydroisomerisation catalysts of the present invention is included in the metal hydrogenation component of selecting the shape mesoporous molecular sieve and randomly comprising catalytic activity on the infusible oxide carrier.Term used herein " mesopore " is meant that when porous inorganic oxide is calcined form effective pore radius is in about 4.0 to about 7.1 scope.Be used for the shape mesoporous molecular sieve of selecting of the invention process and be generally 10,11 or 12 yuan of toroidal molecule sieves of 1-D.The preferred molecular sieve of the present invention is 10 yuan of toroidal molecules of 1-D sieves, and here the first toroidal molecule sieve of 10-(or 11-or 12-) has the atom (T-atom) of the individual tetrahedral coordination that is connected by oxygen in 10 (or 11 or 12).In the 1-D molecular sieve, 10 yuan of rings (or bigger) hole is parallel to each other and does not interconnect.R.M.Barrer is at Zeolites, Science and Technology, editedby F.R.Rodrigues, L.D.Rollman and C.Naccache, NATO ASISeries, explanation zeolite inner duct is categorized as 1-D, 2-D and 3-D in 1984, and the full content of its classification is incorporated (particularly referring to the 75th page) as a reference into.
What be used for hydroisomerization preferably selects the shape mesoporous molecular sieve based on aluminum phosphate, for example SAPO-11, SAPO-31 and SAPO-41.SAPO-11 and SAPO-31 are preferred, and SAPO-11 is most preferred.SM-3 is a kind of particularly preferred shape mesopore SAPO that selects, and its crystalline texture is in the crystalline texture scope of SAPO-11 molecular sieve.The preparation of SM-3 and unique characteristic thereof be at U.S. patent Nos.4, and be open in 943,424 and 5,158,665.The shape mesoporous molecular sieve of preferably selecting that is used for hydroisomerization also has some zeolites, for example ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite and ferrierite like this.SSZ-32 and ZSM-23 are preferred.
The characteristics of preferred mesoporous molecular sieve are the free diameter of crystallography in selected duct, selected crystallite dimension (corresponding to selected orifice throat length) and selected acidity.The free diameter of the crystallography of desirable molecular sieve pore passage is about 4.0 to about 7.1 scopes, and the maximum free diameter of crystallography is not more than 7.1 , and the free diameter of crystallography of minimum is not less than 3.9 .Preferably, the maximum free diameter of crystallography is not more than 7.1 , and the minimum free diameter of crystallography is not less than 4.0 .Most preferably, the maximum free diameter of crystallography is not more than 6.5 , and the minimum free diameter of crystallography is not less than 4.0 .The free diameter of the crystallography of molecular sieve pore passage is in " zeolite framework type atlas ", Fifth Revised Edition, 2001, by Ch.Baerlocher, W.M.Meier, and D.H.Olson, Elsevier delivers among the pp 10-15, here incorporates into as a reference.
The particularly preferred mesoporous molecular sieve that is applicable to present method is for example at US patent No.5, and open in 135,638 and 5,282,958, its full content is incorporated into as a reference.At US patent No.5, in 282,958, the crystallite dimension of such mesoporous molecular sieve is not more than about 0.5 micron, and the minimum diameter in hole is at least about 4.8 , and maximum diameter is about 7.1 .Catalyzer has enough acidity, so that the 0.5g catalyzer makes at least 50% n-Hexadecane transform under the feeding rate of 370 ℃, the hydrogen flow velocity of the pressure of 1200psig, 160ml/min and 1ml/hr when being contained in the tubular reactor.Make 96% normal cetane (n-C when being used in
16) change under the condition of other thing class, catalyzer also demonstrate 40% or bigger isomerization selectivity (the isomerization selectivity is following to be determined: 100 * (side chain C in the product
16Weight %)/(side chain C in the product
16Weight %+ product in C
13-weight %).
The free diameter of the also available crystallography of particularly preferred molecular sieve like this is that about 4.0 hole or ducts to about 7.1 , preferred 4.0 to 6.5 characterize.The free diameter of the crystallography of molecular sieve pore passage is in " zeolite framework type atlas ", Fifth Revised Edition, 2001, by Ch.Baerlocher, W.M.Meier, and D.H.Olson, Elsevier delivers among the pp 10-15, here incorporates into as a reference.
If the free diameter the unknown of the crystallography of molecular sieve pore passage, the effective pore radius available standards adsorption technology of molecular sieve and the hydrocarbon compound of known minimum power diameter are measured so.Referring to Breck, zeolite molecular sieve, 1974 (particularly the 8th chapters); Anderson et al.J.Catalysis 58,114 (1979) and U.S. patent No.4,440,871, here its relative section is incorporated into as a reference.In the absorption of measuring the aperture is measured, use standard techniques.If (p/po=0.5 in less than about 10 minutes; 25 ℃) do not reach at least 95% equilibrium adsorption value on the molecular sieve, be suitable for specific molecule is got rid of.It is the molecule of 5.3-6.5 that mesoporous molecular sieve will be admitted the power diameter usually, does not almost hinder.
Be applicable to that hydroisomerisation catalysts of the present invention randomly comprises the hydrogenation metal of catalytic activity.The existence of catalytic activity hydrogenation metal is improved product, particularly VI and stability.Typical catalytic activity hydrogenation metal comprises chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum and palladium.Metal platinum and palladium are particularly preferred, and platinum is the most particularly preferred.If use platinum and/or palladium, the total amount of active hydrogenation metal is generally the 0.1-5 weight % of whole catalyzer, is generally 0.1-2 weight %, but is no more than 10 weight %.
Refractory oxide can be selected from those oxide carriers that is used for various catalyzer traditionally, comprising silicon oxide, aluminum oxide, silica-alumina, magnesium oxide, titanium oxide and combination thereof.
With adjusting the condition of hydroisomerization, so that had the middle isomerized oil of specific branch character as mentioned above, therefore described condition will depend on the characteristic of used charging.Usually, the hydroisomerization condition is a demulcent among the present invention, so that in the middle of generating in the isomerized oil process, and wax generates transformation efficiency that boiling point is lower than the material of about 700 and is maintained at and is lower than about 35 weight %.
By at the lesser temps of common about 390 to 650 , about 0.5hr usually
-1To about 20hr
-1LHSV down operation reach the mild hydrogenation isomerisation conditions.Pressure is generally about 15psig to about 2500psig, preferred extremely about 2000psig, 100psig about 1500psig extremely more preferably from about of about 50psig.Low pressure improves the isomerization selectivity, thereby makes more isomerization of charging and still less cracking, and productive rate is improved.
In hydroisomerization process, there is hydrogen in the conversion zone, hydrogen/charge ratio is that about 0.5 to 30MSCF/bbl (MSCF (Thousand standard cubic feet)/bucket), preferred about 1 is to about 10MSCF/bbl usually.Hydrogen can be separated from product, and be recycled to conversion zone.
The mild hydrogenation isomerisation conditions that the shape mesoporous molecular sieve is selected in these uses produces the middle isomerized oil that comprises the alkane component (just having a spot of overall branch) with specific branch character.
As mentioned above, as with the assay determination of NMR branch, described in the middle of per 100 carbon of isomerized oil have less than 7.0, preferably less than 6.5 alkyl branches.
Solvent dewaxing
According to the present invention, isomerized oil in the middle of described is carried out solvent dewaxing, obtain comprising the lubricant base of alkane component with optimized branching character.So solvent dewaxing obtains comprising the lubricant base with a spot of overall ramose alkane component, described branch concentrates to the middle part of molecule.
Solvent dewaxing is used for removing residual waxy molecules from middle isomerized oil by following steps: middle isomerized oil is dissolved in solvent for example methylethylketone, methyl iso-butyl ketone (MIBK) or toluene, or make the wax molecule deposition, as at petrochemical technology, 3rd Edition, William Gruseand Donald Stevens, McGraw-Hill Book Company, Inc., New York, 1960, pages 566 to 570.Also referring to US patent 4,477,333,3,773,650 and 3,775,288.In the present invention, advantageously make solvent dewaxing later at hydroisomerization, so that be recovered under the mitigation condition unconverted wax after the hydroisomerization, wherein wax generates boiling point and is lower than the transformation efficiency of material of about 700 less than about 35%.
According to the present invention, traditional method that available those skilled in the art are familiar with is carried out solvent dewaxing.Can realize solvent dewaxing by isomerized oil/solvent mixture in the middle of the cooling under controlled condition, so that make the alkane that exists in the mixture belong to the wax crystallization.In such method, middle isomerized oil and dewaxing solvent are heated to wax dissolved temperature.Material with heating enters cooling section then, in cooling section, cool off with the uniform slow rate of about 0.5 to 4.5 ℃/min, until reach the wax of major portion by the temperature of crystallization (for example-10 ° to-20 ℃), and have selected pour point temperature through the lube base oil production of dewaxing.When reaching desirable dewaxing temperature, the mixture of wax crystalls, middle isomerized oil and solvent is carried out solid-liquid separate, so that reclaim not the oil-solvent solution of the content of wax and the solid wax that contains a small amount of oil.The solid-liquid isolation technique can be used for separating wax crystalls and oil-solvent solution, and they comprise known solid-liquid separation method, for example gravity settling, centrifugal and filtration.The most frequently used is that in various business methods, use is filtered in rotary vacuum filter, then carries out the solvent wash of wax filter cake.Solid wax/oil solution that solid wax obtains after separating is called as gatch (slack wax).
Isolating oil-solvent solution is distilled, so that reclaim the lubricant base product cut of solvent cut and dewaxing.This method is at US patent No.5, and open in 413,695, its content is all incorporated this paper as a reference into.
Known to be suitable for the solvent make dewaxing solvent be the ketone that contains 3-6 carbon atom, for example acetone, methylethylketone (MEK) and methyl iso-butyl ketone (MIBK) (MIBK), the mixture of ketone and ketone and comprise benzene and the mixture of the aromatic hydrocarbons of toluene.Halogenated low molecular weight hydrocarbons that comprises methylene dichloride and ethylene dichloride and composition thereof also is known dewaxing solvent.The solvent cut of wax oil plant makes oil product keep mobile, to be convenient to the handling pressed oil productive rate that obtains best wax-oil separation and obtain the best.The degree of solvent cut depend on concrete middle isomerization oil plant and use solvent, in cooling section, reach the approach of filtration temperature and desirable final solvent/oil ratio in segregation section.
The all wax removed in the step in dewaxing or the wax of part are all recyclable and be recycled to hydroisomerisation step and be used for other purposes (for example be processed into or as vendible wax) for use in method of the present invention and/or through collection.When the wax of all or part of recovery of circulation, described wax can carry out separately hydroisomerisation step of the present invention or can with the combination of other waxy feed.The wax of all or part of recovery of circulating improves the productive rate of method.
After solvent dewaxing, obtain comprising the lubricant base of alkane component with best branch.Optimized branching is meant that lubricant base comprises and has a spot of overall ramose alkane component, and described branch concentrates to the middle part of molecule.The kinematic viscosity of the lubricant base that comprises the alkane component with optimized branching under 100 ℃ that reclaims from the inventive method is greater than about 3.2cSt.In addition, as preamble regulation, the viscosity index of lubricant base that comprises the alkane component with optimized branching is greater than the target viscosities index of oil product.Preferably, the viscosity index of lubricant base of the present invention adds 5 greater than the target viscosities index of oil product.Described lubricant base also have less than-8 ℃, preferably less than-9 ℃, more preferably≤-15 ℃ and even be more preferably less than-15 ℃ pour point.
Usually, the pour point difference in the middle of before the pour point of lubricant base and the solvent dewaxing between the isomerized oil is greater than about 25 .
Hydrofining
Can be with comprising the lubricant base of alkane component or randomly middle isomerized oil being carried out hydrofining, so that improve the quality and the stability of product with optimized branching.In unifining process, total LHSV is about 0.25 to 2.0, preferred about 0.5 to 1.0.The hydrogen dividing potential drop is greater than 200psia, preferably about 500psia is to about 2000psia.The hydrogen cycle rate is usually greater than 50SCF/Bbl, preferred 1000-5000SCF/Bbl.Temperature is that about 300 are to about 750 , preferred 450 -600 .
The Hydrobon catalyst that is fit to comprises VIIIA family precious metal (according to 1975 rules of International Union of Pure and Applied Chemistry), for example at aluminum oxide or contain platinum or palladium on the silicon matrix, and unvulcanized VIIIA and group vib metal, for example at aluminum oxide or contain nickel-molybdenum or nickel-Xi on the silicon matrix.U.S. patent No.3,852,207 disclose a kind of suitable noble metal catalyst and mitigation condition.For example at U.S. patent No.4, other catalyzer that is fit to is disclosed in 157,294 and U.S. patent No.3,904,513.Base metal (for example nickel-molybdenum and/or tungsten and at least about 0.5 nickel and/or the cobalt (measuring) of (usually about 1 to about 15) weight % as corresponding oxide compound.Precious metal (for example platinum) catalyzer contains greater than 0.01% metal, preferred 0.1-1.0% metal.Also can use the combination of precious metal, for example the mixture of platinum and palladium.
Lubricant base with optimized branching
Lubricant base of the present invention comprises the alkane component that branch wherein is optimized.The lubricant base that comprises the alkane component with optimized branching has high viscosity, low pour point and high VI.The kinematic viscosity of lubricant base of the present invention under 100 ℃ greater than about 3.2cSt, be preferably about 3.2 to about 20cSt.In addition, lubricant base of the present invention comprise average carbon number greater than about 27, be preferably greater than about 30, more preferably greater than about 27 and less than about 70 alkane component.
American Petroleum Institute (API) (API) classifies to it according to the chemical constitution of base oil.As API definition, III class oil is the oil (＞120) of very high viscosity index (HVI), its total sulfur content less than 300ppm and saturated compound content more than or equal to 90%.API III class oil traditionally also with harsh hydrocracking and or the wax isomerization produce.Lubricant base of the present invention is classified as AP IIII class base oil usually.When they when for example the charging of f-t synthetic wax matter is produced by the waxy feed of low total sulfur content, lubricant base also will have the total sulfur content less than 300ppm.
The common total sulfur content of lubricant base of the present invention of being produced by the charging of f-t synthetic wax matter is less than about 5ppm, and saturated compound content is greater than 95%, and always naphthene content is 0 to about 8%, preferred 0 to about 5%.Total sulfur is pressed ASTM D 5453-00 with ultraviolet fluorescence method and is measured.
Particularly, described lubricant base comprise per 100 carbon have less than 8 alkyl branches, preferred per 100 carbon have less than 7 alkyl branches, more preferably per 100 carbon have less than 6.5 alkyl ramose alkane components.As with NMR branch assay, in 2 branches less than 20 weight %, preferably less than 15 weight %.Add 3 branch less than 25 weight %, preferably less than 20 weight % 2.In addition, the branch of 5 or 5 above positions greater than 50 weight %, be preferably greater than 60 weight %.The uncombined carbon index of lubricant base of the present invention usually greater than about 3, be preferably greater than about 5.
Lubricant base of the present invention comprises such alkane component, wherein branch degree of being measured by the percentage ratio of methyl hydrogen (BI) and the proximity (CH of branch that is measured by the percentage ratio of multiple mesomethylene carbon (they have four or more carbon apart from an end group or branch)
2＞4) be such: BI-0.5 (CH
2＞4), keep low pour point simultaneously less than 12.Preferably, lubricant base of the present invention has such branch, thus BI-0.5BP less than 10, be more preferably less than 8 even be more preferably less than 6, keep low pour point simultaneously.
Pour point is that the lube base oil samples will begin the mobile temperature under the condition of careful control.Unless add explanation in addition, the pour point that this paper provides is measured with standard method of analysis ASTM D 5950-02.The lubricant base that the present invention has optimized branching has fabulous pour point.The pour point of lubricant base less than-8 ℃, preferably less than-9 ℃, more preferably≤-15 ℃ even be more preferably less than-15 ℃.
Cloud point is to replenish an observed value of pour point, and it is represented as the temperature that the lube base oil samples begins to become turbid under careful defined terms.The for example available ASTM D5773-95 of cloud point measures.The present invention has the cloud point of lubricant base of optimized branching less than 0 ℃.
The viscosity index that comprises the lubricant base of the alkane component with optimized branching is high and greater than the target viscosities index of lubricant base, the target viscosities index that is preferably greater than lubricant base adds 5.The kinematic viscosity range of lubricant base with optimized branching can be about 3.2cSt to about 20cSt (under 100 ℃) greater than 3.2cSt (under 100 ℃).
Owing to use mild hydrogenation isomerization dewaxing method aborning, the total naphthenic hydrocarbon % in the lubricant base normally low or do not have.Usually, when having naphthenic hydrocarbon, naphthenic hydrocarbon almost only is monocycle alkane form.In lubricant base, the naphthenic hydrocarbon total amount of existence is 0 to about 8 weight %, preferred 0 to about 5 weight %.Naphthenic hydrocarbon is measured with field ionization mass spectroscopy (FIMS), as Kramer, D.C., Deng, be 1999 AIChE Spring National Meetingin Houston, the text of a statement or speech that March 16,1999 prepares was described in " II and III class base oil are formed the influence to VI and oxidative stability ".Total naphthenic hydrocarbon percentage composition of lubricant base of the present invention is by measuring with FIMS monocycle alkane %, dicyclo alkane %, three naphthenic hydrocarbon %, Fourth Ring alkane %, five rings alkane % and the six naphthenic hydrocarbon % of each sample measurement being sued for peace.
Because lubricant base of the present invention has extremely low aromatic hydrocarbons and polycyclic naphthene hydrocarbon content, lubricant base has superior oxidative stability.As U.S. patent No.3,852,207 is disclosed, and a method measuring the lubricant base oxidative stability is Oxidator BN test.Oxidator BN test is measured oxidation-resistance with Dornte type oxygen absorption equipment.R.W.Dornte " oxidation of white oil ", Industrial and Engineering Chemistry, Vol.28, page 26,1936.Usually, condition is the next atmospheric pure oxygens of 340 .The result absorbs 1000ml O with 100g oil
2Hours represent.In Oxidator BN test, every 100g oil uses the 0.8ml catalyzer, comprises additive formulations (additive package) in the oil that will test.Catalyzer is the mixture of soluble metal-naphthenate in kerosene, the average metal analysis of the useless crankcase oils of simulation.The concentration of metal in catalyzer is as follows: copper=6,927ppm; Iron=4,083ppm; Plumbous=80,208ppm; Manganese=350ppm and tin=3565ppm.Additive formulations is that the oil that every 100g will test has 80 mmole propylene dimer phenyl zinc dithiophosphates.Oxidator BN measures the response of lubricant base in simulation application.High numerical value, or absorb the long-time of 1 liter of oxygen, showing has good oxidative stability.For general application, the Oxidator BN of lubricant base surpasses 7 hours to wish.For lubricant base of the present invention, Oxidator BN value greater than about 15 hours, be preferably greater than about 30 hours.
Tempered oil
Lubricant base of the present invention can use separately, or can concoct with other base oil that is selected from the group of being made up of conventional I class base oil, conventional I I class base oil, conventional I II class base oil, isomerized petroleum wax, poly-alpha olefins (PAO), poly-internal olefin (PIO), diester, polyol ester, phosphoric acid ester, alkylating aromatic hydrocarbons and composition thereof.
Alkylating aromatic hydrocarbons is aromatic hydrocarbons and haloalkane, alcohol or the alkene ucon oil that alkylation obtains in the presence of Lewis acid or cloth Leinster acid catalyst.At " ucon oil and performance function liquid ", edited by Ronald L.Shubkin, 1993, provide the summary of alkylating aromatic hydrocarbons lubricating oil among the pp 125-144, here incorporate into as a reference.The suitable example of alkylated aromatic hydrocarbons is alkylating naphthalene and alkylating benzene.Alkylating aromatic hydrocarbons has good cryogenic properties, and can with the tempered oil of other base oil in improved additive solvability and performance are provided.
Because lubricant base of the present invention has fabulous cryogenic flowing property, high VI and high oxidative stability, so they are ideal blending oil plants of upgrading conventional lubrication oil base oil.
When lubricant base of the present invention and one or more other lubricant base blendings, preferably below the 95 weight % of the content of other base oil for whole base oil composition of generation.
Finished lube
Lubricant base is a most important component in the finished lube, accounts for more than 70% of finished lube usually.Finished lube comprises lubricant base and at least a additive.Finished lube can be used for automobile, diesel engine, axle, transmission mechanism and industrial application.Finished lube must meet the technical specification that relevant its expection is used, and stipulates as relevant government agencies.
Lubricant base of the present invention is applicable to various finished commercial prods lubricating oil.Because its fabulous VI and cryogenic properties, lubricant base of the present invention are applicable to preparation and are applicable to the finished lube of many application.In addition, the fabulous oxidative stability of lubricant base of the present invention makes them be applicable to the finished lube that many high temperature are used.
Can comprise that with the additive that obtains the finished lube composition those are intended to improve the additive of the selected character of finished lube with lubricant base of the present invention blending.Typical additive for example comprises anti-wear agent, extreme-pressure additive, purification agent, dispersion agent, oxidation inhibitor, pour point depressant, viscosity index improver, viscosity modifier, friction improver, demulsifying agent, foam preventer, corrosion inhibitor, rust-preventive agent, sealing swelling agent, emulsifying agent, wetting agent, lubricity improver, metal passivator, jelling agent, tackiness agent, sterilant, anti-drilling liquid leakage additive, tinting material etc.
Other hydro carbons, U.S. patent Nos.5 for example, those disclosed hydro carbons in 096,883 and 5,189,012, can with described lubricant base blending, condition is that finished lube has required pour point, kinematic viscosity, flash-point and toxicity character.These other hydro carbons comprises the base oil that is specially adapted to drilling fluid.As an example, U.S. patent No.5,096,883 relate to a kind of nontoxic basically base oil, branched paraffin that it is mainly replaced by the ester function base or branched paraffin or its mixture are formed, and each molecule of base oil is preferably had an appointment 18 to about 40 carbon atoms, more preferably each molecule has an appointment 18 to about 32 carbon atoms.U.S. patent No.5,189,012 relate to being selected from by one or more and contain C
2To C
14The synthin of the alkene synthetic branched oligomer of chain length, wherein the molecular-weight average of oligopolymer is 120-1000.
Usually, in the finished lube additive total amount will be approximately finished lube 1 to about 30 weight %.But, because lubricant base of the present invention has fabulous character, comprise low pour point, high VI and fabulous oxidative stability, therefore, may need the additive of less amount than the base oil that makes by other method usually in order to meet the technical specification of finished lube.In the document write up various additives in the application of preparation in the finished lube, be that everybody is familiar with for those skilled in the art.
Embodiment
Further specify the present invention with following illustrative embodiment, these embodiment are not as limitation of the present invention.
Unless add explanation in addition, in this disclosure, all simulation distil boiling Range Distribution Analysis all use standard method of analysis D 6352-98 or its equivalent processes to measure.As used herein, refer to any analytical procedure that can obtain with the substantially the same result of standard method with analytical procedure that D 6352-98 is equal to.
Embodiment 1
Embodiment 1 use and 35 weight %Catapal aluminum oxide adherent Pt/SSZ-32 catalyzer (0.3 weight %Pt) are by n-C
28Charging (buying from Aldrich) makes lubricant base.Once pass through H at 1000psig, 0.8LHSV and 7MSCF/bbl
2Under operate.The temperature of reactor is 575 .The effluent of reactor passes through Pt-Pd/SiO subsequently under 450
2-Al
2O
3Hydrobon catalyst, except temperature, use with isomerization reactor in identical condition.The productive rate of 600 +product is 71.5 weight %.The transformation efficiency that wax generates 600 -boiling range material is 28.5 weight %.The following transformation efficiency of 700 is 33.6 weight %.Tower bottom distillate (75.2 weight %) fractionation under 743 of operation obtains 89.2 weight % bottom products (by whole feed charging meter 67.1 weight %).The character of hydroisomerizing carburetion bottom product is compiled in down Table I:
Table I
The character of hydroisomerizing carburetion bottom product
| Pour point, ℃ | +3 |
| NMR analyzes | |
| C2 branch | 0.26 |
| C3 branch | 0.2 |
| C4 branch | 0.26 |
| C5+ branch | 0.97 |
| Interior ethyl | 0.09 |
| Add up to | 1.78 |
| NMR branch character | |
| Alkyl branch/molecule | 1.78 |
| Alkyl branch/100 carbon | 6.14 |
| 2 ramose percentage ratios | 14.6 |
| 2 add 3 ramose percentage ratios | 25.8 |
| 5 or 5+ position ramose percentage ratio | 54.5 |
Then with these bottom products-15 ℃ of following solvent dewaxings, obtain 84.2 weight % solvent dewaxed oils (by whole feed charging meter 56.5 weight %) and 15.7 weight % waxes.The evaluation of described oil nature is compiled in down Table VI.
Embodiment 2
With n-C
36Charging (buying) isomerization on the Pt/SSZ-32 catalyzer that contains 0.3%Pt and 35%Catapal alumina adhesive from Aldrich.Operational condition is 580 , 1.0LHSV, 1000psig reactor pressure and once passes through hydrogen speed 7MSCF/bbl.The direct feeding of the effluent of reactor is in second reactor of 1000psig equally, and it is equipped with the Pt/Pd Hydrobon catalyst on silica-alumina.Condition in the described reactor: temperature is 450 , and LHSV is 1.0.Transformation efficiency and productive rate are compiled in down Table II:
Table II
| Transformation efficiency＜650 , weight % | 32.2 |
| Transformation efficiency＜700 , weight % | 34.4 |
| Productive rate, weight % | |
| C1-C2 | 0.45 |
| C3-C4 | 5.16 |
| C5-180 | 6.22 |
| 180-350 | 7.40 |
| 350-650 | 13.23 |
| 650+ | 68.09 |
The tower bottom distillate that operation is obtained separates.The character of hydroisomerization bottom product is compiled in down Table III:
Table III
The character of hydroisomerization stripper bottoms product
| Simulation distil, LV%, | |
| Initial boiling point/5 | 677/747 |
| 10/30 | 801/904 |
| 50 | 914 |
| 70/90 | 920/925 |
| 95/ final boiling point | 927/929 |
| Pour point, ℃ | +20 |
Stripper bottoms product is carried out solvent dewaxing with methylethylketone (MEK)/toluene under-15 ℃.Wax content is 31.5 weight %, and oily productive rate is 68.2 weight %.By the feed charging meter of method, the productive rate of 650 +oil of solvent dewaxing is 45.4 weight %.The evaluation of described oil nature is compiled in down Table VI.
Embodiment 3
With f-t synthetic wax isomerization on the Pt/SSZ-32 catalyzer of hydrotreatment, described catalyzer contains 0.3%Pt and 35%Catapal alumina adhesive.Operational condition is 560 , 1.0LHSV, 300psig reactor pressure and once passes through hydrogen speed 6MSCF/bbl.The direct feeding of the effluent of reactor is in second reactor of 300psig equally, and it is equipped with the Pt/Pd Hydrobon catalyst on silica-alumina.Condition in the described reactor: temperature is that 450 and LHSV are 1.0.The character of the f-t synthetic wax of hydrotreatment is compiled in down Table IV.The character of transformation efficiency and productive rate and hydroisomerization stripper bottoms product is compiled in down Table V.
Table IV
The inspection of the f-t synthetic wax of hydrotreatment (951-15-431)
Proportion, API 40.3
Nitrogen, ppm 1.6
Total sulfur, ppm 2
Simulation distil, weight %,
Initial boiling point/5 512/591
10/30 637/708
50 764
70/90 827/911
95/ final boiling point 941/1047
Table V
Under 560 , 1LHSV, 300psig and 6MSCF/bbl H2
The isomerization of f-t synthetic wax on Pt/SSZ-32
Transformation efficiency＜650 , weight % 15.9
Transformation efficiency＜700 , weight % 14.1
Productive rate, weight %
C1-C2 0.11
C3-C4 1.44
C5-180 1.89
180-290 2.13
290-650 21.62
650+ 73.19
Stripper bottoms product:
Productive rate, the weight % 75.9 of charging
Simulation distil, LV%,
Initial boiling point/5 588/662
30/50 779/838
95/99 1070/1142
Pour point, ℃+25
NMR analyzes:
C2 branch 0.28
C3 branch 0.23
C4 branch 0.26
C5+ branch 1.00
Interior ethyl-10 .11
Add up to 1.88
NMR branch character:
Alkyl branch/molecule 1 .88
Alkyl branch/100 carbon 6.21
2 ramose percentage ratios 14.9
2 add 3 ramose percentage ratios 27.1
5 or 5+ position ramose percentage ratio 53.2
Stripper bottoms product is carried out solvent dewaxing with MEK/ toluene down at-15 ℃.Wax content is 33.9 weight %, and oily productive rate is 65.7 weight %.By the feed charging meter of method, the productive rate of 650 +oil of solvent dewaxing is 49.9 weight %.The evaluation of described oil nature is compiled in down Table VI.
Table VI
The character of hydroisomerized wax after the solvent dewaxing
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| NMR analyzes ethyl total in the C5+ branch of C4 branch of C3 branch of C2 branch | 0.24 0.14 0.18 1.12 0.07 1.75 | 0.27 0.22 0.23 1.75 0.13 2.60 | 0.27 0.18 0.21 1.1 0.1 1.86 |
| Branch's index (BI) | 19.7 | 18.8 | 19 |
| Branch's proximity (BP) | 28.5 | 29.6 | 28.1 |
| The alkyl branch of each molecule | 1.68 | 2.47 | 1.76 |
| BI-0.5BP | 5.45 | 4.00 | 4.95 |
| Uncombined carbon index (FCI) | 7.90 | 11.00 | 7.70 |
| The alkyl branch of per 100 carbon | 6.04 | 6.66 | 6.42 |
| 2 ramose percentage ratios | 13.7 | 10.4 | 14.5 |
| 2+3 position ramose percentage ratio | 21.7 | 18.8 | 24.2 |
| 5 or 5+ position ramose percentage ratio | 64.0 | 67.3 | 59.1 |
| Viscosity index | 165 | 182 | 175 |
| Viscosity under 100 ℃ | 3.447 | 5.488 | 3.776 |
| Viscosity under 40 ℃ | 12.43 | 23.62 | 13.90 |
| Pour point, ℃ | -15 | -9 | -18 |
| Cloud point, ℃ | -4 | -3 | -5 |
| Average carbon number | 27.8 | 37.1 | 27.4 |
| Simulation distil, LV%, initial boiling point/5 10,/30 50 70,/90 95/ final boiling point | 683/748 792/902 912 919/923 924/926 | 608/652 670/718 775 890/953 1004/1116 | |
| FIMS analyzes alkane % five rings, % alkane % monocycle alkane % bicyclic alkane % three cycloalkane % Fourth Ring alkane % six cycloalkane and adds up to | 100 0 0 0 0 0 0 100 | 98 1.7 0 0 0 0 0 99.7 | 96 4 0 0 0 0 0 100 |
| Oxidator BN, hour | 31.87 |
For those skilled in the art, under the situation of scope and spirit essence of the present invention, various modifications of the present invention and change all are conspicuous.For those skilled in the art, according to the review to aforementioned content, other purpose and advantage also are conspicuous.
Claims (30)
1. lubricant base, it comprises branch degree is that per 100 carbon have less than 8 alkyl branches and at 2 described alkyl ramose alkane components that have less than 20 weight %; The pour point of described lubricant base is less than-8 ℃; Kinematic viscosity under 100 ℃ is about 3.2cSt or bigger; And viscosity index is greater than the target viscosities index that calculates in order to following equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132.
2. according to the lubricant base of claim 1, wherein to contain branch degree be that per 100 carbon have less than 7 alkyl ramose alkane components to lubricant base.
3. according to the lubricant base of claim 1, wherein to contain branch degree be that per 100 carbon have less than 6.5 alkyl ramose alkane components to lubricant base.
4. according to the lubricant base of claim 1, wherein lubricant base contains 2 and adds 3 described alkyl ramose alkane components that have less than 25 weight %.
5. according to the lubricant base of claim 1, wherein lubricant base contains the described alkyl ramose alkane component that has 5 or bigger position greater than 50 weight %.
6. according to the lubricant base of claim 1, wherein said viscosity index adds 5 greater than the target viscosities index.
7. according to the lubricant base of claim 1, wherein lubricant base contains the described alkyl ramose alkane component that has less than 15 weight % at 2.
8. according to the lubricant base of claim 1, wherein lubricant base contains 2 and adds 3 described alkyl ramose alkane components that have less than 20 weight %.
9. according to the lubricant base of claim 1, wherein lubricant base contains the described alkyl ramose alkane component that has 5 or bigger position greater than 60 weight %.
10. according to the lubricant base of claim 1, it also contains the total naphthene content less than about 5 weight %.
11. according to the lubricant base of claim 1, wherein lubricant base is obtained by Fischer-Tropsch synthesis.
12. according to the lubricant base of claim 1, wherein lubricant base contains alkane component, branch degree of being measured by the percentage ratio of methyl hydrocarbon in the described alkane component (BI) and the proximity (CH of branch that is measured by the percentage ratio of multiple mesomethylene carbon
2＞4) as follows: BI-0.5 (CH
2＞4)＜12; Described multiple mesomethylene carbon has four or more a plurality of carbon apart from an end group or branch.
13. according to the lubricant base of claim 1, wherein lubricant base contains alkane component, branch degree of being measured by the percentage ratio of methyl hydrocarbon in the described alkane component (BI) and the proximity (CH of branch that is measured by the percentage ratio of multiple mesomethylene carbon
2＞4) as follows: BI-0.5 (CH
2＞4)＜10; Described multiple mesomethylene carbon has four or more a plurality of carbon apart from an end group or branch.
14. according to the lubricant base of claim 1, wherein the uncombined carbon index of lubricant base is greater than about 3.
15. according to the lubricant base of claim 11, wherein lubricant base contains the sulphur content less than about 5ppm.
16. according to the lubricant base of claim 1, wherein the Oxidator BN value of lubricant base was greater than 25 hours.
17. according to the lubricant base of claim 1, it also comprises other base oil that is selected from the group of being made up of traditional I class base oil, traditional II class base oil, traditional III class base oil, isomerization petroleum wax, poly-alpha olefins, poly-internal olefin, diester, polyol ester, phosphoric acid ester, alkylated aromatic hydrocarbons and composition thereof.
18. according to the lubricant base that contains alkane component of claim 1, wherein branch degree is that per molecule has less than 2.5 alkyl branches.
19. according to the lubricant base that contains alkane component of claim 1, wherein branch degree is that per molecule has less than 2.0 alkyl branches.
20. according to the lubricant base that contains alkane component of claim 1, wherein the pour point of lubricant base is less than-9 ℃.
21. according to the lubricant base that contains alkane component of claim 1, the pour point of lubricant base≤-15 ℃ wherein.
22. a lubricant base, it comprises:
Pour point less than-8 ℃;
Under 100 ℃ greater than the kinematic viscosity of 3.2cSt; And
Greater than the target viscosities exponential viscosity index of calculating in order to following equation:
Target viscosities index=22 * ln (kinematic viscosity under 100 ℃)+132.
23. according to the lubricant base of claim 22, wherein the pour point of lubricant base is less than-9 ℃.
24. according to the lubricant base of claim 22, wherein the pour point of lubricant base less than≤-15 ℃.
25. a finished lube, it comprises:
The lubricant base of claim 1; And
One or more lubricating oil additives.
26. according to the finished lube of claim 25, it also comprises other base oil that is selected from the group of being made up of traditional I class base oil, traditional II class base oil, traditional III class base oil, isomerization petroleum wax, poly-alpha olefins, poly-internal olefin, diester, polyol ester, phosphoric acid ester, alkylated aromatic hydrocarbons and composition thereof.
27. a finished lube, it comprises:
The lubricant base of claim 22; And
One or more lubricating oil additives.
28. according to the finished lube of claim 27, it also comprises other base oil that is selected from the group of being made up of traditional I class base oil, traditional II class base oil, traditional III class base oil, isomerization petroleum wax, poly-alpha olefins, poly-internal olefin, diester, polyol ester, phosphoric acid ester, alkylated aromatic hydrocarbons and composition thereof.
29. isomerized oil in the middle of a kind, it comprises the branch degree that Fischer-Tropsch process makes is that per 100 carbon have less than 7 alkyl ramose alkane components.
30. according to the middle isomerized oil of claim 29, it is that per 100 carbon have less than 6.5 alkyl ramose alkane components that wherein middle isomerized oil contains branch degree.
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| US10/682,965 US20050077208A1 (en) | 2003-10-14 | 2003-10-14 | Lubricant base oils with optimized branching |
| US10/682,965 | 2003-10-14 | ||
| PCT/US2004/030134 WO2005037964A2 (en) | 2003-10-14 | 2004-09-13 | Lubricant base oils with optimized branching |
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| CN1867653B CN1867653B (en) | 2010-06-16 |
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- 2003-10-14 US US10/682,965 patent/US20050077208A1/en not_active Abandoned
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- 2004-09-13 AU AU2004281378A patent/AU2004281378B2/en not_active Ceased
- 2004-09-13 WO PCT/US2004/030134 patent/WO2005037964A2/en active Application Filing
- 2004-09-13 SG SG200807627-5A patent/SG147434A1/en unknown
- 2004-09-13 CN CN2004800303032A patent/CN1867653B/en not_active Expired - Lifetime
- 2004-09-13 JP JP2006535497A patent/JP5336703B2/en not_active Expired - Fee Related
- 2004-09-13 BR BRPI0415265-4A patent/BRPI0415265B1/en not_active IP Right Cessation
- 2004-09-13 ZA ZA200602725A patent/ZA200602725B/en unknown
- 2004-09-23 GB GB0421204A patent/GB2407326B/en not_active Expired - Lifetime
- 2004-10-14 NL NL1027242A patent/NL1027242C2/en not_active IP Right Cessation
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2012
- 2012-07-13 JP JP2012157107A patent/JP5680028B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741068A (en) * | 2017-06-19 | 2020-01-31 | 奈斯特化学公司 | Production of renewable base oils and diesel by pre-fractionation of fatty acids |
| US11142701B2 (en) | 2017-06-19 | 2021-10-12 | Neste Oyj | Process for the production of renewable base oil, diesel and naphtha |
| US11149206B2 (en) | 2017-06-19 | 2021-10-19 | Neste Oyj | Method for converting carboxylic acids and esters into base oil hydrocarbons |
| US11162033B2 (en) | 2017-06-19 | 2021-11-02 | Neste Oyj | Production of renewable base oil and diesel by pre-fractionation of fatty acids |
| US11162044B2 (en) | 2017-06-19 | 2021-11-02 | Neste Oyj | Renewable base oil in lubricant formulations |
| US11339344B2 (en) | 2017-06-19 | 2022-05-24 | Neste Oyj | TiO2 catalyst in ketonisation reactions to produce RBO |
| CN110799631A (en) * | 2017-06-30 | 2020-02-14 | 埃克森美孚研究工程公司 | 13C-NMR-based composition of premium lubricant base oils and methods enabling their design and production and their performance in finished lubricants |
| CN112352036A (en) * | 2018-05-01 | 2021-02-09 | 诺维有限责任公司 | Hydrocarbon mixtures exhibiting a unique branched structure |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2407326A (en) | 2005-04-27 |
| NL1027242A1 (en) | 2005-04-15 |
| GB0421204D0 (en) | 2004-10-27 |
| BRPI0415265B1 (en) | 2014-06-17 |
| BRPI0415265A (en) | 2006-12-12 |
| SG147434A1 (en) | 2008-11-28 |
| JP2007508441A (en) | 2007-04-05 |
| AU2004281378A1 (en) | 2005-04-28 |
| JP5680028B2 (en) | 2015-03-04 |
| CN1867653B (en) | 2010-06-16 |
| JP2012193385A (en) | 2012-10-11 |
| WO2005037964A3 (en) | 2006-03-09 |
| ZA200602725B (en) | 2008-05-28 |
| AU2004281378B2 (en) | 2010-03-11 |
| JP5336703B2 (en) | 2013-11-06 |
| US20050077208A1 (en) | 2005-04-14 |
| GB2407326B (en) | 2007-05-09 |
| NL1027242C2 (en) | 2005-12-23 |
| WO2005037964A2 (en) | 2005-04-28 |
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