WO2005113734A2 - Lubricant blends with low brookfield viscosities - Google Patents
Lubricant blends with low brookfield viscosities Download PDFInfo
- Publication number
- WO2005113734A2 WO2005113734A2 PCT/US2005/017976 US2005017976W WO2005113734A2 WO 2005113734 A2 WO2005113734 A2 WO 2005113734A2 US 2005017976 W US2005017976 W US 2005017976W WO 2005113734 A2 WO2005113734 A2 WO 2005113734A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lubricant
- base oil
- weight percent
- blend
- lubricant blend
- Prior art date
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- 239000000314 lubricant Substances 0.000 title claims abstract description 511
- 239000000203 mixture Substances 0.000 title claims abstract description 280
- 239000002199 base oil Substances 0.000 claims abstract description 356
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- 230000000994 depressogenic effect Effects 0.000 claims abstract description 56
- 239000012208 gear oil Substances 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000001993 wax Substances 0.000 claims description 195
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- 238000000034 method Methods 0.000 claims description 59
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- 239000002244 precipitate Substances 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000011894 semi-preparative HPLC Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- 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
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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- 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
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/06—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a compound of the type covered by group C10M109/00
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- 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
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
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- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/04—Well-defined cycloaliphatic compounds
- C10M2203/045—Well-defined cycloaliphatic compounds used as base material
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- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- 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
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- 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
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- 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
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
- C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/02—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen and halogen only
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- 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
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- 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
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- 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
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
Definitions
- the present invention is directed to lubricant blends and finished gear oils comprising these lubricant blends, wherein the lubricant blends comprise a lubricant base oil fraction derived from highly paraffimc wax, a petroleum derived base oil, and a pour point depressant.
- the present invention is also directed to processes for making the same. These lubricant blends have good low temperature properties, including surprisingly low Brookfield viscosities.
- lubricant manufacturers must provide finished lubricants that exhibit high performance properties.
- premium quality gear oils have very tough low temperature performance specifications as specified by Brookfield viscosities at -40 °C.
- Finished lubricants, including gear oils consist of two general components: one or more lubricant base oils and additives.
- Lubricant base oil is the major, constituent in these finished lubricants and contributes significantly to the properties of the finished lubricant.
- a few lubricant base oils can be used to manufacture a wide variety of finished lubricants by varying the mixtures of individual lubricant base oils and individual additives.
- Brookfield viscosities are typically adjusted by the addition of pour point depressant to the base oil. Specific viscosities at 100 °C are controlled by blending one or more base oils having different viscosities together.
- lubricant manufacturers are seeking higher quality lubricant base oil blend stocks.
- a growing source of these high quality lubricant base oil blend stocks is synthetic lubricants. Synthetic lubricants can be made from highly paraffimc waxes.
- Synthetic lubricants include Fischer-Tropsch lubricant base oils, and in the search for high performance lubricants, attention has recently been focused on Fischer-Tropsch derived lubricants.
- Fischer-Tropsch lubricant base oils are desirable for their biodegradability and low amounts of undesirable impurities such as sulfur, the Fischer-Tropsch derived lubricants generally do not exhibit all of the desirable performance characteristics.
- additives are generally expensive and thus, can significantly increase the cost of the lubricant base oil.
- the addition of additives may not be sufficient to achieve the desired performance characteristics.
- WO 99/41332 and WO 02/070636 are directed to synthetic lubricant compositions used as automatic transmission fluids and methods for producing these synthetic lubricant base stocks.
- US Patent Application 10/301391 filed on November 20, 2002 and assigned to Chevron U.S.A., relates to lubricant base oil blends comprising a low viscosity Fischer-Tropsch derived base oil fraction and a higher viscosity conventional petroleum derived base oil fraction.
- Patent Application 10/301392 filed on December 23, 2003 and assigned to Chevron U.S.A., discloses a finished lubricant comprising a blend of a Fischer-Tropsch lubricant base oil with high monocycloparaffins and low multicycloparaffins and an additional base oil selected from a group including petroleum derived base oils.
- synthetic lubricants including those comprising Fischer-Tropsch derived lubricant base oils, that exhibit high performance, including good low temperature properties.
- the lubricant blends of the present invention comprising a lubricant base oil fraction derived from highly paraffimc wax, a petroleum derived base oil, and a pour point depressant, exhibit good low temperature properties including excellent low Brookfield viscosities at - 40 °C.
- the present invention relates to a lubricant blend.
- the lubricant blend of the present invention comprises from about 10 to about 80 weight percent based upon the total lubricant blend of a lubricant base oil fraction derived from highly paraffinic wax, from about 20 to about 90 weight percent based upon the total lubricant blend of a petroleum derived base oil, and from about 0.01 to 12 weight percent based upon the total lubricant blend of a pour point depressant, wherein the lubricant blend has a viscosity of about 3 cSt or greater at 100 °C and a Brookfield viscosity at -40 °C of less than 100,000 cP.
- the lubricant base oil fraction derived from highly paraffinic wax has a viscosity of between about 2 cSt and 20 cSt at 100 °C and the lubricant base oil fraction derived from highly paraffinic wax comprises: (i) less than 0.30 weight percent aromatics; (ii) greater than 5 weight percent molecules with cycloparaffimc functionality; and (iii) a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality greater than 15.
- the petroleum derived base oil is selected from the group consisting of a Group II base oil, a Group III base oil, and mixtures thereof.
- the present invention relates to a lubricant blend
- a lubricant blend comprising from about 10 to about 80 weight percent based upon the total lubricant blend of a lubricant base oil fraction derived from highly paraffinic wax, from about 20 to about 90 weight percent based upon the total lubricant blend of a petroleum derived base oil comprising greater than 90 weight percent saturates and less than 300 ppm sulfur, and from about 0.01 to 12 weight percent based upon the total lubricant blend of a pour point depressant.
- the lubricant blend has a viscosity of about 3 cSt or greater at 100 °C and a Brookfield viscosity at -40 °C of less than 100,000 cP.
- the lubricant base oil fraction derived from highly paraffinic wax has a viscosity of between about 2 cSt and 20 cSt at 100 °C and the lubricant base oil fraction derived from highly paraffinic wax comprises: (i) less than 0.30 weight percent aromatics; (ii) greater than 5 weight percent molecules with cycloparaffimc functionality; and (iii) a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality greater than 15.
- the present invention also relates to finished lubricants comprising the lubricant blends having excellent low Brookfield viscosities at - 40 °C as provided herein.
- the finished lubricant is a gear oil comprising the lubricant blends and at least one additive in addition to the pour point depressant.
- the invention relates to a process for producing a lubricant blend comprising providing a lubricant oil fraction derived from highly paraffinic wax having a viscosity of between about 2 cSt and 20 cSt at 100 °C, blending the lubricant oil fraction derived from highly paraffinic wax with a petroleum derived base oil selected from the group consisting of a Group II base oil, a Group III base oil, and mixtures thereof, and a pour point depressant; and isolating a lubricant blend having a Brookfield viscosity at -40 °C of less than 100,000 cP, wherein the lubricant oil fraction derived from highly paraffinic wax comprises less than 0.30 weight percent aromatics; greater than 5 weight percent molecules with cycloparaffinic functionality; and a ratio of weight percent of molecules with monocycl
- Figure 1 illustrates the results of lubricant blends using a 2.5 cSt Fischer-Tropsch derived fraction (FT-2B).
- Figure 2 illustrates the results of lubricant blends using a 4.5 cSt Fischer-Tropsch derived fraction (FT-4A).
- Finished lubricants including gear oils, comprise at least one lubricant base oil and at least one additive.
- Lubricant base oils are the most important component of finished lubricants, generally comprising greater than 70 weight % of the finished lubricants.
- Finished lubricants must meet the specifications for their intended application as defined by the concerned governing organization.
- the finished lubricants according to the present invention are intended for use as gear oils.
- Premium quality gear oils have very tough low temperature performance specifications as specified by Brookfield viscosities at -40 °C.
- the lubricant blends according to the present invention comprise at least one lubricant base oil fraction derived from highly paraffinic wax, a petroleum derived base oil, and a pour point depressant. These lubricant blends have a viscosity of about 3 cSt or greater at 100 °C and have good low temperature properties. In particular, the lubricant blends exhibit a Brookfield viscosities at -40 °C of less than 100,000 cP.
- the lubricant blends exhibit Brookfield viscosities at -40 °C of less than 90,000 cP, more preferably less than 60,000 cP, more preferably less than 50,000 cP, even more preferably less than 35,000 cP, even more preferably less than 25,000 cP, and even more preferably less than 15,000 cP. Accordingly, the lubricant blends of the present invention exhibit exceptional Brookfield viscosities at -40 °C. Thus, the lubricant blends of the present invention can be used to make high quality gear oils.
- Suitable highly paraffinic waxes include Fischer-Tropsch derived wax, slack wax, deoiled slack wax, refined foots oils, waxy lubricant raffinates, n-paraffin waxes, normal alpha olefin (NAO) waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, and mixtures thereof.
- the lubricant base oil fraction derived from highly paraffinic wax of the lubricant blend has a viscosity of between about 2 cSt and 20 cSt at 100 °C.
- the lubricant base oil fraction derived from highly paraffinic wax comprises less than 0.30 weight percent aromatics, greater than 5 weight % molecules with cycloparaffimc functionality, and a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality of greater than 15.
- the lubricant base oil fraction derived from highly paraffinic wax comprises greater than 10 weight percent molecules with cycloparaffimc functionality.
- the lubricant base oil fraction derived from highly paraffinic wax comprises less than 0.30 weight percent aromatics, a weight percent of molecules with monocycloparaffinic functionality of greater than 10, and a weight percent of molecules with multicycloparaffinic functionality of less than 0.1.
- the lubricant base oil fraction derived from highly paraffinic wax comprises a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality of greater than 50.
- the lubricant base oil fraction derived from highly paraffinic wax comprises less than 0.10 weight percent aromatics and more preferably less than 0.05 weight percent aromatics.
- the lubricant base oil fractions derived from highly paraffinic wax of the present invention are prepared from the highly paraffinic wax by a process including hydroisomerization.
- the highly paraffinic wax is hydroisomerized using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component under conditions of about 600°F to 750°F.
- the highly paraffinic wax is a Fischer-Tropsch derived wax and provides a Fischer-Tropsch derived lubricant base oil fraction.
- the lubricant base oil fractions are prepared from the waxy fractions of Fischer-Tropsch syncrude by a process including hydroisomerization.
- the Fischer-Tropsch derived lubricant base oil fractions used in the lubricant blends are made by a process comprising performing a Fischer- Tropsch synthesis to provide a product stream; isolating from the product stream a highly paraffinic wax feed; hydroisomerizing the highly paraffinic wax feed; isolating an isomerized oil; and optionally hydrofinishing the isomerized oil.
- a Fischer-Tropsch derived lubricant base oil fraction comprising less than 0.30 weight percent aromatics, greater than 5 weight % molecules with cycloparaffinic functionality, and a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality of greater than 15 is isolated.
- the above-recited preferred embodiments of the lubricant base oil fractions also may be isolated from this process.
- the highly paraffinic wax feed is hydroisomerized using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component under conditions of about 600°F to 750°F.
- a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component under conditions of about 600°F to 750°F.
- processes for making the Fischer- Tropsch lubricant base oil fractions are described in U.S.S.N. 10/744,870, filed December 23, 2003, herein incorporated by reference in its entirety.
- Examples of embodiments of Fischer- Tropsch lubricant base oil fractions with high monocycloparaffins and low multicycloparaffins are described in U.S.S.N.
- the lubricant blends and the blended finished lubricants comprise lubricant base oils derived from highly paraffinic wax containing high weight percents of molecules with cycloparaffinic functionality because cycloparaffms impart additive solubility and elastomer compatibility.
- Lubricant blends and finished lubricants comprising lubricant base oils derived from highly paraffinic wax containing very high ratios of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality (or high weight percent of molecules with monocycloparaffinic functionality and extremely low weight percent of molecules with multicycloparaffinic functionality) are also desirable because molecules with multicycloparaffinic functionality reduce oxidation stability, lower viscosity index, and increase Noack volatility. Models of the effects of molecules with multicycloparaffinic functionality are given in V.J. Gatto, et al, "The Influence of Chemical Structure on the Physical Properties and Antioxidant Response of Hydrocracked Base Stocks and Polyalphaolefms," J.
- the lubricant blends and finished lubricants according to the present invention comprise a lubricant base oils derived from highly paraffinic wax comprising very low weight percents of molecules with aromatic functionality, a high weight percent of molecules with cycloparaffinic functionality, and a high ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality (or high weight percent of molecules with monocycloparaffinic functionality and very low weight percents of molecules with multicycloparaffinic functionality).
- the lubricant base oils derived from highly paraffinic wax used in the lubricant blends and finished lubricants contain greater than 95 weight % saturates as determined by elution column chromatography, ASTM D 2549-02. Olefins are present in an amount less than detectable by long duration 13 C Nuclear Magnetic Resonance Spectroscopy N ⁇ VTR).
- molecules with aromatic functionality are present in amounts less than 0.3 weight percent by HPLC-UV, and confirmed by ASTM D 5292-99 modified to measure low level aromatics.
- molecules with at least aromatic functionality are present in amounts less than 0.10 weight percent, preferably less than 0.05 weight percent, more preferably less than 0.01 weight percent.
- the petroleum derived base oil fraction of the lubricant blend comprises greater than 90 weight % saturates and less than 300 ppm sulfur.
- the petroleum derived base oil fraction is selected from the group consisting of a Group II base oil, a Group III base oil, and mixtures thereof.
- the petroleum derived base oil fraction can be a heavy neutral base oil, a medium neutral base oil, or a mixture thereof.
- the lubricant blends of the present invention comprise from about 10 to 80 weight % lubricant base oils derived from highly paraffinic wax, from about 20 to 90 weight % petroleum derived base oil, and from about 0.01 to 12 weight % pour point depressant.
- the lubricant blends of the present invention comprise from about 20 to 80 weight % lubricant base oils derived from highly paraffinic wax, from about 20 to 75 weight % petroleum derived base oil, and from about 0.05 to 10 weight % pour point depressant.
- the gear oils of the present invention comprise the lubricant blend and one additive in addition to the pour point depressant.
- the gear oils comprise (a) from about 49 to about 99.9 weight % of the lubricant blend according to the present invention and (b) from about 0.1 to about 51 weight % at least one additive in addition to the pour point depressant.
- the term "derived from a Fischer-Tropsch process” or “Fischer-Tropsch derived,” means that the product, fraction, or feed originates from or is produced at some stage by a Fischer-Tropsch process.
- the term "derived from a petroleum” or “petroleum derived” means that the product, fraction, or feed originates from the vapor overhead streams from distilling petroleum c de and the residual fuels that are the non-vaporizable remaining portion.
- a source of the petroleum derived can be from a gas field condensate.
- Highly paraffinic wax means a wax having a high content of n-paraffins, generally greater than 40 weight %, preferably greater than 50 weight %, and more preferably greater than 75 weight %.
- the highly paraffinic waxes used in the present invention also have very low levels of nitrogen and sulfur, generally less than 25 ppm total combined nitrogen and sulfur and preferably less than 20 ppm.
- highly paraffinic waxes examples include slack waxes, deoiled slack waxes, refined foots oils, waxy lubricant raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, Fischer- Tropsch waxes, and mixtures thereof.
- the pour points of the highly paraffinic waxes useful in this invention are greater than 50°C and preferably greater than 60°C.
- the term "derived from highly paraffinic wax" means that the product, fraction, or feed originates from or is produced at some stage by from a highly paraffinic wax.
- Representative examples include, but are not limited to, benzene, biphenyl, naphthalene, and the like.
- Molecules with cycloparaffinic functionality mean any molecule that is, or contains as one or more substituents, a monocyclic or a fused multicyclic saturated hydrocarbon group. The cycloparaffinic group may be optionally substituted with one or more, preferably one to three, substituents.
- Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, decahydronaphthalene, octahydropentalene, (pentadecan-6-yl)cyclohexane, 3,7,10-tricyclohexylpentadecane, decahydro-l-(pentadecan-6- yl)naphthalene, and the like.
- Molecules with monocycloparaffinic functionality mean any molecule that is a monocyclic saturated hydrocarbon group of three to seven ring carbons or any molecule that is substituted with a single monocyclic saturated hydrocarbon group of three to seven ring carbons.
- the cycloparaffinic group may be optionally substituted with one or more, preferably one to three, substituents. Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, (pentadecan-6-yl)cyclohexane, and the like.
- Molecules with multicycloparaffinic functionality mean any molecule that is a fused multicyclic saturated hydrocarbon ring group of two or more fused rings, any molecule that is substituted with one or more fused multicyclic saturated hydrocarbon ring groups of two or more fused rings, or any molecule that is substituted with more than one monocyclic saturated hydrocarbon group of three to seven ring carbons.
- the fused multicyclic saturated hydrocarbon ring group preferably is of two fused rings.
- the cycloparaffinic group may be optionally substituted with one or more, preferably one to three, substituents.
- Brookfield Viscosity ASTM D 2983-03 is used to determine the low-shear-rate viscosity of automotive fluid lubricants at low temperatures. The low-temperature, low- shear-rate viscosity of automatic transmission fluids, gear oils, torque and tractor fluids, and industrial and automotive hydraulic oils are frequently specified by Brookfield viscosities.
- the GM 2003 DEXRON® III automatic transmission fluid specification requires a maximum Brookfield viscosity at -40°C of 20,000 cP.
- the Ford MERCON® V specification requires a Brookfield viscosity between 5,000 and 13,000 cP.
- Viscosity Classification SAE J306 for 75W gear lubricants has a low temperature viscosity specification such that the maximum temperature for a viscosity of 150,000 cP is -40°C.
- the lubricant blends of this invention will have a Brookfield viscosity at -40°C of less than 100,000 cP, preferably less than 60,000 cP, preferably less than 50,000 cP, more preferably less than 35,000 cP, even more preferably less than 25,000 cP, and even more preferably less than 15,000 cP.
- the lubricant blends and finished gear oils comprising these lubricant blends exhibit desirable properties in addition to exception low Brookfield viscosities at -40°C, including good kinematic viscosity, low Noack volatility, and high oxidative stability, and low pour and cloud points.
- Kinematic viscosity is a measurement of the resistance to flow of a fluid under gravity. Many lubricant base oils, finished lubricants made from them, and the co ⁇ ect operation of equipment depends upon the appropriate viscosity of the fluid being used. Kinematic viscosity is determined by ASTM D 445-01. The results are reported in centistokes (cSt ).
- the lubricant blends of the present invention have a kinematic viscosity of about 3.0 cSt or greater at 100°C. In one embodiment, the lubricant blends have a kinematic viscosity of about 3.0 cSt or greater and less than about 5.0 cSt at 100°C. In another embodiment, the lubricant blends have a kinematic viscosity of about 5.0 cSt or greater and less than about 7.0 cSt at 100°C.
- the lubricant base oil fractions derived from highly paraffinic wax have a kinematic viscosity of between about 2.0 cSt and 20 cSt at 100°C.
- the lubricant base oil fractions derived from highly paraffinic wax may be of varying kinematic viscosities within this range at 100°C.
- lubricant base oil fractions derived from highly paraffinic wax have a kinematic viscosity of between about 2.0 cSt and 12.0 cSt at 100°C.
- the lubricant base oil fractions derived from highly paraffinic wax have a kinematic viscosity of between about 2.0 cSt and 3.0 cSt at 100°C.
- the lubricant base oil fractions derived from highly paraffinic wax have a kinematic viscosity of between about 3.0 cSt and 6.0 cSt at l00°C.
- Viscosity Index (VI) is an empirical, unitless number indicating the effect of temperature change on the kinematic viscosity of the oil. Liquids change viscosity with temperature, becoming less viscous when heated; the higher the VI of an oil, the lower its tendency to change viscosity with temperature. High VI lubricants are needed wherever relatively constant viscosity is required at widely varying temperatures. For example, in an automobile, engine oil must flow freely enough to permit cold starting, but must be viscous enough after warm-up to provide full lubrication.
- the lubricant blends of the present invention have a viscosity index of greater than 120.
- the "Viscosity Index Factor" of the lubricant base oil fractions derived from highly paraffinic wax is an empirical number derived from kinematic viscosity of the lubricant base oil fraction derived from highly paraffinic wax.
- Viscosity Index Factor 28 x ln(Kinematic Viscosity of lubricant base oil fraction derived from highly paraffinic wax at 100°C) + 95
- the lubricant base oil fractions derived from highly paraffinic wax may have a Viscosity Index greater than the Viscosity Index Factor.
- Pour point is a measurement of the temperature at which a sample of lubricant base oil will begin to flow under carefully controlled conditions. Pour point may be determined as described in ASTM D 5950-02. The results are reported in degrees Celsius. Many commercial lubricant base oils have specifications for pour point.
- Cloud point is a measurement complementary to the pour point, and is expressed as a temperature at which a sample of the lubricant base oil begins to develop a haze under carefully specified conditions. Cloud point may be determined by, for example, ASTM D 5773-95. Lubricant base oils having pour-cloud point spreads below about 35°C are desirable. Higher pour-cloud point spreads require processing the lubricant base oil to very low pour points in order to meet cloud point specifications.
- the pour-cloud point spreads of the lubricant blends and the blended finished lubricants of this invention are generally less than about 35°C, preferably less than about 25°C, more preferably less than about 10°C.
- Noack volatility is defined as the mass of oil, expressed in weight %, which is lost when the oil is heated at 250°C and 20 mrnHg (2.67 kPa; 26.7 mbar) below atmospheric in a test crucible through which a constant flow of air is drawn for 60 minutes, according to ASTM D5800.
- a more convenient method for calculating Noack volatility and one which correlates well with ASTM D5800 is by using a thermo gravimetric analyzer test (TGA) by ASTM D6375.
- TGA Noack volatility is used throughout this disclosure unless otherwise stated. Noack volatility of engine oil, as measured by TGA Noack and similar methods, has been found to co ⁇ elate with oil consumption in passenger car engines. Strict requirements for low volatility are important aspects of several recent engine oil specifications, such as, for example, ACE A A-3 and B-3 in Europe and ILSAC GF-3 in North America.
- the lubricant base oil fractions derived from highly paraffinic wax of the present invention may have a Noack volatility of less than 50 weight %.
- the "Noack Volatility Factor" of the lubricant base oil fraction derived from highly paraffinic wax is an empirical number derived from kinematic viscosity of the lubricant base oil fraction derived from highly paraffinic wax.
- the lubricant base oil fractions derived from highly paraffinic wax have a Noack Volatility less than a Noack Volatility Factor as calculated by the above equation.
- the Oxidator BN with L-4 Catalyst Test is a test measuring resistance to oxidation by means of a Dornte-type oxygen absorption apparatus (R.W. Dornte "Oxidation of White Oils," industrial and Engineering Chemistry, Vol. 28, page 26, 1936).
- the conditions are one atmosphere of pure oxygen at 340°F, reporting the hours to absorption of 1000 ml of 0 2 by 100 g of oil.
- 0.8 ml of catalyst is used per 100 grams of oil.
- the catalyst is a mixture of soluble metal naphthenates in kerosene simulating the average metal analysis of used crankcase oil.
- the mixture of soluble metal naphthenates simulates the average metal analysis of used crankcase oil.
- the additive package is 80 millimoles of zinc bispolypropylenephenyldithio-phosphate per 100 grams of oil, or approximately 1.1 grams of OLOA® 260.
- the Oxidator BN with L-4 Catalyst Test measures the response of a finished lubricant in a simulated application. High values, or long times to adsorb one liter of oxygen, indicate good stability.
- OLOA® is an acronym for Oronite Lubricating Oil Additive®, which is a registered trademark of ChevronTexaco Oronite Company.
- the Oxidator BN with L-4 Catalyst Test results should be above about 7 hours.
- the Oxidator BN with L-4 value will be greater than about 10 hours.
- the Fischer-Tropsch derived lubricant base oil fractions of the lubricant blend of the present invention have results much greater than 10 hours.
- the Fischer-Tropsch derived lubricant base oil fractions of the lubricant blends of the present invention have an Oxidator BN with L-4 Catalyst test result of greater than 25 hours.
- the highly paraffinic wax used in making the lubricant base oil fractions of the present invention can be any wax having a high content of n-paraffins.
- the highly paraffinic wax comprise greater than 40 weight % n-paraffins, preferably greater than 50 weight %, and more preferably greater than 75 weight %.
- the highly paraffinic waxes used in the present invention also have very low levels of nitrogen and sulfur, generally less than 25 ppm total combined nitrogen and sulfur and preferably less than 20 ppm.
- highly paraffinic waxes examples include slack waxes, deoiled slack waxes, refined foots oils, waxy lubricant raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures thereof.
- the pour points of the highly paraffinic waxes useful in this invention are greater than 50°C and preferably greater than 60°C.
- these highly paraffinic waxes can be processed to provide lubricant base oil fractions containing a high weight percent of molecules with cycloparaffinic functionality and containing a very high ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality (or high weight percent of molecules with moncycloparaffmic functionality and extremely low weight percent of molecules with multicycloparaffinic functionality).
- These lubricant base oil fractions can be used to provide lubricant blends exhibiting exceptionally good Brookfield viscosities at -40°C.
- these lubricant base oil fractions can be used to make high quality gear oils.
- the highly paraffinic wax is a Fischer-Tropsch derived wax and provides a Fischer-Tropsch derived lubricant base oil fraction.
- Process for Providing Oil Fraction The lubricant blends according to the present invention comprise at least one lubricant base oil fraction derived from highly paraffinic wax, a petroleum derived base oil, and a pour point depressant.
- the lubricant base oil fractions derived from highly paraffinic wax of the present invention are prepared from the highly paraffinic wax by a process including hydroisomerization.
- the highly paraffinic wax is hydroisomerized using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component under conditions of about 600°F to 750°F.
- the product from the hydroisomerization is fractionated to provide one or more fractions having a kinematic viscosity of between about 2 cSt and 20 cSt at 100°C and comprising less than 0.30 weight percent aromatics, greater than 5 weight percent molecules with cycloparaffinic functionality, and a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality greater than 15.
- the lubricant base oil fractions are used to provide a lubricant blend having a kinematic viscosity of between about 3 cSt or greater at 100°C and a Brookfield viscosity at -40°C of less than 100,000 cP.
- the highly paraffinic wax is a Fischer-Tropsch derived wax and provides a Fischer-Tropsch derived lubricant base oil fraction.
- These lubricant base oil fractions are made by process comprising providing a highly paraffinic wax and then hydroisomerizing the highly paraffinic wax to provide an isomerized oil.
- the process may further comprise fractionating the isomerized oil obtained from the hydroisomerization process to provide one or more fractions a kinematic viscosity of between about 2 cSt and 20 cSt at 100°C, preferably between about 2 cSt and 12 cSt at 100 °C.
- Lubricant base oil fractions are obtained that have the above set forth properties.
- the lubricant base oil fraction according to the present invention is a Fischer-Tropsch derived lubricant base oil fraction.
- the Fischer-Tropsch derived lubricant base oil fraction used in a lubricant blend exhibiting exceptionally good Brookfield viscosity is made by a Fischer-Tropsch synthesis process followed by hydroisomerization of the waxy fractions of the Fischer-Tropsch syncrude.
- Fischer-Tropsch Synthesis In Fischer-Tropsch chemistry, syngas is converted to liquid hydrocarbons by contact with a Fischer-Tropsch catalyst under reactive conditions. Typically, methane and optionally heavier hydrocarbons (ethane and heavier) can be sent through a conventional syngas generator to provide synthesis gas. Generally, synthesis gas contains hydrogen and carbon monoxide, and may include minor amounts of carbon dioxide and/or water. The presence of sulfur, nitrogen, halogen, selenium, phosphorus and arsenic contaminants in the syngas is undesirable. For this reason and depending on the quality of the syngas, it is prefe ⁇ ed to remove sulfur and other contaminants from the feed before performing the Fischer-Tropsch chemistry.
- Means for removing these contaminants are well known to those of skill in the art.
- ZnO guardbeds are prefe ⁇ ed for removing sulfur impurities.
- Means for removing other contaminants are well known to those of skill in the art. It also may be desirable to purify the syngas prior to the Fischer-Tropsch reactor to remove carbon dioxide produced during the syngas reaction and any additional sulfur compounds not already removed. This can be accomplished, for example, by contacting the syngas with a mildly alkaline solution (e.g., aqueous potassium carbonate) in a packed column.
- a mildly alkaline solution e.g., aqueous potassium carbonate
- Fischer-Tropsch process contacting a synthesis gas comprising a mixture of H 2 and CO with a Fischer-Tropsch catalyst under suitable temperature and pressure reactive conditions forms liquid and gaseous hydrocarbons.
- the Fischer-Tropsch reaction is typically conducted at temperatures of about 300-700°F (149-371°C), preferably about 400-550°F (204-228°C); pressures of about 10-600 psia, (0.7-41 bars), preferably about 30-300 psia, (2- 21 bars); and catalyst space velocities of about 100-10,000 cc/g/hr, preferably about 300- 3,000 cc/g/hr. Examples of conditions for performing Fischer-Tropsch type reactions are well known to those of skill in the art.
- the products of the Fischer-Tropsch synthesis process may range from Cj to C 200+ with a majority in the C 5 to C10 0 + range.
- the reaction can be conducted in a variety of reactor types, such as fixed bed reactors containing one or more catalyst beds, slu ⁇ y reactors, fluidized bed reactors, or a combination of different type reactors. Such reaction processes and reactors are well known and documented in the literature.
- the slu ⁇ y Fischer-Tropsch process which is prefe ⁇ ed in the practice of the invention, utilizes superior heat (and mass) transfer characteristics for the strongly exothermic synthesis reaction and is able to produce relatively high molecular weight, paraffinic hydrocarbons when using a cobalt catalyst.
- a syngas comprising a mixture of hydrogen and carbon monoxide is bubbled up as a third phase through a slu ⁇ y which comprises a particulate Fischer-Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in a slu ⁇ y liquid comprising hydrocarbon products of the synthesis reaction which are liquid under the reaction conditions.
- the mole ratio of the hydrogen to the carbon monoxide may broadly range from about 0.5 to about 4, but is more typically within the range of from about 0.7 to about 2.75 and preferably from about 0.7 to about 2.5.
- a particularly preferred Fischer-Tropsch process is taught in EP 0609079, also completely incorporated herein by reference for all purposes.
- Fischer-Tropsch catalysts contain a Group VIII transition metal on a metal oxide support.
- the catalysts may also contain a noble metal ⁇ romoter(s) and/or crystalline molecular sieves.
- Suitable Fischer-Tropsch catalysts comprise one or more of Fe, Ni, Co, Ru and Re, with cobalt being preferred.
- a prefe ⁇ ed Fischer-Tropsch catalyst comprises effective amounts of cobalt and one or more of Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, preferably one which comprises one or more refractory metal oxides.
- the amount of cobalt present in the catalyst is between about 1 and about 50 weight percent of the total catalyst composition.
- the catalysts can also contain basic oxide promoters such as Th0 2 , La 2 0 3 , MgO, and Ti0 2 , promoters such as Zr0 2 , noble metals (Pt, Pd, Ru, Rh, Os, Ir), coinage metals (Cu, Ag, Au), and other transition metals such as Fe, Mn, Ni, and Re.
- Suitable support materials include alumina, silica, magnesia and titania or mixtures thereof.
- Prefe ⁇ ed supports for cobalt containing catalysts comprise titania.
- Useful catalysts and their preparation are known and illustrated in U.S. Pat. No. 4,568,663, which is intended to be illustrative but non-limiting relative to catalyst selection.
- Certain catalysts are known to provide chain growth probabilities that are relatively low to moderate, and the reaction products include a relatively high proportion of low molecular (C 2-8 ) weight olefins and a relatively low proportion of high molecular weight (C 0+ ) waxes. Certain other catalysts are known to provide relatively high chain growth probabilities, and the reaction products include a relatively low proportion of low molecular (C 2-8 ) weight olefins and a relatively high proportion of high molecular weight (C 30+ ) waxes. Such catalysts are well known to those of skill in the art and can be readily obtained and/or prepared. The product from a Fischer-Tropsch process contains predominantly paraffins.
- the products from Fischer-Tropsch reactions generally include a light reaction product and a waxy reaction product.
- the light reaction product i.e., the condensate fraction
- the waxy reaction product includes hydrocarbons boiling above about 600°F (e.g., vacuum gas oil through heavy paraffins), largely in the C 20+ range, with decreasing amounts down to Cio- Both the light reaction product and the waxy product are substantially paraffinic.
- the waxy product generally comprises greater than 70 weight % normal paraffins, and often greater than 80 weight % normal paraffins.
- the light reaction product comprises paraffinic products with a significant proportion of alcohols and olefins. In some cases, the light reaction product may comprise as much as 50 weight %, and even higher, alcohols and olefins. It is the waxy reaction product (i.e., the wax fraction) that is used as a feedstock to the process for providing the Fischer-Tropsch derived lubricant base oil fraction used in the lubricant blends and blended finished lubricants of the present invention.
- the Fischer-Tropsch wax useful in this invention has a weight ratio of products of carbon number 60 or greater to products of carbon number 30 or greater of less than 0.18.
- the weight ratio of products of carbon number 60 or greater to products of carbon number 30 or greater is determined as follows: 1) measuring the boiling point distribution of the Fischer-Tropsch wax by simulated distillation using ASTM D 6352; 2) converting the boiling points to percent weight distribution by carbon number, using the boiling points of n- paraffins published in Table 1 of ASTM D 6352-98; 3) summing the weight percents of products of carbon number 30 or greater; 4) summing the weight percents of products of carbon number 60 or greater; and 5) dividing the sum of weight percents of products of carbon number 60 or greater by the sum of weight percents of products of carbon number 30 or greater.
- Fischer-Tropsch wax having a weight ratio of products of carbon number 60 or greater to products of carbon number 30 or greater of less than 0.15, and preferably of less than 0.10.
- the Fischer-Tropsch lubricant base oil fractions used in the lubricant blends are prepared from the waxy fractions of the Fischer-Tropsch syncrude by a process including hydroisomerization.
- the Fischer-Tropsch lubricant base oils are made by a process as described in U.S.S.N.10/744,870, filed December 23, 2003, herein incorporated by reference in its entirety.
- the Fischer-Tropsch lubricant base oil fractions used in the lubricant blends and blended finished lubricants of the present invention may be manufactured at a site different from the site at which the components of the lubricant blend are received and blended.
- Hydroisomerization The highly paraffinic waxes are subjected to a process comprising hydroisomerization to provide the lubricant base oil fractions used in the lubricant blends according to the present invention. Hydroisomerization is intended to improve the cold flow properties of the lubricant base oil by the selective addition of branching into the molecular structure. Hydroisomerization ideally will achieve high conversion levels of the Fischer-Tropsch wax to non-waxy iso-paraffins while at the same time minimizing the conversion by cracking.
- the conditions for hydroisomerization in the present invention are controlled such that the conversion of the compounds boiling above about 700 °F in the wax feed to compounds boiling below about 700 °F is maintained between about 10 wt % and 50 wt%, preferably between 15 wt% and 45 wt%.
- hydroisomerization is conducted using a shape selective intermediate pore size molecular sieve.
- Hydroisomerization catalysts useful in the present invention comprise a shape selective intermediate pore size molecular sieve and optionally a catalytically active metal hydrogenation component on a refractory oxide support.
- intermediate pore size means an effective pore aperture in the range of from about 3.9 to about 7.1 A when the porous inorganic oxide is in the calcined form.
- the shape selective intermediate pore size molecular sieves used in the practice of the present invention are generally 1-D 10-, 11- or 12-ring molecular sieves.
- the prefe ⁇ ed molecular sieves of the invention are of the 1-D 10-ring variety, where 10-(or 11-or 12-) ring molecular sieves have 10 (or 11 or 12) tetrahedrally-coordinated atoms (T-atoms) joined by oxygens.
- the 10-ring (or larger) pores are parallel with each other, and do not interconnect.
- 1-D 10-ring molecular sieves which meet the broader definition of the intermediate pore size molecular sieve but include intersecting pores having 8-membered rings may also be encompassed within the definition of the molecular sieve of the present invention.
- the classification of intrazeolite channels as 1-D, 2-D and 3-D is set forth by R. M. Ba ⁇ er in Zeolites, Science and Technology, edited by F. R. Rodrigues, L.D. Rollman and C. Naccache, NATO ASI Series, 1984 which classification is incorporated in its entirety by reference (see particularly page 75).
- Prefe ⁇ ed shape selective intermediate pore size molecular sieves used for hydroisomerization are based upon aluminum phosphates, such as SAPO-11, SAPO-31, and SAPO-41.
- SAPO-11 and SAPO-31 are more prefe ⁇ ed, with SAPO-11 being most prefe ⁇ ed.
- SM-3 is a particularly prefe ⁇ ed shape selective intermediate pore size SAPO, which has a crystalline structure falling within that of the SAPO-11 molecular sieves. The preparation of SM-3 and its unique characteristics are described in U.S. Pat. Nos. 4,943,424 and 5,158,665.
- prefe ⁇ ed shape selective intermediate pore size molecular sieves used for hydroisomerization are zeolites, such as ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite, and ferrierite. SSZ-32 and ZSM-23 are more prefe ⁇ ed.
- a prefe ⁇ ed intermediate pore size molecular sieve is characterized by selected crystallographic free diameters of the channels, selected crystallite size (co ⁇ esponding to selected channel length), and selected acidity.
- Desirable crystallographic free diameters of the channels of the molecular sieves are in the range of from about 3.9 to about 7.1 Angstrom, having a maximum crystallographic free diameter of not more than 7.1 and a minimum crystallographic free diameter of not less than 3.9 Angstrom.
- the maximum crystallographic free diameter is not more than 7.1 and the minimum crystallographic free diameter is not less than 4.0 Angstrom.
- the maximum crystallographic free diameter is not more than 6.5 and the minimum crystallographic free diameter is not less than 4.0 Angstrom.
- the catalyst has sufficient acidity so that 0.5 grams thereof when positioned in a tube reactor converts at least 50% of hexadecane at 370°C, a pressure of 1200 psig, a hydrogen flow of 160 ml/min, and a feed rate of 1 ml/hr.
- the catalyst also exhibits isomerization selectivity of 40 percent or greater (isomerization selectivity is determined as follows: 100 x (weight % branched C ⁇ 6 in product) / (weight % branched C ⁇ 6 in product + weight % Cj 3- in product) when used under conditions leading to 96% conversion of normal hexadecane (n-Cj 6 ) to other species.
- Such a particularly prefe ⁇ ed molecular sieve may further be characterized by pores or channels having a crystallographic free diameter in the range of from about 4.0 to about 7.1 A, and preferably in the range of 4.0 to 6.5 A.
- the crystallographic free diameters of the channels of molecular sieves are published in the "Atlas of Zeolite Framework Types", Fifth Revised Edition, 2001, by Ch. Baerlocher, W.M. Meier, and D.H. Olson, Elsevier, pp 10-15, which is incorporated herein by reference.
- the effective pore size of the molecular sieve can be measured using standard adsorption techniques and hydrocarbonaceous compounds of known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 (especially Chapter 8); Anderson et al. J. Catalysis 58, 114 (1979); and U.S. Pat. No. 4,440,871, the pertinent portions of which are incorporated herein by reference. In performing adsorption measurements to determine pore size, standard techniques are used.
- Hydroisomerization catalysts useful in the present invention comprise a catalytically active hydrogenation metal.
- a catalytically active hydrogenation metal leads to product improvement, especially VI and stability.
- Typical catalytically active hydrogenation metals include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum, and palladium.
- the metals platinum and palladium are especially preferred, with platinum most especially prefe ⁇ ed. If platinum and/or palladium is used, the total amount of active hydrogenation metal is typically in the range of 0.1 to 5 weight percent of the total catalyst, usually from 0.1 to 2 weight percent, and not to exceed 10 weight percent.
- the refractory oxide support may be selected from those oxide supports, which are conventionally used for catalysts, including silica, alumina, silica-alumina, magnesia, titania and combinations thereof.
- the conditions for hydroisomerization will be tailored to achieve a lubricant base oil fraction comprising less than about 0.3 weight % aromatics, greater than 5 weight % molecules with cycloparaffinic functionality, and a ratio of weight percent of molecules with moncycloparaffinic functionality of weight percent of molecules with multicycloparaffnic functionality of greater than 15.
- the conditions provide a lubricant base oil fraction comprising less than about 0.3 weight % aromatics, greater than 10 weight % molecules with cycloparaffinic functionality, and a ratio of weight percent of molecules with moncycloparaffinic functionality of weight percent of molecules with multicycloparaffnic functionality of greater than 15.
- the conditions provide a lubricant base oil fraction comprising less than about 0.3 weight % aromatics, a weight percent of molecules with monocycloparaffinic functionality of greater than 10, and a weight percent of molecules with multicycloparaffinic functionality of less than 0.1.
- the conditions for hydroisomerization will depend on the properties of feed used, the catalyst used, whether or not the catalyst is sulfided, the desired yield, and the desired properties of the lubricant base oil.
- Conditions under which the hydroisomerization process of the cu ⁇ ent invention may be ca ⁇ ied out include temperatures from about 500°F to about 775°F (260°C to about 413°C), preferably 600°F to about 750°F (315°C to about 399°C), more preferably about 600°F to about 700°F (315°C to about 371°C); and pressures from about 15 to 3000 psig, preferably 100 to 2500 psig.
- the hydroisomerization pressures in this context refer to the hydrogen partial pressure within the hydroisomerization reactor, although the hydrogen partial pressure is substantially the same (or nearly the same) as the total pressure.
- the liquid hourly space velocity during contacting is generally from about 0.1 to 20 hr "1 , preferably from about 0.1 to about 5 hr "1 .
- the hydrogen to hydrocarbon ratio falls within a range from about 1.0 to about 50 moles H 2 per mole hydrocarbon, more preferably from about 10 to about 20 moles H 2 per mole hydrocarbon. Suitable conditions for performing hydroisomerization are described in U.S. Pat. Nos. 5,282,958 and 5,135,638, the contents of which are incorporated by reference in their entirety.
- Hydrogen is present in the reaction zone during the hydroisomerization process, typically in a hydrogen to feed ratio from about 0.5 to 30 MSCF/bbl (thousand standard cubic feet per barrel), preferably from about 1 to about 10 MSCF/bbl. Hydrogen may be separated from the product and recycled to the reaction zone.
- Hydrotreating refers to a catalytic process, usually carried out in the presence of free hydrogen, in which the primary purpose is the removal of various metal contaminants, such as arsenic, aluminum, and cobalt; heteroatoms, such as sulfur and nitrogen; oxygenates; or aromatics from the feed stock.
- metal contaminants such as arsenic, aluminum, and cobalt
- heteroatoms such as sulfur and nitrogen
- oxygenates or aromatics from the feed stock.
- cracking of the hydrocarbon molecules i.e., breaking the larger hydrocarbon molecules into smaller hydrocarbon molecules, is minimized, and the unsaturated hydrocarbons are either fully or partially hydrogenated.
- Catalysts used in carrying out hydrotreating operations are well known in the art. See, for example, U.S. Pat. Nos.
- Suitable catalysts include noble metals from Group VIIIA (according to the 1975 rules of the International Union of Pure and Applied Chemistry), such as platinum or palladium on an alumina or siliceous matrix, and Group VIII and Group V ⁇ 3, such as nickel-molybdenum or nickel-tin on an alumina or siliceous matrix.
- Group VIIIA accordinging to the 1975 rules of the International Union of Pure and Applied Chemistry
- Group VIII and Group V ⁇ 3 such as nickel-molybdenum or nickel-tin on an alumina or siliceous matrix.
- U.S. Pat. No. 3,852,207 describes a suitable noble metal catalyst and mild conditions.
- Other suitable catalysts are described, for example, in U.S. Pat. Nos. 4,157,294 and 3,904,513.
- non-noble hydrogenation metals such as nickel- molybdenum
- the non-noble hydrogenation metals are usually present in the final catalyst composition as oxides, but are usually employed in their reduced or sulfided forms when such sulfide compounds are readily formed from the particular metal involved.
- Prefe ⁇ ed non-noble metal catalyst compositions contain in excess of about 5 weight percent, preferably about 5 to about 40 weight percent molybdenum and or tungsten, and at least about 0.5, and generally about 1 to about 15 weight percent of nickel and or cobalt determined as the co ⁇ esponding oxides.
- Catalysts containing noble metals, such as platinum contain in excess of 0.01 percent metal, preferably between 0.1 and 1.0 percent metal. Combinations of noble metals may also be used, such as mixtures of platinum and palladium. Typical hydrotreating conditions vary over a wide range. In general, the overall
- LHSV is about 0.25 to 2.0, preferably about 0.5 to 1.5.
- the hydrogen partial pressure is greater than 200 psia, preferably ranging from about 500 psia to about 2000 psia.
- Hydrogen recirculation rates are typically greater than 50 SCF/Bbl, and are preferably between 1000 and 5000 SCF/Bbl.
- Temperatures in the reactor will range from about 300°F to about 750°F (about 150°C to about 400°C), preferably ranging from 450°F to 725°F (230°C to 385°C).
- Hydrofmishing is a hydrotreating process that may be used as a step following hydroisomerization to provide lubricant base oil fractions derived from highly paraffinic wax. Hydrofmishing is intended to improve oxidation stability, UV stability, and appearance of the lubricant base oil product by removing traces of aromatics, olefins, color bodies, and solvents.
- UV stability refers to the stability of the lubricant base oil or the finished lubricant when exposed to UV light and oxygen. Instability is indicated when a visible precipitate forms, usually seen as floe or cloudiness, or a darker color develops upon exposure to ultraviolet light and air.
- the lubricant base oil fractions of the present invention may be hydro finished to improve product quality and stability.
- overall liquid hourly space velocity (LHSV) is about 0.25 to 2.0 hr "1 , preferably about 0.5 to 1.0 hr "1 .
- the hydrogen partial pressure is greater than 200 psia, preferably ranging from about 500 psia to about 2000 psia.
- Hydrogen recirculation rates are typically greater than 50 SCF/Bbl, and are preferably between 1000 and 5000 SCF/Bbl.
- Suitable hydrofmishing catalysts include noble metals from Group VIIIA (according to the 1975 rules of the International Union of Pure and Applied Chemistry), such as platinum or palladium on an alumina or siliceous matrix, and unsulfided Group VIIIA and Group VLB, such as nickel-molybdenum or nickel-tin on an alumina or siliceous matrix.
- noble metals from Group VIIIA such as platinum or palladium on an alumina or siliceous matrix
- unsulfided Group VIIIA and Group VLB such as nickel-molybdenum or nickel-tin on an alumina or siliceous matrix.
- U.S. Pat. No. 3,852,207 describes a suitable noble metal catalyst and mild conditions.
- Other suitable catalysts are described, for example, in U.S. Pat. Nos. 4,157,294 and 3,904,513.
- the non-noble metal such as nickel-molybdenum and/or tungsten, and at least about 0.5, and generally about 1 to about 15 weight percent of nickel and/or cobalt determined as the co ⁇ esponding oxides.
- the noble metal (such as platinum) catalyst contains in excess of 0.01 percent metal, preferably between 0.1 and 1.0 percent metal. Combinations of noble metals may also be used, such as mixtures of platinum and palladium. Clay treating to remove impurities is an alternative final process step to provide lubricant base oil fractions derived from highly paraffinic wax.
- the process to provide the lubricant base oil fractions optionally may include fractionating the highly paraffinic wax feed prior to hydroisomerization.
- the process to provide the lubricant base oil fractions may include fractionating the isomerized oil obtained from the hydroisomerization process to provide multiple lubricant base oil fractions.
- the fractionation of the highly paraffinic wax feed or the isomerized oil into fractions is generally accomplished by either atmospheric or vacuum distillation, or by a combination of atmospheric and vacuum distillation.
- Atmospheric distillation is typically used to separate the lighter distillate fractions, such as naphtha and middle distillates, from a bottoms fraction having an initial boiling point above about 600°F to about 750°F (about 315°C to about 399°C). At higher temperatures thermal cracking of the hydrocarbons may take place leading to fouling of the equipment and to lower yields of the heavier cuts.
- Vacuum distillation is typically used to separate the higher boiling material, such as the lubricant base oil fractions, into different boiling range cuts. Fractionating the lubricant base oil into different boiling range cuts typically enables the lubricant base oil manufacturing plant to produce more than one grade, or viscosity, of lubricant base oil. According to the present invention, fractionating the isomerized oil into different boiling range cuts may enable a lubricant base oil fraction with the properties as set forth herein to be obtained.
- the isomerized oil may be fractionated to provide one or more fractions having a kinematic viscosity of between about 2 cSt and 20 cSt at 100°C, preferably between about 2 cSt and 12 cSt at 100°C.
- the lubricant blend of the present invention may comprise one or more fractions obtained from the isomerized oil by fractionation having the properties as set forth herein.
- Solvent Dewaxing The process to make the lubricant base oil fractions derived from highly paraffinic wax may also include a solvent dewaxing step following the hydroisomerization process. Solvent dewaxing optionally may be used to remove small amounts of remaining waxy molecules from the lubricant base oil after hydroisomerization. Solvent dewaxing is done by dissolving the lubricant base oil in a solvent, such as methyl ethyl ketone, methyl iso-butyl ketone, or toluene, or precipitating the wax molecules as discussed in Chemical Technology of Petroleum, 3rd Edition, William Gruse and Donald Stevens, McGraw-Hill Book Company, Inc., New York, 1960, pages 566 to 570. Solvent dewaxing is also described in U.S. Pat. Nos. 4,477,333, 3,773,650 and 3,775,288.
- the lubricant blends according to the present invention comprise a lubricant base oil fraction derived from highly paraffinic wax, synthesized as described herein.
- the lubricant base oil fraction according to the present invention is a Fischer- Tropsch derived lubricant base oil fraction.
- the lubricant base oil fraction derived from highly paraffinic wax has a viscosity of between about 2 cSt and 20 cSt at 100 °C, preferably between about 2 cSt and 12 cSt at 100 °C.
- the lubricant base oil fractions derived from highly paraffinic wax may be of varying kinematic viscosities.
- the lubricant base oil fraction derived from highly paraffinic wax has a viscosity of between about 2 cSt and 3 cSt at 100 °C. In another embodiment, the lubricant base oil fraction derived from highly paraffinic wax has a viscosity of between about 2 cSt and 20 cSt at 100 °C.
- the Noack volatility of these lubricant base oil fractions is much lower than that of a petroleum derived conventional Group I and Group II base oil of similar kinematic viscosity.
- the Noack volatility of the lubricant base oil fraction derived from highly paraffinic wax is less than the Noack Volatility Factor as calculated by the following equation:
- Noack Volatility Factor 1000(Kinematic Viscosity of the lubricant base oil fraction derived from highly paraffinic wax at 100 °C) "2'7
- the lubricant base oil fraction When a Fischer-Tropsch derived lubricant base oil fraction, the lubricant base oil fraction preferably has a Noack volatility of less than 50 weight percent.
- the lubricant base oil fractions derived from highly paraffinic wax comprise extremely low levels of unsaturates.
- the lubricant base oil fractions derived from highly paraffinic wax comprise less than 0.30 weight percent aromatics, greater than 5 weight % molecules with cycloparaffimc functionality, and a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality of greater than 15.
- the lubricant base oil fractions derived from highly paraffinic wax comprise greater than 10 weight percent molecules with cycloparaffinic functionality.
- the lubricant base oil fractions derived from highly paraffinic wax comprise less than 0.30 weight percent aromatics, a weight percent of molecules with monocycloparaffinic functionality of greater than 10, and a weight percent of molecules with multicycloparaffinic functionality of less than 0.1.
- the lubricant base oil fractions derived from highly paraffinic wax comprise a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality of greater than 50.
- the lubricant base oil fractions derived from highly paraffinic wax comprise less than 0.10 weight percent aromatics and more preferably less than 0.05 weight percent aromatics.
- the lubricant base oil fractions derived from highly paraffinic wax used in the lubricant blends and finished lubricants contain greater than 95 weight % saturates as determined by elution column chromatography, ASTM D 2549-02. Olefins are present in an amount less than detectable by long duration C Nuclear Magnetic Resonance Spectroscopy (NMR).
- NMR Nuclear Magnetic Resonance Spectroscopy
- molecules with aromatic functionality are present in amounts less than 0.3 weight percent by HPLC-UV, and confirmed by ASTM D 5292-99 modified to measure low level aromatics.
- molecules with at least aromatic functionality are present in amounts less than 0.10 weight percent, preferably less than 0.05 weight percent, more preferably less than 0.01 weight percent.
- Sulfur is present in amounts less than 25 ppm, more preferably less than 1 ppm as determined by ultraviolet fluorescence by ASTM D 5453-00.
- Aromatics Measurement by HPLC-UV The method used to measure low levels of molecules with aromatic functionality in the lubricant base oil fractions uses a Hewlett Packard 1050 Series Quaternary Gradient High Performance Liquid Chromatography (HPLC) system coupled with a HP 1050 Diode- A ⁇ ay UV-Vis detector interfaced to an HP Chem-station. Identification of the individual aromatic classes in the highly saturated lubricant base oils was made on the basis of their UV spectral pattern and their elution time. The amino column used for this analysis differentiates aromatic molecules largely on the basis of their ring- number (or more co ⁇ ectly, double-bond number).
- HPLC Hewlett Packard 1050 Series Quaternary Gradient High Performance Liquid Chromatography
- HPLC-UV Calibration HPLC-UV is used for identifying these classes of aromatic compounds even at very low levels. Multi-ring aromatics typically absorb 10 to 200 times more strongly than single- ring aromatics. Alkyl-substitution also affected absorption by about 20%. Therefore, it is important to use HPLC to separate and identify the various species of aromatics and know how efficiently they absorb. Five classes of aromatic compounds were identified. With the exception of a small overlap between the most highly retained alkyl-cycloalkyl-1-ring aromatics and the least highly retained alkyl naphthalenes, all of the aromatic compound classes were baseline resolved. Integration limits for the co-eluting 1-ring and 2-ring aromatics at 272nm were made by the perpendicular drop method.
- Wavelength dependent response factors for each general aromatic class were first determined by constructing Beer's Law plots from pure model compound mixtures based on the nearest spectral peak absorbances to the substituted aromatic analogs.
- alkyl-cyclohexylbenzene molecules in base oils exhibit a distinct peak absorbance at 272nm that co ⁇ esponds to the same (forbidden) transition that unsubstituted tetralin model compounds do at 268nm.
- the concentration of alkyl-cycloalkyl- 1-ring aromatics in base oil samples was calculated by assuming that its molar absorptivity response factor at 272nm was approximately equal to tetralin's molar absorptivity at 268nm, calculated from Beer's law plots. Weight percent concentrations of aromatics were calculated by assuming that the average molecular weight for each aromatic class was approximately equal to the average molecular weight for the whole base oil sample. This calibration method was further improved by isolating the 1-ring aromatics directly from the lubricant base oils via exhaustive HPLC chromatography. Calibrating directly with these aromatics eliminated the assumptions and uncertainties associated with the model compounds.
- the isolated aromatic sample had a lower response factor than the model compound because it was more highly substituted.
- the substituted benzene aromatics were separated from the bulk of the lubricant base oil using a Waters semi-preparative HPLC unit. 10 grams of sample was diluted 1 :1 in n-hexane and injected onto an amino-bonded silica column, a 5cm x 22.4mm ID guard, followed by two 25cm x 22.4mm ID columns of 8-12 micron amino-bonded silica particles, manufactured by Rainin Instruments, Emeryville, California, with n-hexane as the mobile phase at a flow rate of 18mls/min.
- the standard D 5292-99 method was modified to give a minimum carbon sensitivity of 500: 1 (by ASTM standard practice E 386).
- Al 5-hour duration run on a 400-500 MHz NMR with a 10-12 mm Nalorac probe was used.
- Acorn PC integration software was used to define the shape of the baseline and consistently integrate.
- the carrier frequency was changed once during the run to avoid artifacts from imaging the aliphatic peak into the aromatic region. By taking spectra on either side of the ca ⁇ ier spectra, the resolution was improved significantly.
- the weight percent of olefins was determined by Proton-NMR (PROTON NMR) as set forth in the following steps, A-D: a) Prepare a solution of 5-10 weight % of the test hydrocarbon in deuterochlorofomi. b) Acquire a normal proton spectrum of at least 12 ppm spectral width and accurately reference the chemical shift (ppm) axis. The instalment used must have sufficient gain range to acquire a signal without overloading the receiver/ADC. When a 30 degree pulse is applied, the instrument must have a minimum signal digitization dynamic range of 65,000. Preferably the dynamic range will be 260,000 or more.
- the weight percent olefins by PROTON NMR calculation procedure as set forth is step d) works best when the resulting weight percent of olefins is low, less than about 15 weight percent.
- the olefins must be "conventional" olefins; i.e. a distributed mixture of those olefin types having hydrogens attached to the double bond carbons such as: alpha, vinylidene, cis,trans, and trisubstituted. These olefin types will have a detectable allylic to olefin integral ratio between 1 and about 2.5. When this ratio exceeds about 3, it indicates a higher percentage of tri or tetra substituted olefins are present and that different assumptions must be made to calculate the number of double bonds in the sample.
- Cycloparaf ⁇ n Distribution by FIMS Paraffins are considered more stable than cycloparaffms towards oxidation, and therefore, more desirable. Monocycloparaffins are considered more stable than multicycloparaffins towards oxidation. However, when the weight percent of all molecules with at least one cycloparaffinic function is very low in an oil, the additive solubility is low and the elastomer compatibility is poor. Examples of oils with these properties are Fischer- Tropsch oils (GTL oils) with less than about 5% cycloparaffms. To improve these properties in finished products, expensive co-solvents such as esters must often be added.
- GTL oils Fischer- Tropsch oils
- the oil fractions derived from highly paraffinic wax and used as dielectric fluids, comprise a high weight percent of molecules with monocycloparaffinic functionality and a low weight percent of molecules with multicycloparaffinic functionality such that the oil fractions have high oxidation stability, low volatility, good miscibility with other oils, good additive solubility, and good elastomer compatibility.
- the lubricant base oils of this invention were characterized by FLMS into alkanes and molecules with different numbers of unsaturations. The distribution of molecules in the oil fractions was determined by field ionization mass spectroscopy (FIMS). FIMS spectra were obtained on a Micromass VG 70VSE mass spectrometer.
- the samples were introduced via a solid probe into the spectrophotometer, preferably by placing a small amount (about 0.1 mg) of the base oil to be tested in a glass capillary tube.
- the capillary tube was placed at the tip of a solids probe for a mass spectrometer, and the probe was heated from about 40°C up to 500°C at a rate of 50°C per minute, operating under vacuum at approximately 10 "6 Ton.
- the mass spectrometer was scanned from m/z 40 to m/z 1000 at a rate of 5 seconds per decade. The acquired mass spectra were summed to generate one "averaged" spectrum. Each spectrum was 13 C co ⁇ ected using a software package from PC-MassSpec.
- the acquired mass spectra were summed to generate one "averaged" spectrum.
- the output from the FLMS analysis is the average weight percents of alkanes, 1 -unsaturations, 2-unsaturations, 3 -unsaturations, 4-unsaturations, 5- unsaturations, and 6-unsaturations in the test sample.
- the molecules with different numbers of unsaturations may be comprised of cycloparaffms, olefins, and aromatics. If aromatics were present in significant amounts in the lubricant base oil they would most likely be identified in the FLMS analysis as 4- unsaturations.
- the total of the 2-unsaturations, 3-unsaturations, 4-unsaturations, 5-unsaturations, and 6- unsaturations from the FIMS analysis, minus the weight percent of aromatics by HPLC-UV is the weight percent of molecules with multicycloparaffinic functionality in the oils of this invention. Note that if the aromatics content was not measured, it was assumed to be less than 0.1 wt% and not included in the calculation for total weight percent of molecules with cycloparaffin functionality.
- the lubricant base oils derived from highly paraffinic wax have a weight percent of molecules with cycloparaffinic functionality greater than 10, preferably greater than 15, more preferably greater than 20.
- the lubricant base oils derived from highly paraffinic wax have a weight percent of molecules with monocycloparaffinic functionality greater than 10, and a weight percent of molecules with multicycloparaffinic functionality less than 0.1, or even no molecules with multicycloparaffinic functionality.
- the lubricant base oils derived from highly paraffinic wax may have a kinematic viscosity at 100°C between about 2 cSt and about 20 cSt, preferably between about 2 cSt and about 12 cSt.
- lubricant base oils derived from highly paraffinic wax there is a relationship between the weight percent of all molecules with at least one cycloparaffinic functionality and the kinematic viscosity of the lubricant base oils of this invention. That is, the higher the kinematic viscosity at 100°C in cSt, the higher the amount of molecules with cycloparaffinic functionality that are obtained.
- the lubricant base oils derived from highly paraffinic wax have a weight percent of molecules with cycloparaffinic functionality greater than the kinematic viscosity in cSt multiplied by three, preferably greater than 15, more preferably greater than 20; and a ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality greater than 15, preferably greater than 50, more preferably greater than 100.
- the lubricant base oils derived from highly paraffinic wax have a kinematic viscosity at 100°C between about 2 cSt and about 20 cSt, preferably between about 2 cSt and about 12 cSt.
- Examples of these base oils may have a kinematic viscosity at 100°C of between about 2 cSt and about 3.3 cSt and have a weight percent of molecules with cycloparaffinic functionality that is high, but less than 10 weight percent.
- the modified ASTM D 5292-99 and HPLC-UV test methods used to measure low level aromatics, and the FIMS test method used to characterize saturates are described in D.C. Kramer, et al., "Influence of Group II & III Base Oil Composition on VI and Oxidation Stability," presented at the 1999 AIChE Spring National Meeting in Houston, March 16, 1999, the contents of which is incorporated herein in its entirety.
- olefins can polymerize to form higher molecular weight products that can color the base oil or cause sediment.
- olefins can be removed during the process of this invention by hydrofmishing or by clay treatment.
- Table II The properties of exemplary Fischer-Tropsch derived lubricant base oils suitable for use in the lubricant blends are summarized in Table II in the Examples.
- Lubricant base oils typically contain less than 1% aromatics.
- Fischer-Tropsch derived lubricant base oils are generally classified as API Group III base oils and have a low sulfur content of less than 5 ppm, a saturates content of greater than 95%, a high viscosity index of greater than 120, and excellent cold flow properties.
- the lubricant blends according to the present invention also comprise a petroleum derived base oil fraction.
- the petroleum derived base oil fraction used in the lubricant blends of the present invention comprises greater than 90 weight % saturates and less than 300 ppm sulfur.
- Petroleum derived base oils are often referred to as neutral oils. In general, neutral oils are classified as heavy, medium, and light. Heavy neutral base oil has a normal boiling range of from about 900 °F to about 1000 °F, a pour point not greater than about -7 °C, and a kinematic viscosity at 100 °C of about 8 cSt to about 20 cSt.
- Medium neutral base oil has a normal boiling range of from about 800 °F to about 900 °F, a pour point intermediate of heavy and light neutral oil, and a kinematic viscosity at 100 °C of from about 5 cSt to about 8 cSt.
- Light neutral base oil has a normal boiling range of from about 700 °F to about 800 °F, a pour point not greater than about -15 °C, and a kinematic viscosity at 100 °C of about 4 cSt to about 5 cSt.
- the petroleum derived base oil fraction used in the lubricant blends of the present invention can a heavy neutral base oil, a medium neutral base oil, or a mixture thereof.
- the petroleum derived base oil fraction is selected from the group consisting of a Group LT base oil, a Group III base oil, and mixtures thereof.
- lubricant blends with petroleum derived Group II base oils have substantially lower Brookfield viscosities than blends with Group I base oils. It is expected that lubricant blends with petroleum derived Group III base oils also exhibit substantially lower Brookfield viscosities than blends with Group I base oils.
- the specifications for lubricant base oils are defined in the API Interchange Guidelines (API Publication 1509) using sulfur content, saturates content, and viscosity index, as follows:
- Plants that make Group I base oils typically use solvents to extract the lower viscosity index (VI) components and increase the VI of the crude to the specifications desired. These solvents are typically phenol or furfural. Solvent extraction gives a product with less than 90 % saturates and more than 300 ppm sulfur. The majority of the lubricant production in the world is in the Group I category. Plants that make Group II base oils typically employ hydroprocessing such as hydrocracking or severe hydrotreating to increase the VI of the crude oil to the specification value. The use of hydroprocessing typically increases the saturates content above 90 and reduces the sulfur below 300 ppm. Approximately 20 % of the lubricant base oil production in the world is in the Group II category, and about 50 % of U.S.
- VI viscosity index
- Group II Plants that make Group III base oils typically employ wax isomerization technology to make very high VI products. Since the starting feed is waxy vacuum gas oil (VGO) or wax which contains all saturates and little sulfur, the Group III products have saturate contents above 90 and sulfur contents below 300 ppm. Fischer-Tropsch wax is an ideal feed for a wax isomerization process to make Group III lubricant oils. Only a small fraction of the world's lubricant supply is in the Group III category.
- Group rV lubricant base oils are derived by oligomerization of normal alpha olefins and are called poly alpha olefin (PAO) lubricant base oils. Group V lubricant base oils are all others.
- This group includes synthetic esters, silicon lubricants, halogenated lubricant base oils and lubricant base oils with VI values below 80.
- the latter can be described as petroleum-derived Group V lubricant base oils.
- Petroleum-derived Group V lubricant base oils typically are prepared by the same processes used to make Group I and II lubricant base oils, but under less severe conditions.
- the petroleum derived base oil fraction is selected from the group consisting of a Group II base oil, a Group III base oil, and mixtures thereof.
- pour point depressant The lubricant blends of the present invention further comprise at least one pour point depressant.
- Pour point depressants are known in the art and include, but are not limited to esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffm waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkyl phenol formaldehyde condensation resins, alkyl vinyl ethers, olefin copolymers, and mixtures thereof.
- the pour point depressant is polymethacrylate.
- the pour point depressant utilized in the present invention may also be a pour point depressing base oil blending component prepared from an isomerized Fischer-Tropsch derived bottoms product, as described in U.S. Patent Application 10/704,031, filed on
- the pour point depressing base oil blending component reduces the pour point of the lubricant blend at least 3 °C below the pour point of the lubricant blend in the absence of the pour point depressing base oil blending component.
- the pour point depressing base oil blending component is an isomerized Fischer-Tropsch derived bottoms product having a pour point that is at least 3 °C higher than the pour point of the lubricant blend comprising the lubricant base oil fraction derived from highly paraffinic wax and the petroleum derived base oil (i.e., the blend in the absence of a pour point depressant).
- the target pour point of the lubricant blend is -9 °C and the pour point of the lubricant blend in the absence of pour point depressant is greater than -9 °C
- an amount of the pour point depressing base oil blending component of the invention will be blended with the lubricant blend in sufficient proportion to lower the pour point of the blend to the target value.
- the isomerized Fischer-Tropsch derived bottoms product used to lower the pour point of the lubricant blend is usually recovered as the bottoms from the vacuum column of a Fischer-Tropsch operation.
- the average molecular weight of the pour point depressing base oil blending component usually will fall within the range of from about 600 to about 1100 with an average molecular weight between about 700 and about 1000 being prefe ⁇ ed.
- the pour point of the pour point depressing base oil blending component will be between about -9 °C and about 20 °C.
- the 10 percent point of the boiling range of the pour point depressing base oil blending component usually will be within the range of from about 850 °F and about 1050 °F.
- the pour point depressing base oil blending component will have an average degree of branching in the molecules between about 6.5 and about 10 alkyl branches per 100 carbon atoms.
- the lubricant blend may comprise a pour point depressant well known in the art and an isomerized Fischer-Tropsch derived bottoms product.
- the lubricant blend comprises 0.05 to 15 weight % isomerized Fischer-Tropsch derived bottoms product.
- the lubricant blends of the present invention comprise the lubricant base oil fraction derived from highly paraffinic wax, the petroleum derived base oil, and the pour point depressant.
- the lubricant blend preferably comprises the lubricant base oil fraction derived from highly paraffinic wax in an amount of about 10 to 80 weight %, the petroleum derived base oil in an amount of about 20 to 90 weight %, and the pour point depressant in an amount of about 0.01 to 12 weight % based on the total lubricant blend.
- the lubricant blends exhibit surprisingly low Brookfield viscosities.
- the lubricant blends exhibit Brookfield viscosities at -40 °C of less than 100,000 cP.
- the lubricant blends of this invention will have a Brookfield viscosity at -40°C of less than 90,000 cP, more preferably less than 60,000 cP, more preferably less than 50,000 cP, more preferably less than 35,000 cP, even more preferably less than 25,000 cP, and even more preferably less than 15,000 cP.
- the lubricant blends and finished gear oils comprising these lubricant blends exhibit desirable properties in addition to exceptionally low Brookfield viscosities at -40°C, including good kinematic viscosity, low Noack volatility, and high oxidative stability, and low pour and cloud points.
- the lubricant blends of the present invention can be used to make high quality gear oils.
- lubricant blends have a viscosity of about 3 cSt or greater at 100 °C and have good low temperature properties.
- the lubricant blends have a viscosity index of greater than 120.
- the lubricant blends have a kinematic viscosity of about 3.0 cSt or greater and less than about 5.0 cSt at 100°C.
- the lubricant blends have a kinematic viscosity of about 5.0 cSt or greater and less than about 7.0 cSt at lOO°C.
- the lubricant blend comprises a lubricant base oil fraction derived from highly paraffinic wax having a kinematic viscosity of between about 2 cSt and about 20 cSt at
- the lubricant base oil fraction derived from highly paraffinic wax may be of varying kinematic viscosities within this range and the Brookfield viscosity of the lubricant blend may vary in accordance with the kinematic viscosity of the lubricant base oil fraction derived from highly paraffinic wax.
- the lubricant blend comprises a lubricant base oil fraction derived from highly paraffinic wax having a kinematic viscosity of between about 2 cSt and 3 cSt at 100°C.
- the lubricant blend has a
- the lubricant blend comprises a lubricant base oil fraction derived from highly paraffinic wax having a kinematic viscosity of between about 3 cSt and 6 cSt at 100°C. In this embodiment, preferably the lubricant blend has a Brookfield viscosity at -40°C of less than 60,000 cP. hi yet another embodiment, the lubricant blend comprises a lubricant base oil fraction derived from highly paraffinic wax having a kinematic viscosity of between about 2 cSt and 12 cSt at 100°C.
- the lubricant blend has a Brookfield viscosity at -40°C of less than 90,000 cP.
- the lubricant blend may be made by blending the lubricant base oil fraction derived from highly paraffinic wax, the petroleum derived base oil, and the pour point depressant by techniques known to those of skill in the art.
- the lubricant blend components may be blended in a single step going from the individual components (i.e., a Fischer-Tropsch derived lubricant base oil fraction, a petroleum derived base oil, and a pour point depressant) directly to provide the lubricant blend.
- the lubricant base oil fraction derived from highly paraffinic wax and the petroleum derived lubricant base oil may be blended initially and then the resulting blend may be mixed with the pour point depressant.
- the blend of the lubricant base oil fraction derived from highly paraffinic wax and the petroleum derived lubricant base oil may be isolated as such or the addition of the pour point depressant may occur immediately.
- the lubricant base oil fraction derived from highly paraffinic wax is a Fischer-Tropsch derived lubricant base oil fraction.
- the lubricant blend according to the present invention is mixed with at least one additive in addition to the pour point depressant.
- the gear oil When the lubricant blends of the present invention are blended with at least one additive in addition to the pour point depressant to provide a gear oil, the gear oil also exhibits exceptional low temperature properties, including low Brookfield viscosities at -40 °C.
- the additive in addition to the pour point depressant, may be selected from the group consisting of antiwear additives, EP agents, detergents, dispersants, antioxidants, viscosity index improvers, ester co-solvents, viscosity modifiers, friction modifiers, demulsifiers, antifoaming agents, co ⁇ osion inhibitors, rust inhibitors, seal swell agents, emulsifiers, wetting agents, lubricity improvers, metal deactivators, gelling agents, tackiness agents, bactericides, fluid-loss additives, colorants, thickeners, and combinations thereof.
- viscosity index improvers When viscosity index improvers are added, preferably they are present in an amount less than 8 weight percent, and when ester co-solvents are added, preferably they are present in an amount less than 3 weight percent.
- a thickener additive may be utilized to formulate gear oils with high kinematic viscosities, such as ISO 68 and higher.
- ISO Viscosity Grades for Industrial Fluid Lubricants are as follows:
- the gear oils may be made by blending the lubricant blend according to the present invention with at least one additive, in addition to the pour point depressant, by techniques known to those of skill in the art.
- the gear oils may be blended in a single step going from the individual components (i.e., a Fischer-Tropsch derived lubricant base oil fraction, a petroleum derived base oil, and a pour point depressant) directly to provide the gear oil.
- the lubricant base oil fraction derived from highly paraffinic wax, the petroleum derived base oil, and the pour point depressant may be blended initially to provide the lubricant blend and then the lubricant blend may be mixed with an additive in addition to the pour point depressant.
- the lubricant blend may be isolated as such or the addition of the additional additive may occur immediately.
- the components of the lubricant blend may be manufactured at a site different from the site at which the components of the lubricant blend are received and blended.
- the gear oil may be manufactured at a site different from the site at which the components of the lubricant blend are received and blended.
- the lubricant blend and the gear oil are made at the same site, which site is different from the site at which the components of the lubricant blend are originally made.
- the components of the lubricant blend i.e., a Fischer-Tropsch derived lubricant base oil fraction, a petroleum derived base oil, and a pour point depressant
- the Fischer-Tropsch lubricant base oil fraction is manufactured at a remote site (i.e., a location away from a refinery or market that may have a higher cost of construction than the cost of construction at the refinery or market.
- a remote site i.e., a location away from a refinery or market that may have a higher cost of construction than the cost of construction at the refinery or market.
- the distance of transportation between the remote site and the refinery or market is at least 100 miles, preferably more than 500 miles, and most preferably more than 1000 miles).
- the Fischer-Tropsch lubricant base oil is manufactured as a first remote site and shipped to a second site.
- the petroleum derived base oil may be manufactured at a site that is the same as the first remote site or at a third remote site.
- the second site receives the Fischer-Tropsch lubricant base oil, the petroleum derived base oil, and the additives including the pour point depressant, and the lubricant blend is manufactured at this second site.
- the gear oil is also made at this second site.
- the Oxidator BN with L-4 Catalyst Test is a test measuring resistance to oxidation by means of a Dornte-type oxygen absorption apparatus (R.W. Dornte "Oxidation of White Oils," Industrial and Engineering Chemistry, Vol. 28, page 26, 1936). Normally, the conditions are one atmosphere of pure oxygen at 340°F, reporting the hours to absorption of 1000 ml of O 2 by 100 g of oil. In the Oxidator BN with L-4 Catalyst test, 0.8 ml of catalyst is used per 100 grams of oil. The catalyst is a mixture of soluble metal naphthenates simulating the average metal analysis of used crankcase oil.
- the Oxidator Bn with L-4 Catalyst Test measures the response of a finished lubricant in a simulated application. High values, or long times to adsorb one liter of oxygen, indicate good stability.
- the Fischer-Tropsch waxes had a weight ratio of compounds having at least 60 carbons atoms to compounds having at least 30 carbon atoms of less than 0.18 and a T 90 boiling point between 900°F and 1000°F.
- Three samples of the Fischer-Tropsch waxes (one sample of FT Wax A and two samples of FT Wax B) were hydroisomerized over a Pt/SAPO- 11 catalyst on an alumina binder. Operating conditions included temperatures between 652°F and 695°F (315°C and 399°C), LHSVs of 0.6 to 1.0 hr "1 , reactor pressure of 1000 psig, and once-through hydrogen rates of between 6 and 7 MSCF/bbl.
- FT Wax A was used to make a 4.5 cSt Fischer-Tropsch derived lubricant base oil fraction (FT-4A) and FT Wax B was used to make a 2.5 cSt Fischer-Tropsch derived lubricant base oil fraction (FT- 2B) and an 8 cSt Fischer-Tropsch derived lubricant base oil fraction (FT-8B).
- FT-4A 4.5 cSt Fischer-Tropsch derived lubricant base oil fraction
- FT Wax B was used to make a 2.5 cSt Fischer-Tropsch derived lubricant base oil fraction (FT- 2B) and an 8 cSt Fischer-Tropsch derived lubricant base oil fraction (FT-8B).
- Table II Test data on specific fractions useful as the Fischer-Tropsch derived lubricant base oil fraction are shown below in Table II.
- Example 2 Preparation of Lubricant Blends
- the Fischer-Tropsch derived lubricant base oil fractions prepared above (FT-2B, FT- 4 A, and FT-8B) were used to make lubricant blends with petroleum base oils.
- the Petroleum Base Oils used to blend with the Fischer-Tropsch derived lubricant base oils fractions are as follows:
- the comparison lubricant blend with all Fischer-Tropsch derived lubricant base oil fractions and polymethacrylate pour point depressant had an unacceptably high Brookfield viscosity at -40°C, greater than a million cP.
- the blends of FT-4A with petroleum derived Group I base oils had Brookfield viscosities at -40 °C above 100,000 cP so were not optimal.
- the blends with petroleum derived Group II base oil had Brookfield viscosities at -40 °C well below 100,000 cP, making them suitable lubricant blends of this invention.
- the blends with petroleum derived Group II base oils had significantly lower Brookfield viscosities than the blends with petroleum derived Group I base oils.
- a sample of the FT Wax C was hydroisomerized over a Pt/SAPO-11 catalyst on an alumina binder. Operating conditions included temperatures between 652°F and 695°F (315°C and 399°C), LHSVs of 1.0 hr "1 , reactor pressure of 1000 psig, and once-through hydrogen rates of between 6 and 7 MSCF/bbl.
- the reactor effluent passed directly to a second reactor containing a Pt/Pd on silica-alumina hydrofmishing catalyst also operated at 1000 psig. Conditions in the second reactor included a temperature of 450°F (232°C) and an LHSV of 1.0 hr "1 .
- FT-6.3 nor FT-14.6 met the desired ratio of weight percent of molecules with monocycloparaffinic functionality to weight percent of molecules with multicycloparaffinic functionality. The ratio for both of these samples was only 11.6.
- the Fischer-Tropsch derived lubricant base oil fractions prepared above were each used to make a lubricant blend with the Group II Heavy Neutral petroleum base oil, as characterized in Table III, and polymethacrylate as the pour point depressant. The composition and properties of the two resulting blends are summarized in Table VIII below.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0510941-8A BRPI0510941A (en) | 2004-05-19 | 2005-05-19 | lubricant mixture, gear oil, and process for producing a lubricant mixture |
AU2005245970A AU2005245970B2 (en) | 2004-05-19 | 2005-05-19 | Lubricant blends with low brookfield viscosities |
JP2007527526A JP2007538144A (en) | 2004-05-19 | 2005-05-19 | Lubricant mixture with low Brookfield viscosity |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/847,996 US7384536B2 (en) | 2004-05-19 | 2004-05-19 | Processes for making lubricant blends with low brookfield viscosities |
US10/847,996 | 2004-05-19 | ||
US10/847,997 | 2004-05-19 | ||
US10/847,997 US7273834B2 (en) | 2004-05-19 | 2004-05-19 | Lubricant blends with low brookfield viscosities |
US11/000,892 US7473345B2 (en) | 2004-05-19 | 2004-12-02 | Processes for making lubricant blends with low Brookfield viscosities |
US11/000,952 US7572361B2 (en) | 2004-05-19 | 2004-12-02 | Lubricant blends with low brookfield viscosities |
US11/000,892 | 2004-12-02 | ||
US11/000,952 | 2004-12-02 |
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Publication Number | Publication Date |
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WO2005113734A2 true WO2005113734A2 (en) | 2005-12-01 |
WO2005113734A3 WO2005113734A3 (en) | 2006-06-22 |
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PCT/US2005/017976 WO2005113734A2 (en) | 2004-05-19 | 2005-05-19 | Lubricant blends with low brookfield viscosities |
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JP (1) | JP2007538144A (en) |
AU (1) | AU2005245970B2 (en) |
BR (1) | BRPI0510941A (en) |
GB (1) | GB2415435B (en) |
WO (1) | WO2005113734A2 (en) |
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US7252753B2 (en) | 2004-12-01 | 2007-08-07 | Chevron U.S.A. Inc. | Dielectric fluids and processes for making same |
GB2440218A (en) * | 2006-07-14 | 2008-01-23 | Afton Chemical Corp | Lubricant compositions |
JP2008031459A (en) * | 2006-06-30 | 2008-02-14 | Sanyo Chem Ind Ltd | Viscosity index improver and lubricating oil composition |
US7510674B2 (en) | 2004-12-01 | 2009-03-31 | Chevron U.S.A. Inc. | Dielectric fluids and processes for making same |
JP2010511734A (en) * | 2006-09-26 | 2010-04-15 | シェブロン ユー.エス.エー. インコーポレイテッド | Heat transfer oil with high self-ignition temperature |
JP2010513698A (en) * | 2006-12-20 | 2010-04-30 | シェブロン ユー.エス.エー. インコーポレイテッド | Lubricant base oil blend with low NOACK volatility (wt%) |
JP2010531923A (en) * | 2007-06-28 | 2010-09-30 | シェブロン ユー.エス.エー. インコーポレイテッド | Functional fluid composition |
JP2010531922A (en) * | 2007-06-28 | 2010-09-30 | シェブロン ユー.エス.エー. インコーポレイテッド | Method for producing shock absorber fluid |
JP2010538120A (en) * | 2007-08-28 | 2010-12-09 | シェブロン ユー.エス.エー. インコーポレイテッド | Sliding surface lubricant composition, its production and use |
JP2010538116A (en) * | 2007-08-27 | 2010-12-09 | シェブロン ユー.エス.エー. インコーポレイテッド | Method for producing two-cycle gasoline engine lubricant |
US7906465B2 (en) | 2006-07-14 | 2011-03-15 | Afton Chemical Corp. | Lubricant compositions |
US8003584B2 (en) | 2006-07-14 | 2011-08-23 | Afton Chemical Corporation | Lubricant compositions |
AU2011201609B2 (en) * | 2004-05-04 | 2011-09-22 | Chevron U.S.A. Inc. | Process for improving the lubricating properties of base oils using isomerized petroleum product |
JP2012052145A (en) * | 2011-12-12 | 2012-03-15 | Jx Nippon Oil & Energy Corp | Lubricant base oil |
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US7932217B2 (en) * | 2007-08-28 | 2011-04-26 | Chevron U.S.A., Inc. | Gear oil compositions, methods of making and using thereof |
US8034752B2 (en) * | 2008-03-11 | 2011-10-11 | Afton Chemical Corporation | Lubricating composition |
EP2186872A1 (en) * | 2009-12-16 | 2010-05-19 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
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- 2005-05-18 GB GB0510149A patent/GB2415435B/en not_active Expired - Fee Related
- 2005-05-19 JP JP2007527526A patent/JP2007538144A/en not_active Ceased
- 2005-05-19 BR BRPI0510941-8A patent/BRPI0510941A/en not_active IP Right Cessation
- 2005-05-19 WO PCT/US2005/017976 patent/WO2005113734A2/en active Application Filing
- 2005-05-19 AU AU2005245970A patent/AU2005245970B2/en not_active Ceased
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AU2011201609B2 (en) * | 2004-05-04 | 2011-09-22 | Chevron U.S.A. Inc. | Process for improving the lubricating properties of base oils using isomerized petroleum product |
US7510674B2 (en) | 2004-12-01 | 2009-03-31 | Chevron U.S.A. Inc. | Dielectric fluids and processes for making same |
US7252753B2 (en) | 2004-12-01 | 2007-08-07 | Chevron U.S.A. Inc. | Dielectric fluids and processes for making same |
JP2008031459A (en) * | 2006-06-30 | 2008-02-14 | Sanyo Chem Ind Ltd | Viscosity index improver and lubricating oil composition |
US7906465B2 (en) | 2006-07-14 | 2011-03-15 | Afton Chemical Corp. | Lubricant compositions |
GB2440218A (en) * | 2006-07-14 | 2008-01-23 | Afton Chemical Corp | Lubricant compositions |
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US8003584B2 (en) | 2006-07-14 | 2011-08-23 | Afton Chemical Corporation | Lubricant compositions |
JP2010511734A (en) * | 2006-09-26 | 2010-04-15 | シェブロン ユー.エス.エー. インコーポレイテッド | Heat transfer oil with high self-ignition temperature |
JP2010513698A (en) * | 2006-12-20 | 2010-04-30 | シェブロン ユー.エス.エー. インコーポレイテッド | Lubricant base oil blend with low NOACK volatility (wt%) |
JP2010531922A (en) * | 2007-06-28 | 2010-09-30 | シェブロン ユー.エス.エー. インコーポレイテッド | Method for producing shock absorber fluid |
JP2010531923A (en) * | 2007-06-28 | 2010-09-30 | シェブロン ユー.エス.エー. インコーポレイテッド | Functional fluid composition |
JP2010538116A (en) * | 2007-08-27 | 2010-12-09 | シェブロン ユー.エス.エー. インコーポレイテッド | Method for producing two-cycle gasoline engine lubricant |
JP2010538120A (en) * | 2007-08-28 | 2010-12-09 | シェブロン ユー.エス.エー. インコーポレイテッド | Sliding surface lubricant composition, its production and use |
JP2012052145A (en) * | 2011-12-12 | 2012-03-15 | Jx Nippon Oil & Energy Corp | Lubricant base oil |
Also Published As
Publication number | Publication date |
---|---|
JP2007538144A (en) | 2007-12-27 |
GB0510149D0 (en) | 2005-06-22 |
AU2005245970B2 (en) | 2010-11-04 |
BRPI0510941A (en) | 2007-11-27 |
GB2415435B (en) | 2007-09-05 |
WO2005113734A3 (en) | 2006-06-22 |
AU2005245970A1 (en) | 2005-12-01 |
GB2415435A (en) | 2005-12-28 |
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