EP2531582B1 - Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction - Google Patents

Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction Download PDF

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EP2531582B1
EP2531582B1 EP11705319.9A EP11705319A EP2531582B1 EP 2531582 B1 EP2531582 B1 EP 2531582B1 EP 11705319 A EP11705319 A EP 11705319A EP 2531582 B1 EP2531582 B1 EP 2531582B1
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group
oil
base
oils
viscosity
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EP2531582A1 (fr
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Kathleen H. Tellier
Vincent Mark Carey
Kevin Louis Crouthamel
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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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
    • 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
    • C10M111/04—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 macromolecular organic compound
    • 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
    • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Definitions

  • Gas engine oil of enhanced life as evidenced by an increase in the resistance of the oil to oxidation, nitration and deposit formation is the subject of U.S. Patent No. 5,726,133 .
  • the gas engine oil of that patent is a low ash gas engine oil comprising a major amount of a base oil of lubricating viscosity and a minor amount of an additive mixture comprising a mixture of detergents comprising at least one alkali or alkaline earth metal salt having a Total Base Number (TBN) of about 250 and less and a second alkali or alkaline earth metal salt having a TBN lower than the aforesaid component.
  • TBN of this second alkali or alkaline earth metal salt will typically be about half or less that of the aforesaid component.
  • U.S. Published Application US2005/0059563 is directed to a lubricating oil composition, automotive gear lubricating composition and fluids useful in the preparation of finished automotive gear lubricants and gear oil comprising a blend of a PAO having a viscosity of between about 40 cSt (mm 2 /s) and 1000 cSt (mm 2 /s) @ 100°C, and an ester having a viscosity of less than or equal to about 2.0 cSt (mm 2 /s) @ 100°C wherein the blend of PAO and ester has a viscosity index greater than or equal to the viscosity index of the PAO.
  • the composition may further contain thickeners, anti-oxidants, inhibitor packages, anti-rust additives, dispersants, detergents, friction modifiers, traction improving additives, demulsifiers, defoamants, dyes and haze inhibitors.
  • U.S. Published Application 2007/0289897 is directed to a lubricating oil blend comprising at least two base stocks with a viscosity difference between the first and second base stock of greater than 96 cSt (mm 2 /s) @ 100°C, the lubricant exhibiting improved air release.
  • the blend contains at least one synthetic PAO having a viscosity of less than 10 cSt (mm 2 /s) but greater than 2 cSt (mm 2 /s) @ 100°C and a second synthetic oil having a viscosity greater than 100 cSt (mm 2 /s) but less than 300 cSt (mm 2 /s) @ 100°C.
  • the lubricant can contain anti-wear, anti-oxidant, defoamant, demulsifier, detergent, dispersant, metal passivator, friction reducer, rust inhibitor additive and mixtures thereof.
  • the difference in viscosity between the first and second stocks is greater than 30 cSt (mm 2 /s) @ 100°C.
  • the first high viscosity stock is a metallocene catalyzed PAO base stock.
  • the second stock can be selected from GTL lubricants, wax-derived lubricants, PAO, brightstock, brightstock with PIB, Group I base stocks, Group II base stocks, Group III base stocks and mixtures thereof.
  • the lubricant can contain additives including detergents.
  • the first stock has a viscosity of greater than 300 cSt (mm 2 /s) @ 100°C
  • the second stock has a viscosity of between 1.5 cSt (mm 2 /s) to 6 cSt (mm 2 /s) @ 100°C.
  • the difference in viscosity between the first and second stocks is greater than 96 cSt (mm 2 /s) @ 100°C.
  • the difference in viscosity between the first and second stocks is greater than 250 cSt (mm 2 /s) @ 100°C.
  • the first high kinematic viscosity stock is a metallocene catalyzed PAO base stock.
  • the second stock can be chosen from GTL base stock, wax-derived base stock, PAO, brightstock, brightstock with PIB, Group I base stock, Group II base stock, Group III base stock, Group V base stock, Group VI base stock and mixtures thereof.
  • the lubricant can contain additives including detergents.
  • U.S. Patent 6,140,281 is directed to long life gas engine lubricating oils containing detergents.
  • the lubricating oil comprises a major amount of a base oil of lubricating viscosity and a minor amount of a mixture of one or more metal sulfonate(s) and/or phenate(s) and one or more metal salicylate(s) detergents, all detergents in the mixture having the same or substantially the same Total Base Number (TBN).
  • TBN Total Base Number
  • the lubricating oil base stock is any natural or synthetic lubricating base stock fraction typically having a kinematic viscosity at 100°C of about 5 to 20 cSt, more preferably about 7 to 16 cSt, most preferably about 9 to 13 cSt.
  • the use of the viscosity index improver permits the omission of oil of viscosity 20 cSt or more at 100°C from the lube base oil fraction used to make the present formulation. Therefore, a preferred base oil is one which contains little, if any, heavy fractions; e.g., little, if any, lube oil fraction of viscosity 20 cSt or higher at 100°C.
  • the lubricating oil base stock can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable base stocks include those in API categories I, II and III, where saturates level and Viscosity Index are:
  • Suitable lubricating oil base stocks include base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
  • the detergent is a mixture of one or more metal sulfonate(s) and/or metal phenate(s) with one or more metal salicylate(s).
  • the metals are any alkali or alkaline earth metals; e.g., calcium, barium, sodium, lithium, potassium, magnesium, more preferably calcium, barium and magnesium. It is a feature of the lubricating oil that each of the metal salts used in the mixture has the same or substantially the same TBN as the other metal salts in the mixture.
  • U.S. Patent 6,645,922 is directed to a lubricating oil for two-stroke cross-head marine diesel engines comprising a base oil and an oil-soluble overbased detergent additive in the form of a complex wherein the basic material of the detergent is stabilized by more than one surfactant.
  • the more than one surfactants can be mixtures of: (1) sulfurized and/or non-sulfurized phenols and one other surfactant which is not a phenol surfactant; (2) sulfurized and/or non-sulfurized salicylic acid and one other surfactant which is not a salicylic surfactant; or (3) at least three surfactants which are sulfurized or non-sulfurized phenol, sulfurized or non-sulfurized salicylic acid and one other surfactant which is not a phenol or salicylic surfactant; or (4) at least three surfactants which are sulfurized or non-sulfurized phenol, sulfurized or non-sulfurized salicylic acid and at least one sulfuric acid surfactant.
  • the base stock is an oil of lubricating viscosity and may be any oil suitable for the system lubrication of a cross-head engine.
  • the lubricating oil may suitably be an animal, vegetable or a mineral oil.
  • the lubricating oil is a petroleum-derived lubricating oil, such as naphthenic base, paraffinic base or mixed base oil.
  • the lubricating oil may be a synthetic lubricating oil.
  • Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tri-decyl adipate, or polymeric hydrocarbon lubricating oils, for example, liquid polyisobutene and polyalpha olefins. Commonly, a mineral oil is employed.
  • the lubricating oil may generally comprise greater than 60, typically greater than 70 % by mass of the lubricating oil composition and typically have a kinematic viscosity at 100°C of from 2 to 40, for example, from 3 to 15, mm 2 /s, and a viscosity index from 80 to 100, for example, from 90 to 95.
  • Brightstock refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C from 28 to 36 mm 2 /s, and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5 mass%, based on the mass of the lubricating oil composition.
  • U.S. Patent 6,613,724 is directed to gas fueled engine lubricating oil comprising an oil of lubricating viscosity, a detergent including at least one calcium salicylate having a TBN in the range 70 to 245, 0 to 0.2 mass% of nitrogen, based on the mass of the oil composition, of a dispersant and minor amounts of one or more co-additive.
  • the base oil can be any animal, vegetable or mineral oil or synthetic oil.
  • the base oil is used in a proportion of greater than 60 mass% of the composition.
  • the oil typically has a viscosity at 100°C of from 2 to 40, for example 3 to 15 mm 2 /s and a viscosity index of from 80 to 100.
  • Hydrocracked oils can also be used which have viscosities of 2 to 40 mm 2 /s at 100°C and viscosity indices of 100 to 110.
  • Brightstock having a viscosity at 100°C of from 28 to 36 mm 2 /s can also be used, typically in a proportion less than 30, preferably less than 20, most preferably less than 5 mass%.
  • U.S. Patent 7,101,830 is directed to a gas engine oil having a boron content of more than 95 ppm comprising a major amount of a lubricating oil having a viscosity index of 80 to 120, at least 90 mass% saturates, 0.03 mass% or less sulfur and at least one detergent.
  • Metal salicylate is a preferred detergent.
  • U.S. Patent 4,956,122 is directed to a lubricating oil composition containing a high viscosity synthetic hydrocarbon such as high viscosity PAO, liquid hydrogenated polyisoprenes, or ethylene-alpha olefin copolymers having a viscosity of 40-1000 cSt (mm 2 /s) at 100°C, a low viscosity synthetic hydrocarbon having a viscosity of between 1 and 10 cSt (mm 2 /s) at 100°C, optionally a low viscosity ester having a viscosity of between 1 and 10 cSt (mm 2 /s) at 100°C and optionally up to 25 wt% of an additive package.
  • a high viscosity synthetic hydrocarbon such as high viscosity PAO, liquid hydrogenated polyisoprenes, or ethylene-alpha olefin copolymers having a viscosity of 40-1000 cSt (mm 2 /s) at 100
  • the invention is directed to the use of a lubricating oil for improving the fuel economy of large low and medium speed engines in which the velocity at which interfacing surfaces of the engine move past each other when the engine is operating reach es at least 30 mm/s, more preferably at least 50 mm/s , wherein said interfacing surfaces are selected from the group consisting of piston and cylinder wall and/or interfacing bearing surfaces .
  • the difference in viscosity between the first and second base stocks is at least 34 cSt (mm 2 /s), more preferably at least 110 cSt (mm 2 /s), still more preferably at least 140 cSt (mm 2 /s).
  • surface speed is meant the velocity at which interfacing surfaces of an engine, e.g. piston and cylinder wall, interfacing bearing surfaces, etc. move past each other when the engine is operating. This surface speed is a primary factor in influencing whether the lubrication regime for the interfacing surfaces is boundary, hydrodynamic or mixed (boundary/hydrodynamic).
  • the present invention utilizes a bimodal mixture of base stocks.
  • bimodal in the present specification is meant a mixture of at least two base stocks each having a different kinematic viscosity at 100°C wherein the difference in kinematic viscosity at 100°C between the at least two base stocks in the bimodal blend is at least 30 mm 2 /s.
  • the mixture of at least two base stocks comprises one or more low kinematic viscosity base stock(s) having a kinematic viscosity at 100°C of from 2 to 12 mm 2 /s, which base stock is selected from the group consisting of Group III, and Group IV base stocks using the API classification in combination with one or more high kinematic viscosity Group IV base stocks having a kinematic viscosity at 100°C of at least 38 mm 2 /s.
  • Group I base stocks are conventional oil stocks classified by the American Petroleum Institute (API) as oils containing less than 90% saturates, greater than 0.03 wt% sulfur and a viscosity index greater than or equal to 80 and less than 120.
  • API American Petroleum Institute
  • Group II base stocks are classified by the American Petroleum Institute as oils containing greater than or equal to 90% saturates, less than or equal to 0.03 wt% sulfur and a viscosity index greater than or equal to 80 and less than 120.
  • Group III stocks also embrace non-conventional or unconventional base stocks and/or base oils which include one or a mixture of base stock(s) and/or base oil(s) derived from: (1) one or more Gas-to-Liquids (GTL) materials; as well as (2) hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) derived from synthetic wax, natural wax or waxy feeds, waxy feeds including mineral and/or non-mineral oil waxy feed stocks such as gas oils, slack waxes (derived from the solvent dewaxing of natural oils, mineral oils or synthetic; e.g., Fischer-Tropsch feed stocks) and waxy stocks such as waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, foots oil or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials recovered from coal liquefaction or shale
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes and butynes.
  • GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
  • GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/ fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed
  • GTL base stock(s) and/or base oil(s) derived from GTL materials are characterized typically as having kinematic viscosities at 100°C of from about 2 mm 2 /s to about 50 mm 2 /s (ASTM D445). They are further characterized typically as having pour points of -5°C to about -40°C or lower (ASTM D97). They are also characterized typically as having viscosity indices of about 80 to about 140 or greater (ASTM D2270).
  • GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this material especially suitable for the formulation of low SAP products.
  • the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
  • compositions of GTL base stock(s) and/or base oil(s), hydrodewaxed or hydroisomerized/cat (and/or solvent) dewaxed F-T material derived base stock(s), and wax-derived hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s), such as wax isomerates or hydrodewaxates, are recited in U.S. Patent Nos. 6,080,301 ; 6,090,989 , and 6,165,949 , for example.
  • Base stock(s) and/or base oil(s) derived from waxy feeds which are also suitable for use as the Group III stocks in this invention, are paraffinic fluids of lubricating viscosity derived from hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed waxy feed stocks of mineral oil, non-mineral oil, non-petroleum, or natural source origin, e.g.
  • Slack wax is the wax recovered from any waxy hydrocarbon oil including synthetic oil such as F-T waxy oil or petroleum oils by solvent or auto-refrigerative dewaxing.
  • Solvent dewaxing employs chilled solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK/MIBK, mixtures of MEK and toluene, while auto-refrigerative dewaxing employs pressurized, liquefied low boiling hydrocarbons such as propane or butane.
  • Slack waxes secured from synthetic waxy oils such as F-T waxy oil will usually have zero or nil sulfur and/or nitrogen containing compound content.
  • Slack wax(es) secured from petroleum oils may contain sulfur and nitrogen-containing compounds.
  • Such heteroatom compounds must be removed by hydrotreating (and not hydrocracking), as for example by hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) so as to avoid subsequent poisoning/ deactivation of the hydroisomerization catalyst.
  • the process of making the lubricant oil base stocks from waxy stocks may be characterized as an isomerization process. If slack waxes are used as the feed, they may need to be subjected to a preliminary hydrotreating step under conditions already well known to those skilled in the art to reduce (to levels that would effectively avoid catalyst poisoning or deactivation) or to remove sulfur- and nitrogen-containing compounds which would otherwise deactivate the hydroisomerization or hydrodewaxing catalyst used in subsequent steps.
  • F-T waxes are used, such preliminary treatment is not required because such waxes have only trace amounts (less than about 10 ppm, or more typically less than about 5 ppm to nil) of sulfur or nitrogen compound content.
  • some hydrodewaxing catalyst fed F-T waxes may benefit from prehydrotreatment for the removal of oxygenates while others may benefit from oxygenates treatment.
  • the hydroisomerization or hydrodewaxing process may be conducted over a combination of catalysts, or over a single catalyst.
  • the hydroprocessing used for the production of base stocks from such waxy feeds may use an amorphous hydrocracking/hydroisomerization catalyst, such as a lube hydrocracking (LHDC) catalysts, for example catalysts containing Co, Mo, Ni, W, Mo, etc., on oxide supports, e.g., alumina, silica, silica/alumina, or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC lube hydrocracking
  • oxide supports e.g., alumina, silica, silica/alumina, or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • catalytic dewaxing the hydroisomerate is reacted with hydrogen in the presence of a suitable dewaxing catalyst at conditions effective to lower the pour point of the hydroisomerate.
  • Catalytic dewaxing also converts a portion of the hydroisomerate to lower boiling materials which are separated from the heavier base stock fraction. This base stock fraction can then be fractionated into two or more base stocks. Separation of the lower boiling material may be accomplished either prior to or during fractionation of the heavy base stock fraction material into the desired base stocks.
  • the first base stock of the bimodal mixture can also be a Group IV base stock which for the purposes of this specification and the appended claims is identified as polyalpha olefins.
  • the polyalpha olefins in general are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of polyalphaolefins which include, but are not limited to, C 2 to C 32 alphaolefins with the C 8 to C 16 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like, being preferred.
  • the preferred polyalphaolefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and mixed olefin-derived polyolefins.
  • the homo-polymer mPAO composition is made from single alphaolefin choosing from C 3 to C 30 range, preferably C 3 to C 16 , most preferably C 3 to C 14 or C 3 to C 12 .
  • the homo-polymers can be isotactic, atactic, syndiotactic polymers or any other form of appropriate taciticity.
  • the taciticity can be carefully tailored by the polymerization catalyst and polymerization reaction condition chosen or by the hydrogenation condition chosen.
  • the phrase "at least two alphaolefins” will be understood to mean “at least two different alphaolefins” (and similarly “at least three alphaolefins” means “at least three different alphaolefins", and so forth).
  • the process employs a catalyst system comprising a metallocene compound (Formula 1, below) together with an activator such as a non-coordinating anion (NCA) (Formula 2, below) or methylaluminoxane (MAO) 1111 (Formula 3, below):
  • NCA non-coordinating anion
  • MAO methylaluminoxane
  • mpolyalphaolefins described herein may have monomer units represented by Formula 4 in addition to the all regular 1,2-connection: where j, k and m are each, independently, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, n is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by proton NMR.
  • mpolyalphaolefins may have a Mn (number average molecular weight) of 50,000 or less, preferably between 200 and 40,000, preferably between 250 and 30,000, preferably between 500 and 20,000 g/mol.
  • Mw/Mn Molecular weight distribution
  • GPC gel permeation chromatography
  • the GPC solvent was HPLC Grade tetrahydrofuran, uninhibited, with a column temperature of 30°C, a flow rate of 1 ml/min, and a sample concentration of 1 wt%, and the Column Set is a Phenogel 500 A, Linear, 10E6A.
  • any of the m-polyalphaolefins (mPAO) described herein may have a substantially minor portion of a high end tail of the molecular weight distribution.
  • the mPAO has not more than 5.0 wt% of polymer having a molecular weight of greater than 45,000 Daltons.
  • the amount of the mPAO that has a molecular weight greater than 45,000 Daltons is not more than 1.5 wt%, or not more than 0.10 wt%.
  • the amount of the mPAO that has a molecular weight greater than 60,000 Daltons is not more than 0.5 wt%, or not more than 0.20 wt%, or not more than 0.1 wt%.
  • the mass fractions at molecular weights of 45,000 and 60,000 can be determined by GPC, as described above.
  • Any mPAO described herein may have a pour point of less than 0°C (as measured by ASTM D97), preferably less than -10°C, preferably less than 20°C, preferably less than -25°C, preferably less than -30°C, preferably less than -35°C, preferably less than -50°C, preferably between -10°C and -80°C, preferably between -15°C and -70°C.
  • mPolyalphaolefins (mPAO) made using metallocene catalysis may have a kinematic viscosity at 100°C from about 1.5 to about 5,000 cSt, preferably from about 2 to about 3,000 cSt, preferably from about 3 cSt to about 1,000 cSt, more preferably from about 4 cSt to about 1,000 cSt, and yet more preferably from about 8 cSt to about 500 cSt as measured by ASTM D445.
  • PAOs useful in the present invention include those made by the process disclosed in U.S. Patent 4,827,064 and U.S. Patent 4,827,073 .
  • Those PAO materials, which are produced by the use of a reduced valence state chromium catalyst, are olefin oligomers of polymers which are characterized by very high viscosity indices which give them very desirable properties to be useful as lubricant base stocks and, with higher viscosity grades, as VI improvers. They are referred to as High Viscosity Index PAOs or HVI-PAOs.
  • the preferred catalyst comprises a reduced valence state chromium on a silica support, prepared by the reduction of chromium using carbon monoxide as the reducing agent.
  • the oligomerization is carried out at a temperature selected according to the viscosity desired for the resulting oligomer, as described in U.S. Patent Nos. 4,827,064 and 4,827,073 .
  • Higher viscosity materials may be produced as described in U.S. Patent No. 5,012,020 and U.S. Patent No. 5,146,021 where oligomerization temperatures below about 90°C are used to produce the higher molecular weight oligomers.
  • the oligomers after hydrogenation when necessary to reduce residual unsaturation, have a branching index (as defined in U.S. Patent Nos. 4,827,064 and 4,827,073 ) of less than 0.19.
  • the HVI-PAO normally have a viscosity in the range of about 12 to 5,000 cSt.
  • HVI-PAOs generally can be characterized by one or more of the following: C 30 to C 1300 hydrocarbons having a branch ratio of less than 0.19, a weight average molecular weight of between 300 and 45,000, a number average molecular weight of between 300 and 18,000, a molecular weight distribution of between 1 and 5.
  • HVI-PAOs are fluids with 100°C viscosity ranging from 3 to 5000 mm 2 /s or more.
  • the fluids with viscosity at 100°C of 3 mm 2 /s to 5000 mm 2 /s have VI calculated by ASTM method D2270 greater than 130. Usually they range from 130 to 350.
  • the fluids all have low pour points, below -15°C.
  • the products usually are distilled to remove any low molecular weight compositions such as those boiling below 600°F ( 316°C) , or with carbon numbers less than C 20 , if they are produced from the polymerization reaction or are carried over from the starting material. This distillation step usually improves the volatility of the finished fluids.
  • the fluids made directly from the polymerization already have very low degree of unsaturation, such as those with viscosities greater than 150 cSt at 100°C. They have bromine numbers less than 5 or even below 2. In these cases, it can be used as is without hydrotreating, or it can be hydrotreated to further improve the base stock properties.
  • Group V base stocks are classified by the American Petroleum Institute as those oils which do not fall within Groups I, II, III or IV. Such oils, therefore, include esters, polyol esters, silicone oils, alkylated aromatics, alkyl phosphates, etc.
  • the first low kinematic viscosity fluid can be employed as a single component oil or as a mixture of oils provided the single oil or mixture of oils has a low kinematic viscosity in the range of 2 to 12 mm 2 /s at 100°C.
  • the low kinematic viscosity fluid can constitute a single base stock/oil falling within the recited kinematic viscosity limits or it can be made up of two or more base stocks/oils, each individually falling within the recited kinematic viscosity limits. Further, the low kinematic viscosity fluid can be made up of mixtures of one, two or more low viscosity stocks/oils, e.g. stocks/oils with kinematic viscosities in the range of 2 to 12 mm 2 /s at 100°C combined with one, two or more high kinematic viscosity stocks/oils, e.g.
  • the second oil used in the bimodal blend is a high kinematic viscosity Group IV fluid, i.e. a PAO with a kinematic viscosity at 100°C of at least 38 mm 2 /s, preferably a kinematic viscosity in the range of 38 to 1200 mm 2 /s, more preferably 38 to 600 mm 2 /s.
  • a high kinematic viscosity Group IV fluid i.e. a PAO with a kinematic viscosity at 100°C of at least 38 mm 2 /s, preferably a kinematic viscosity in the range of 38 to 1200 mm 2 /s, more preferably 38 to 600 mm 2 /s.
  • the second, high kinematic viscosity base stock it can be made up of a single PAO base stock/oil meeting the recited kinematic viscosity limit or it may be made up of two or more PAO base stocks/oils, each of which meet the recited kinematic viscosity limit.
  • this second high kinematic viscosity PAO base stock/oil can be a mixture of one, two or more lower kinematic PAO base stocks/oils, e.g.
  • Such higher kinematic viscosity PAO fluids can be made using the same techniques previously recited.
  • the high kinematic viscosity PAO fluid which is the second fluid of the bimodal mixture is made employing metallocene catalysis or the process described in U.S. Patent 4,827,064 or U.S. Patent 4,827,073 .
  • the PAO fluid used as the second base stock of the bimodal blend is a high kinematic viscosity PAO having a KV at 100°C of at least 38 mm 2 /s, preferably 38 to 1200 mm 2 /s, more preferably 38 to 600 mm 2 /s, the only proviso being that the PAO stock used be liquid at ambient temperature.
  • the present invention achieves its reduction in traction coefficient by use of a lubricant comprising a bimodal blend of two different base stock, the first being one or more oils selected from the group consisting of Group III, and Group IV base stocks, most preferably one or more Group III base stocks having a KV at 100°C of from 2 to 12 mm 2 /s and the second being one or more Group IV base stocks having a KV at 100°C of at least 38, preferably 38 to 1200 mm 2 /s, more preferably 38 to 600 mm 2 /s, provided there is a difference in KV between the first and second base stock of at least 30 mm 2 /s and the blend has a KV at 100°C of 16 mm 2 /s or less.
  • the method for reducing traction coefficient uses engine lubricating oil composition as described above containing the bimodal base stock blend as a minimum necessary and essential component.
  • the method can use engine lubricating oils containing additional performance additives provided the base stock comprises the essential bimodal blend base stock.
  • Formulated lubricating oil using the bimodal blend of base stocks as recited in the present specification may additionally contain one or more of the commonly used lubricating oil performance additives including but not limited to dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other anti-wear and/or extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, other friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • the commonly used lubricating oil performance additives including but not limited to dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other anti-wear and/or extreme pressure additives, anti-seizure agents, wax modifiers,
  • a series of engine oils was evaluated in regard to the effect base stock composition has on traction coefficient.
  • the engine oils were unadditized base stock blends.
  • the traction coefficient was measured employing the MTM Traction Rig, which is a fully automated Mini Traction Machine traction measurement instrument.
  • the rig is manufactured by PCS Instruments and identified as Model MTM.
  • the test specimens and apparatus configuration are such that realistic pressures, temperatures and speeds can be attained without requiring very large loads, motors or structures.
  • a small sample of fluid (50 ml) is placed in the test cell and the machine automatically runs through a range of speeds, slide-to-roll ratios, temperatures and loads to produce a comprehensive traction map for the test fluid without operational intervention.
  • the standard test specimens are a polished 19.05 mm ball and a 50.0 mm diameter disc manufactured from AISI 52100 bearing steel.
  • the specimens are designed to be single use, throw away items.
  • the ball is loaded against the face of the disc and the ball and disc are driven independently by DC servo motors and drives to allow high precision speed control, particularly at low slide/roll ratios.
  • Each specimen is end mounted on shafts in a small stainless steel test fluid bath.
  • the vertical shaft and drive system which supports the disk test specimen is fixed.
  • the shaft and drive system which supports the ball test specimen is supported by a gimbal arrangement such that it can rotate around two orthogonal axes. One axis is normal to the load application direction, the other to the traction force direction.
  • the ball and disk are driven in the same direction.
  • the traction coefficient is the ratio of the traction force to the applied load. As shown in Figures 1-4 , the traction coefficient was measured over a range of speeds. In Figures 1-4 , the speed on the x-axis is the entrainment speed, which is half the sum of the ball and disk speeds. These entrainment speeds simulate the range of surface speeds, or at least a portion of the range of surface speeds, reached when the engine is operating.
  • test results presented herein were generated under the following test conditions: Temperature 100°C Load 1.0 GPa Slide-to-roll ratio (SRR) 50% Speed gradient 0-3000 mm/sec in 480 seconds
  • Figure 3 shows that the blend of Group III stock with a Group IV stock (Oil III, Oil IV and Oil V) exhibited a reduction in traction coefficient at all speeds tested (as low as 3 mm/s) compared to Reference oil A and all other Oils evaluated.

Claims (6)

  1. Utilisation d'une huile lubrifiante composée d'une huile de base comprenant un mélange bimodal de deux huiles de base différentes,
    la première huile de base étant une ou plusieurs huiles choisies dans le groupe constitué par les huiles de base du groupe III et du groupe IV, ladite première huile de base ayant une viscosité cinématique à 100 °C de 2 à 12 mm2/s et
    une seconde huile de base étant une ou plusieurs huiles choisies dans les huiles de base du groupe IV ayant une viscosité cinématique à 100 °C d'au moins 38 mm2/s,
    la différence de viscosité cinématique entre les première et seconde huiles de base étant d'au moins 30 mm2/s, et
    la combinaison des première et seconde huiles de base ayant une viscosité cinématique à 100 °C de 16 mm2 ou moins,
    comme huile pour moteurs destinée à lubrifier de gros moteurs à basse et moyenne vitesse dans lesquels la vitesse à laquelle des surfaces en interaction du moteur se déplacent l'une devant l'autre quand le moteur fonctionne atteint au moins 30 mm/s pour améliorer l'économie de carburant desdits moteurs, lesdites surfaces en interaction étant choisies dans le groupe constitué par un piston et une paroi de cylindre et/ou des surfaces en interaction des paliers,
    l'amélioration de l'économie de carburant étant mise en évidence par le fait que le coefficient de traction de l'huile pour moteurs employant le mélange bimodal est inférieur au coefficient de traction d'huiles pour moteurs qui ne sont pas des mélanges bimodales ou qui ne sont pas bimodales au même degré tel qu'énoncé ou qui sont basées sur des mélanges d'au moins deux huiles, de base du groupe I ou des mélanges d'au moins deux huiles de base du groupe II ou des mélanges d'huiles de base du groupe I et du groupe II, et
    le coefficient de traction étant mesuré en utilisant un instrument de mesure à minimachine de traction automatisée (banc de traction MTM) à une température de 100 °C, sous une charge de 1,0 GPa, un taux de glissement (SRR) de 50 % et un gradient de vitesse de 0-3000 mm/s en 480 secondes.
  2. Utilisation selon la revendication 1 dans laquelle la première huile de base est une huile de base du groupe III.
  3. Utilisation selon la revendication 1 dans laquelle la première huile de base est une huile de base du groupe IV.
  4. Utilisation selon la revendication 1 dans laquelle l'huile de base, du groupe IV, qu'elle soit la première ou la seconde huile de base est une huile PAO.
  5. Utilisation selon la revendication 4 dans laquelle l'huile PAO est élaborée en employant la catalyse métallocène.
  6. Utilisation selon la revendication 4 dans laquelle l'huile de base PAO est caractérisée en ce que pas plus de 5,0 % en poids du polymère n'a une masse moléculaire de plus de 45 000 Daltons.
EP11705319.9A 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction Not-in-force EP2531582B1 (fr)

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US33720510P 2010-02-01 2010-02-01
US33721310P 2010-02-01 2010-02-01
US33720410P 2010-02-01 2010-02-01
US33721510P 2010-02-01 2010-02-01
US33718210P 2010-02-01 2010-02-01
PCT/US2011/022965 WO2011094571A1 (fr) 2010-02-01 2011-01-28 Procédé permettant d'améliorer le rendement du carburant par l'utilisation de compositions d'huiles moteurs pour gros moteurs à bas et moyen régimes par réduction du coefficient de traction

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EP11706660.5A Active EP2531584B1 (fr) 2010-02-01 2011-01-28 Utilisation pour ameliorer le rendement énergétique de compositions d'huile moteur pour moteurs à faible, moyenne et grande vitesses, par réduction du coefficient de traction
EP19167432.4A Withdrawn EP3527650A1 (fr) 2010-02-01 2011-01-28 Utilisation pour ameliorer le rendement énergétique de compositions d'huile moteur pour moteurs à faible, moyenne et grande vitesses, par réduction du coefficient de traction
EP11705319.9A Not-in-force EP2531582B1 (fr) 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction
EP11706663.9A Not-in-force EP2531585B1 (fr) 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteur pour ameliorer le rendement énergétique de moteurs rapides, lents et semi-rapides par réduction du coefficient de traction
EP11705318.1A Active EP2531581B1 (fr) 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction
EP11705321.5A Not-in-force EP2531583B1 (fr) 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction
EP19167430.8A Withdrawn EP3527649A1 (fr) 2010-02-01 2011-01-28 Utilisation pour ameliorer le rendement énergétique de compositions d'huile moteur pour moteurs à faible, moyenne et grande vitesses, par réduction du coefficient de traction

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EP19167432.4A Withdrawn EP3527650A1 (fr) 2010-02-01 2011-01-28 Utilisation pour ameliorer le rendement énergétique de compositions d'huile moteur pour moteurs à faible, moyenne et grande vitesses, par réduction du coefficient de traction

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EP11705318.1A Active EP2531581B1 (fr) 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction
EP11705321.5A Not-in-force EP2531583B1 (fr) 2010-02-01 2011-01-28 Utilisation de compositions d'huiles moteurs pour améliorer le rendement du carburant de gros moteurs à bas et moyen régimes par réduction du coefficient de traction
EP19167430.8A Withdrawn EP3527649A1 (fr) 2010-02-01 2011-01-28 Utilisation pour ameliorer le rendement énergétique de compositions d'huile moteur pour moteurs à faible, moyenne et grande vitesses, par réduction du coefficient de traction

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Publication number Publication date
EP2531581A1 (fr) 2012-12-12
JP5755253B2 (ja) 2015-07-29
SG182502A1 (en) 2012-08-30
EP2531584A1 (fr) 2012-12-12
SG182699A1 (en) 2012-08-30
WO2011094582A1 (fr) 2011-08-04
JP5755252B2 (ja) 2015-07-29
EP2531585A1 (fr) 2012-12-12
JP2016000827A (ja) 2016-01-07
EP3527649A1 (fr) 2019-08-21
WO2011094575A1 (fr) 2011-08-04
JP2013518936A (ja) 2013-05-23
JP5755251B2 (ja) 2015-07-29
SG182700A1 (en) 2012-08-30
WO2011094571A1 (fr) 2011-08-04
WO2011094571A8 (fr) 2012-10-11
EP2531585B1 (fr) 2018-06-20
JP5852012B2 (ja) 2016-02-03
SG182697A1 (en) 2012-08-30
EP2531582A1 (fr) 2012-12-12
JP5755254B2 (ja) 2015-07-29
JP6050450B2 (ja) 2016-12-21
EP2531583A1 (fr) 2012-12-12
WO2011094566A1 (fr) 2011-08-04
EP2531584B1 (fr) 2019-06-19
JP2013518937A (ja) 2013-05-23
JP2013518938A (ja) 2013-05-23
WO2011094562A1 (fr) 2011-08-04
JP2013518935A (ja) 2013-05-23
JP2013518939A (ja) 2013-05-23
EP2531583B1 (fr) 2018-07-18
EP2531581B1 (fr) 2018-07-11
SG182504A1 (en) 2012-08-30
EP3527650A1 (fr) 2019-08-21

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