EP3645688B1 - Schmierölzusammensetzung - Google Patents

Schmierölzusammensetzung Download PDF

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Publication number
EP3645688B1
EP3645688B1 EP18734961.8A EP18734961A EP3645688B1 EP 3645688 B1 EP3645688 B1 EP 3645688B1 EP 18734961 A EP18734961 A EP 18734961A EP 3645688 B1 EP3645688 B1 EP 3645688B1
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EP
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Prior art keywords
engine
lubricating oil
oil composition
diesel engine
base
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EP18734961.8A
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English (en)
French (fr)
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EP3645688A1 (de
Inventor
John Dominic PALAZZOTTO
Martin Joseph Brown
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Chevron Oronite Co LLC
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Chevron Oronite Co LLC
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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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02—Specified values of viscosity or viscosity index
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M9/00—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
    • F01M9/10—Lubrication of valve gear or auxiliaries
    • 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
    • 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
    • C10M2205/026—Butene
    • 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
    • C10M2205/026—Butene
    • C10M2205/0265—Butene 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
    • C10M2290/00—Mixtures of base materials or thickeners or additives
    • C10M2290/02—Mineral base oils; Mixtures of fractions
    • 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
    • C10N2030/02—Pour-point; 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/40—Low content or no content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2030/74—Noack Volatility
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • 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
    • 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
    • C10N2040/255—Gasoline engines

Definitions

  • the present disclosure relates to lubricants for use in engines operated under sustained high load conditions, such as natural gas-fueled engines and low-speed or medium-speed diesel-fueled engines, and to methods for enhancing the deposit control capacity of the lubricants used in such engines, particularly those equipped with steel pistons.
  • WO 2014/057641 A1 discloses a system lubrication oil composition for a crosshead diesel engine, the composition having minimal formation of deposits even when a Group II or III base oil is used, and having excellent high-temperature cleanness and coking resistance.
  • a natural gas engine lubricating oil composition comprising: (a) a first base oil component selected from a Group I base stock, a Group II base stock, a Group III base stock, or a combination thereof, each having a kinematic viscosity at 100°C of from 8.5 to 15 mm 2 /s; and (b) a second base oil component selected from a Group I base stock, a Group II base stock, a Group III base stock, or a combination thereof, each having a kinematic viscosity at 100°C of from 4.0 to less than 8.5 mm 2 /s; wherein the weight ratio of the first base oil component to the second base oil component is in a range of from 1:10 to 1:1.15.
  • a low-speed or medium-speed diesel engine lubricating oil composition comprising: (a) a first base oil component selected from a Group I base stock, a Group II base stock, a Group III base stock, or a combination thereof, each having a kinematic viscosity at 100°C of from 8.5 to 15 mm 2 /s; and (b) a second base oil component selected from a Group I base stock, a Group II base stock, a Group III base stock, or a combination thereof, each having a kinematic viscosity at 100°C of from 4.0 to less than 8.5 mm 2 /s; wherein the weight ratio of the first base oil component to the second base oil component is in a range of from 1:10 to 1:1.15.
  • a method of controlling deposit formation in an internal combustion engine selected from a natural gas engine, a low-speed diesel engine or a medium-speed diesel engine which comprises operating the internal combustion engine with the lubricating oil composition disclosed herein.
  • lubricating oil composition described herein for the purpose of controlling deposit formation in an internal combustion engine selected from a natural gas engine, a low-speed diesel engine or a medium-speed diesel engine.
  • a “major amount” means 50 wt. % or more of a composition.
  • a “minor amount” means less than 50 wt. % of a composition.
  • base stock and “base oil” are used synonymously and interchangeably.
  • a “dual-fuel engine” refers to an engine that can run on a mixture of natural gas and diesel.
  • the combination of natural gas and diesel may comprise at least 60% natural gas.
  • the lubricating oil composition disclosed herein is utilized in a natural gas engine, a low-speed diesel engine or a medium-speed diesel engine.
  • the engine may be a two-stroke engine, three-stroke engine, four-stroke engine, five-stroke engine, or six-stroke engine.
  • the engine may also include any number of combustion chambers, pistons, and associated cylinders (e.g., 1-24).
  • the engine may be a large-scale industrial reciprocating engine having 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16, 18, 20, 24 or more pistons reciprocating in cylinders.
  • the piston may be an aluminum piston or a steel piston (e.g., steel or any of a variety of steel alloys, such as 42CrMo4V or 38MnVS6).
  • the natural gas engine may be a stationary natural gas engine, a stationary biogas engine, a stationary landfill gas engine, a stationary unconventional natural gas engine, or a dual-fuel engine.
  • Diesel engines may generally be classified as low-speed, medium-speed or high-speed engines.
  • a “low-speed” diesel engine means a compression-ignition internal combustion engine that is driven at a rotational speed that is less than 500 revolutions per minute (rpm), such as marine crosshead diesel engines;
  • a “medium-speed” diesel engine means a compression-ignition internal combustion engine that is driven at a rotational speed of 500 to 1800 rpm, such as locomotive diesel engines, marine trunk piston diesel engines, or land-based stationary power diesel engines;
  • a "high-speed” diesel engine means a compression-ignition internal combustion engine that is driven at a rotational speed that is higher than 1800 rpm, such as diesel engines for highway vehicles.
  • the lubricating oil composition disclosed herein may be utilized in controlling deposits in engines operating under high sustained load conditions, such as a Brake Mean Effective Pressure (BMEP) of at least 20 bar (2.0 MPa), e.g., at least 22 bar (2.2 MPa), at least 24 bar (2.4 MPa), at least 26 bar (2.6 MPa), 20 to 30 bar (2.0 to 3.0 MPa), 22 to 30 bar (2.2 to 3.0 MPa), 22 to 28 bar (2.2 to 2.8 MPa), or 24 to 30 bar (2.4 to 3.0 MPa).
  • BMEP Brake Mean Effective Pressure
  • the lubricating oil composition of the present disclosure may provide advantaged deposit control performance in any of a number of mechanical components of an engine.
  • the mechanical component may be a piston, a piston ring, a cylinder liner, a cylinder, a cam, a tappet, a lifter, a gear, a valve, a valve guide, or a bearing including a journal, a roller, a tapered, a needle, or a ball bearing.
  • the mechanical component comprises steel.
  • Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509 - Appendix E) to create guidelines for lubricant base oils.
  • Group I base stocks contain less than 90% saturates and/or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120.
  • Group II base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120.
  • Group III base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120.
  • Group IV base stocks are polyalphaolefins.
  • Group V base stocks include all other base stocks not included in Groups I, II, III or IV. Table 1 summarizes properties of each of these five groups. TABLE 1 Base Oil Properties Group ( 1) Saturates (2) Sulfur (3) Viscosity Index (4) Group I ⁇ 90% and/or >0.03% 80 to ⁇ 120 Group II ⁇ 90% ⁇ 0.03% 80 to ⁇ 120 Group III ⁇ 90% ⁇ 0.03% ⁇ 120 Group IV Polyalphaolefins (PAOs) Group V All other base stocks not included in Groups I, II, III or IV (1) Groups I-III are mineral oil base stocks (2) ASTM D2007 (3) ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927 (4) ASTM D2270
  • the lubricating oil composition of the present disclosure is a mixture of at least two base oil components.
  • the mixture of the at least two base oil components comprises a minor amount of first base oil component having a kinematic viscosity at 100°C of from 8.5 to 15.0 mm 2 /s (e.g., 9.0 to 14.0 mm 2 /s or 10.0 to 13.0 mm 2 /s or 10.0 to 12.0 mm 2 /s ), which base oil component is selected from one or more of a Group I base stock, a Group II base stock, and a Group III base stock, in combination with a major amount of a second base oil component having a kinematic viscosity at 100°C of from 4.0 to less than 8.5 mm 2 /s (e.g.
  • the base oil component is selected from one or more of a Group I base stock, a Group II base stock and a Group III base stock.
  • the first base oil component may be selected from a Group II base stock, a Group III base stock, or a combination thereof.
  • the second base oil component may be selected from a Group II base stock, a Group III base stock, or a combination thereof.
  • the first base oil component of high viscosity can be made up of a single base stock meeting the recited kinematic viscosity range or be made up of two or more base stocks, each meeting the recited kinematic viscosity limits.
  • the second base oil component of low viscosity can be made up of a single base stock meeting the recited kinematic viscosity range or it may be made up of two or more base stocks, each of which meet the recited kinematic viscosity limit.
  • the weight ratio of the first base oil component to the second base oil component may range from 1:10 to 1:1.15 (e.g., 1:10 to 1:6, 1:8 to 1:5, 1:5 to 1:1.15, 1:6 to 1:4, 1:4 to 1:2, 1:3 to 1:1.15, 1:6 to 1:2, or 1:3 to 1:1.15).
  • the lubricating oil composition of this disclosure are identified by viscosity standards of the Society of Automotive Engineers (SAE) for engine oils (i.e., the SAE J300 standard).
  • SAE J300 viscosity grades are summarized in Table 2.
  • the lubricating oil composition of this disclosure is a monograde engine oil of SAE 40, SAE 50 or SAE 60 viscosity grade.
  • a thickener may be added to the lubricating oil composition to increase its viscosity.
  • Any suitable thickener may be used such as polyisobutylene (PIB).
  • PIB is a commercially available material from several manufacturers.
  • Polyisobutylene is typically a viscous oil-miscible liquid having a number average molecular weight of 800 to 5000 (e.g., 1000 to 2500) and a kinematic viscosity at 100°C of 200 to 5000 mm 2 /s (e.g., 200 to 1000 mm 2 /s).
  • the amount of PIB added to the lubricating oil composition will normally be from 1 to 20 wt. % (e.g., 2 to 15 wt. % or 4 to 12 wt. %) of the finished oil.
  • the lubricating oil composition may contain low levels of sulfated ash, as determined by ASTM D874.
  • the composition may have a sulfated ash content of less than 1.0 wt. % (e.g., less than 0.6 wt. % or even less than 0.15 wt. %), based on the total weight of the composition.
  • the lubricating oil composition may be substantially zinc-free.
  • the lubricating oil composition is free of bright stock.
  • the lubricating oil compositions of the present disclosure may contain one or more performance additives that can impart or improve any desirable property of the lubricating oil composition.
  • Any additive known to those of skill in the art may be used in the lubricating oil composition disclosed herein.
  • Some suitable additives have been described by R.M. Mortier et al. "Chemistry and Technology of Lubricants,”3rd Edition, Springer (2010 ) and L.R. Rudnik “Lubricant Additives: Chemistry and Applications," Second Edition, CRC Press (2009 ).
  • the concentration of each of the additives in the lubricating oil composition when used, may range from 0.001 to 10 wt. % (e.g., 0.01 to 5 wt. %, or 0.05 to 2.5 wt. %) of the lubricating oil composition. Further, the total amount of additives in the lubricating oil composition may range from 0.001 to 20 wt. % (e.g., 0.01 to 15 wt. % or 0.1 to 10 wt. %) of the lubricating oil composition.
  • the present lubricating oil composition may additionally contain one or more of the other commonly used lubricating oil performance additives including antioxidants, anti-wear agent, metal detergents, dispersants, friction modifiers, corrosion inhibitors, demulsifiers, viscosity modifiers, pour point depressants, foam inhibitors, and others.
  • other commonly used lubricating oil performance additives including antioxidants, anti-wear agent, metal detergents, dispersants, friction modifiers, corrosion inhibitors, demulsifiers, viscosity modifiers, pour point depressants, foam inhibitors, and others.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • Useful antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols and alkali and alkaline earth metal salts thereof.
  • the hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
  • suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di- tert -butylphenol, 2,2'-methylenebis(6- tert- butyl-4-methylphenol), 4,4'-bis(2,6-di- tert -butylphenol) and 4,4'-methylenebis(2,6-di-tert-butylphenol).
  • the hindered phenol antioxidant may be an ester or an addition product derived from 2,6-di- tert -butylphenol and an alkyl acrylate, wherein the alkyl group may contain from 1 to 18 carbon atoms.
  • Suitable aromatic amine antioxidants include diarylamines such as alkylated diphenylamines (e.g., dioctyl diphenylamine, dinonyl diphenylamine), phenyl-alpha-naphthalene and alkylated phenyl-alpha-naphthalenes.
  • diarylamines such as alkylated diphenylamines (e.g., dioctyl diphenylamine, dinonyl diphenylamine), phenyl-alpha-naphthalene and alkylated phenyl-alpha-naphthalenes.
  • Anti-wear agents reduce wear of metal parts.
  • anti-wear agents include phosphorus-containing anti-wear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites.
  • the anti-wear agent may be a zinc dialkyldithiophosphate.
  • Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
  • a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
  • the anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • the lubricating oil composition provided herein comprises at least a neutral or overbased metal detergent as an additive, or additive components.
  • the metal detergents in lubricating oil compositions acts as a neutralizer of acidic products within the oil.
  • the metal detergent prevents the formation of deposits on the surface of an engine.
  • the detergent may have additional functions, for example, antioxidant properties.
  • lubricating oil compositions contain metal detergents comprising either overbased detergents or mixtures of neutral and overbased detergents. The term "overbased" is intended to define additives which contain a metal content in excess of that required by the stoichiometry of the particular metal and the particular organic acid used.
  • the excess metal exists in the form of particles of inorganic base (e.g., a hydroxide or carbonate) surrounded by a sheath of metal salt.
  • the sheath serves to maintain the particles in dispersion in a liquid oleaginous vehicle.
  • the amount of excess metal is commonly expressed as the ratio of total equivalence of excess metal to equivalence of organic acid and is typically in a range of 0.1 to 30.
  • suitable metal detergents include sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an alkyl or alkenyl multiacid, and chemical and physical mixtures thereof.
  • suitable metal detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates and combinations thereof.
  • the metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate detergents.
  • suitable metals include alkali metals, alkaline metals and transition metals.
  • the metal is Ca, Mg, Ba, K, Na, Li or the like.
  • An exemplary metal detergent which may be employed in the lubricating oil compositions includes overbased calcium phenate.
  • a dispersant is an additive whose primary function is to hold solid and liquid contaminations in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Dispersants are usually "ashless", being non-metallic organic materials that form substantially no ash on combustion, in contrast to metal-containing, and hence ash-forming materials. They comprise a long hydrocarbon chain with a polar head, the polarity being derived from inclusion of at least one nitrogen, oxygen or phosphorus atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example, 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric backbone.
  • a preferred class of olefin polymers is constituted by polybutylenes, specifically polyisobutylenes (PIB) or poly-n-butylenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • PIB polyisobutylenes
  • poly-n-butylenes such as may be prepared by polymerization of a C 4 refinery stream.
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • a noteworthy group of dispersants is constituted by hydrocarbon-substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine.
  • Typical commercially available polyisobutylene-based succinimide dispersants contain polyisobutylene polymers having a number average molecular weight ranging from 900 to 2500, functionalized by maleic anhydride, and derivatized with polyamines having a molecular weight of from 100 to 350.
  • Suitable dispersants include succinic esters and ester-amides, Mannich bases, polyisobutylene succinic acid (PIBSA), and other related components.
  • PIBSA polyisobutylene succinic acid
  • Succinic esters are formed by the condensation reaction between hydrocarbon-substituted succinic anhydrides and alcohols or polyols.
  • the condensation product of a hydrocarbon-substituted succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinic ester-amides are formed by condensation reaction between hydrocarbon-substituted succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine is propoxylated hexamethylenediamine.
  • Mannich bases are made from the reaction of an alkylphenols, formaldehyde, and a polyalkylene polyamines. Molecular weights of the alkylphenol may range from 800 to 2500.
  • Nitrogen-containing dispersants may be post-treated by conventional methods to improve their properties by reaction with any of a variety of agents.
  • boron compounds e.g., boric acid
  • cyclic carbonates e.g., ethylene carbonate
  • a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Friction modifiers include alkoxylated fatty amines, borated fatty epoxides, fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters and fatty imidazolines.
  • fatty means a hydrocarbon chain having 10 to 22 carbon atoms, typically a straight hydrocarbon chain.
  • Other known friction modifiers comprise oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and anti-wear credits to a lubricating oil composition. Suitable oil-soluble organo-molybdenum compounds have a molybdenum-sulfur core. As examples, there may be mentioned dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof. The molybdenum compound may be dinuclear or trinuclear.
  • Corrosion inhibitors protect lubricated metal surfaces against chemical attack by water or other contaminants.
  • Suitable corrosion inhibitors include polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles and anionic alkyl sulfonic acids.
  • Viscosity modifiers provide lubricants with high and low temperature operability. These additives increase the viscosity of the oil composition at elevated temperatures which increases film thickness, while having limited effect on viscosity at low temperatures.
  • Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant.
  • Typical molecular weights of these polymers are in a range of 1000 to 1,000,000 (e.g., 2000 to 500,000 or 25,000 to 100,000).
  • suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity modifier.
  • Another suitable viscosity modifier is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
  • Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
  • pour point depressants lower the minimum temperature at which a fluid will flow or can be poured.
  • Suitable pour point depressants include C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like.
  • Foam inhibitors retard the formation of stable foams.
  • suitable foam inhibitors include polysiloxanes, polyacrylates, and the like.
  • lubricating oil compositions were prepared having the formulations set forth in the following Examples.
  • the compositions were prepared by mixing the base oil(s) with additive packages according to conventional preparation methods.
  • Base oil properties are listed in Table 3.
  • Deposit performance of the lubricant oil compositions was measured using the Penn State Micro-Oxidation Test after 35 minutes at 260°C (SAE Technical Paper 801362).
  • TABLE 3 Base Oil Properties Property ASTM Method Base Oil 1 Base Oil 2 Kinematic Viscosity, 100°C, mm 2 /s D445 11.46 6.58 Viscosity Index D2270 106 105 Saturates, % D2007 97.2 97.6 Aromatics, % D2007 2.6 2.5 Sulfur, wt.
  • Lubricating oil compositions 1 and 2 were formulated to meet ashless natural gas engine oil specifications and major natural gas engine manufacturers' requirements. The results are presented in Table 4. TABLE 4 Example 1 Example 2 Base Oil 1, wt. % 93.40 18.68 Base Oil 2, wt. % - 74.72 Additive Package, wt. % 6.60 6.60 Physical Properties of Lubricant SAE Viscosity Grade 40 20 Kinematic Viscosity, 100°C, mm 2 /s 12.96 8.06 Sulfated Ash, wt. % 0.03 0.03 Test Results Deposit, wt. % 24.42 14.37
  • Lubricating oil compositions 3 and 4 were formulated to meet dual fuel engine oil specifications and major dual fuel engine manufacturers' requirements. The results are presented in Table 5. TABLE 5 Example 3 Example 4 Base Oil 1, wt. % 90.54 18.11 Base Oil 2, wt. % - 72.43 Additive Package, wt. % 9.46 9.46 Physical Properties of Lubricant SAE Viscosity Grade 40 20 Kinematic Viscosity, 100°C, mm 2 /s 13.46 8.37 Sulfated Ash, wt. % 0.70 0.70 Test Results Deposit, wt. % 14.37 12.39
  • Lubricating oil compositions 5 and 6 were formulated to meet low ash natural engine oil specifications and major natural gas engine manufacturers' requirements. The results are presented in Table 6. TABLE 6 Example 5 Example 6 Base Oil 1, wt. % 91.8 18.36 Base Oil 2, wt. % - 73.44 Additive Package, wt. % 8.20 8.20 Physical Properties of Lubricant SAE Viscosity Grade 40 20 Kinematic Viscosity, 100°C, mm 2 /s 13.64 8.61 Sulfated Ash, wt. % 0.45 0.45 Test Results Deposit, wt. % 28.76 13.73
  • Lubricating oil compositions 7 and 8 were formulated to meet marine engine oil specifications and major marine engine manufacturers' requirements. The results are presented in Table 7. TABLE 7 Example 7 Example 8 Base Oil 1, wt. % 88.60 17.72 Base Oil 2, wt. % - 70.88 Additive Package, wt. % 11.40 11.40 Physical Properties of Lubricant SAE Viscosity Grade 40 20 Kinematic Viscosity, 100°C, mm 2 /s 13.40 8.55 Sulfated Ash, wt. % 3.10 3.10 Test Results Deposit, wt. % 2.51 1.28
  • Lubricating oil compositions 9 and 10 were formulated to meet locomotive engine oil requirements and major locomotive engine manufacturers' requirements. The results are listed in Table 8. TABLE 8 Example 9 Example 10 Base Oil 1, wt. % 90.30 18.06 Base Oil 2, wt. % - 72.24 Additive Package, wt. % 9.70 9.70 Physical Properties of Lubricant SAE Viscosity Grade 40 20 Kinematic Viscosity, 100°C, mm 2 /s 14.02 8.79 Sulfated Ash, wt. % 1.15 1.15 Test Results Deposit, wt. % 24.7 9.62
  • Examples 1-10 show that lubricating oil compositions containing a heavy base stock in combination with a light base stock provided improved deposit control over lubricating oil compositions containing solely heavy base stock.
  • Lubricating oil compositions 11-13 were formulated to meet natural gas engine oil specifications and major natural gas engine manufacturers' requirements. The results are presented in Table 9. TABLE 9 Example 11 Example 12 Example 13 Base Oil 1 wt. % 39.33 15.73 88.67 Base Oil 2, wt. % 39.34 62.94 - Additive Package, wt. % 11.33 11.33 11.33 2300 MW Polyisobutylene, wt. % 10 10 0 Physical Properties of Lubricant SAE Viscosity Grade 40 40 40 Kinematic Viscosity, 100°C, mm 2 /s 15.98 13.61 13.56 Sulfated Ash, wt. % 0.71 0.71 0.71 Test Results Deposit, wt. % 13.46 8.43 20.19

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Claims (12)

  1. Schmierölzusammensetzung für einen Erdgasmotor, einen niedertourigen Dieselmotor oder einen mitteltourigen Dieselmotor, umfassend:
    (a) eine erste Basisölkomponente ausgewählt aus einem Basismaterial der Gruppe I, einem Basismaterial der Gruppe II, einem Basismaterial der Gruppe III oder einer Kombination davon, wobei jedes eine kinematische Viskosität bei 100 °C von 8,5 bis 15 mm2/s hat; und
    (b) eine zweite Basisölkomponente ausgewählt aus einem Basismaterial der Gruppe I, einem Basismaterial der Gruppe II, einem Basismaterial der Gruppe III oder einer Kombination davon, wobei jedes eine kinematische Viskosität bei 100 °C von 4,0 bis weniger als 8,5 mm2/s hat; und
    wobei das Gewichtsverhältnis der ersten Basisölkomponente zu der zweite Basisölkomponente im Bereich von 1:10 bis 1:1,15 liegt;
    wobei die Schmierölzusammensetzung ein Motoröl der Viskositätsklasse SAE 40, SAE 50 oder SAE 60 ist; und
    wobei die Schmierölzusammensetzung frei von Brightstock ist.
  2. Schmierölzusammensetzung nach Anspruch 1, wobei das Gewichtsverhältnis der ersten Basisölkomponente zu der zweite Basisölkomponente im Bereich von 1:5 bis 1:1,15 liegt.
  3. Schmierölzusammensetzung nach Anspruch 1, wobei die Schmierölzusammensetzung für den mitteltourigen Dieselmotor im Wesentlichen zinkfrei ist.
  4. Verwendung der Schmierölzusammensetzung nach Anspruch 1 zum Schmieren eines Erdgasmotors ausgewählt aus einem stationären Erdgasmotor, einem stationären Biogasmotor, einem stationären Deponiegasmotor, einem stationären unkonventionellen Erdgasmotor oder einem Dual-Fuel-Motor.
  5. Verwendung der Schmierölzusammensetzung nach Anspruch 1 zum Schmieren eines niedertourigen Dieselmotors, und wobei der niedertourige Dieselmotor ein Kreuzkopf-Schiffsdieselmotor ist.
  6. Verwendung der Schmierölzusammensetzung nach Anspruch 1 zum Schmieren eines mitteltourigen Dieselmotors ausgewählt aus einem Lokomotivendieselmotor, einem Tauchkolben-Schiffsdieselmotor oder einem bodengebundenen Dieselmotor zur stationären Energieversorgung.
  7. Schmierölzusammensetzung nach Anspruch 1, des Weiteren umfassend 1 bis 20 Gew.%, bezogen auf das Gesamtgewicht der Zusammensetzung, eines Polyisobutylens mit einer kinematischen Viskosität bei 100 °C von 200 bis 5000 mm2/s.
  8. Schmierölzusammensetzung nach Anspruch 1, des Weiteren umfassend mindestens ein Additiv ausgewählt aus einem Antioxidans, Antiverschleißmittel, Metalldetergens, Dispergiermittel, Reibungsmodifizierungsmittel, Korrosionsschutzmittel, Demulgator, Viskositätsmodifizierungsmittel, Stockpunktsenker, Schaumverhütungsmittel und Mischungen davon.
  9. Verfahren zur Kontrolle der Bildung von Ablagerungen in einer mechanischen Komponente eines Verbrennungsmotors ausgewählt aus einem Erdgasmotor, einem niedertourigen Dieselmotor oder einem mitteltourigen Dieselmotor, wobei das Verfahren Betreiben des Verbrennungsmotors mit einer Schmierölzusammensetzung nach einem der Ansprüche 1 bis 3, 7 bis 8 umfasst.
  10. Verfahren nach Anspruch 9, wobei die mechanische Komponente ein Kolben, ein Kolbenring, eine Zylinderlaufbuchse, ein Zylinder, ein Nocken, ein Stößel, ein Heber, ein Zahnrad, ein Ventil, eine Ventilführung oder ein Lager ist, einschließlich eines Zapfenlagers, eines Wälzlagers, eines konischen Lagers, eines Nadellagers oder eines Kugellagers.
  11. Verfahren nach Anspruch 9, wobei die mechanische Komponente Stahl umfasst.
  12. Verfahren nach Anspruch 9, wobei der Verbrennungsmotor unter einer Last mit einem mittleren Effektivdruck größer als 20 bar (2,0 MPa) betrieben wird.
EP18734961.8A 2017-06-27 2018-06-05 Schmierölzusammensetzung Active EP3645688B1 (de)

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CN113831945B (zh) * 2020-06-24 2022-11-22 中国石油化工股份有限公司 一种改善涡轮增压器结焦问题的柴油发动机油及制备工艺
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US20070117726A1 (en) * 2005-11-18 2007-05-24 Cartwright Stanley J Enhanced deposit control for lubricating oils used under sustained high load conditions
US20070151526A1 (en) * 2005-12-02 2007-07-05 David Colbourne Diesel engine system
US8034752B2 (en) * 2008-03-11 2011-10-11 Afton Chemical Corporation Lubricating composition
US8642523B2 (en) * 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
JP5898691B2 (ja) * 2010-12-17 2016-04-06 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎｖｅｎｎｏｏｔｓｈａｐ 潤滑組成物
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US20150099675A1 (en) * 2013-10-03 2015-04-09 Exxonmobil Research And Engineering Company Compositions with improved varnish control properties
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CA3065428A1 (en) 2019-01-03
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