EP3112447B1 - Additivpaket für die schmierung eines schiffsmotors - Google Patents

Additivpaket für die schmierung eines schiffsmotors Download PDF

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Publication number
EP3112447B1
EP3112447B1 EP16174815.7A EP16174815A EP3112447B1 EP 3112447 B1 EP3112447 B1 EP 3112447B1 EP 16174815 A EP16174815 A EP 16174815A EP 3112447 B1 EP3112447 B1 EP 3112447B1
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Prior art keywords
composition
oil
additive
mass
additive package
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English (en)
French (fr)
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EP3112447A1 (de
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Luciana ANGONESI
Peter Watts
Robert HOUGH
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives 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
    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/14—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 hydroxy groups
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16—Ethers
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing 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
    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • 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
    • C10N2030/04—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
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2040/10—Running-in-oil ; Grinding
    • 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

  • This invention relates to the lubrication of two-stroke and four-stroke marine diesel internal combustion engines, the former usually being referred to as cross-head engines and the latter as trunk piston engines.
  • Respective lubricants for these applications are usually known as marine diesel cylinder lubricants ("MDCL's”) and trunk piston engine oils (“TPEO's").
  • Cross-head engines are slow engines with a high to very high power range. They include two separately-lubricated parts: the piston/cylinder assembly lubricated, with total-loss lubrication, by a highly viscous oil (an MDCL); and the crankshaft lubricated by a less viscous lubricant, usually referred to as a system oil.
  • MDCL highly viscous oil
  • system oil a less viscous lubricant
  • Trunk piston engines may be used in marine, power-generation and rail traction applications, and have a higher speed than cross-head engines.
  • a single lubricant (TPEO) is used for crankcase and cylinder lubrication. All major moving parts of the engine, i.e. the main and big end bearings, camshaft and valve gear, are lubricated by means of a pumped circulation system.
  • the cylinder liners are lubricated partially by splash lubrication and partially by oil from the circulation systems that finds its way to the cylinder wall through holes in the piston skirt via the connecting rod and gudgeon pin.
  • Marine lubricants are routinely formulated with metal detergent additives.
  • a practical problem in use of detergents for this purpose is that certain combinations of salicylate and sulfonate detergents exhibit stability problems evidenced by gel or phase separation.
  • US2005/137098 discloses additive concentrates containing overbased calcium sulfonate detergents and overbased calcium salicylate detergents and lubricating oil compositions made with these additive concentrates. The aim of this invention is to reduce or overcome such problems.
  • the present invention provides in one aspect an additive package for a two-stroke or four-stroke marine engine lubricating oil composition, comprising less than 50 mass % of an oil of lubricating viscosity; more than 50 mass % of (A) an overbased metal hydroxybenzoate detergent additive and (B) an overbased metal sulfonate detergent additive; and (C) an oil-soluble hydrocarbylphenol-aldehyde condensate additive in an amount in the range of 1 to 10, preferably 3 to 6, mass %; wherein the ratio of (A) to (B), expressed as mmol of soap, is in the range of 90:10 to 10:90, preferably 80:20 to 20:80.
  • a two-stroke marine engine lubricating oil composition comprising an oil of lubricating viscosity, in a major amount, blended with a minor amount of the additive package defined above; wherein the composition has a TBN of 10 to 120, preferably 40 to 100, using ASTM D2896, or a four-stroke marine engine lubricating oil composition comprising an oil of lubricating viscosity, in a major amount, blended with a minor amount of the additive package defined above; wherein the composition has a TBN of 25 to 60, using ASTM D2896.
  • the additive package is preferably used at a treat rate of 15 to 30 mass % to produce the two-stroke composition, and at a treat rate of 10 to 20 mass % for the four-stroke engine composition.
  • the lubricating oil composition preferably includes from 0.15 to 1.5 mass % of the oil-soluble hydrocarbylphenol-aldehyde condensate additive for the two-stroke composition, and from 0.1 to 1 mass % of the oil-soluble hydrocarbylphenol-aldehyde condensate additive for the four-stroke engine.
  • the present invention comprises:-
  • the lubricant composition contains a major proportion of an oil of lubricating viscosity.
  • Such lubricating oils may range in viscosity from light distillate mineral oils to heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40, such as 3 to 15, mm 2 /sec, as measured at 100°C, and has a viscosity index of 80 to 100, such as 90 to 95.
  • the lubricating oil may comprise greater than 60, typically greater than 70, mass % of the composition.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivatives, analogues and homologues thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • alkyl and aryl ethers of polyoxyalkylene polymers e.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linole
  • esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • Unrefined, refined and re-refined oils can be used in lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further treatment are unrefined oils.
  • the present invention preferably embraces those of the above oils containing greater than or equal to 90% saturates and less than or equal to 0.03% sulphur as the oil of lubricating viscosity, e.g. Group II, III, IV or V. They also include basestocks derived from hydrocarbons synthesised by the Fischer-Tropsch process. In the Fischer-Tropsch process, synthesis gas containing carbon monoxide and hydrogen (or 'syngas') is first generated and then converted to hydrocarbons using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil.
  • the syngas may, for example, be made from gas such as natural gas or other gaseous hydrocarbons by steam reforming, when the basestock may be referred to as gas-to-liquid ("GTL”) base oil; or from gasification of biomass, when the basestock may be referred to as biomass-to-liquid (“BTL” or "BMTL”) base oil; or from gasification of coal, when the basestock may be referred to as coal-to-liquid (“CTL”) base oil.
  • GTL gas-to-liquid
  • BTL biomass-to-liquid
  • CTL coal-to-liquid
  • the invention is not however limited to use of the above-mentioned base stocks; thus it may, for example, include use of Group I basestocks and of bright stock.
  • the oil of lubricating viscosity in this invention contains 50 mass % or more of said basestocks. It may contain 60, such as 70, 80 or 90, mass % or more of said basestock or a mixture thereof.
  • the oil of lubricating viscosity may be substantially all of said basestock or a mixture thereof.
  • Each of these is a detergent, being an additive that reduces formation of deposits, for example, high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely-divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
  • a detergent comprises a polar head with a long hydrophobic tail.
  • Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • a metal compound such as an oxide or hydroxide
  • an acidic gas such as carbon dioxide
  • the detergent is preferably an alkali metal or alkaline earth metal additive such as an overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salt of a surfactant selected from an acid, wherein the overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilized in an oleaginous diluent by the oil-soluble salt of the surfactant.
  • the metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt.
  • the metal, whether the metal of the oil-soluble or oil-insoluble salt is calcium.
  • the TBN of the detergent may be low, i.e. less than 50 mg KOH/g, medium, i.e. 50-150 mg KOH/g, or high, i.e. over 150 mg KOH/g, as determined by ASTM D2896.
  • the TBN is medium or high, i.e. more than 50 TBN.
  • the TBN is at least 60, more preferably at least 100, more preferably at least 150, and up to 500, such as up to 350 mg KOH/g, as determined by ASTM D2896.
  • the surfactant is selected from a hydroxybenzoic acid, a particular example being a salicylic acid and wherein the salt is a salicylate.
  • Salicylate detergents are well known in the art.
  • the surfactant is selected from a sulfonic acid wherein the salt is a sulfonate.
  • Sulfonate detergents are also well known in the art.
  • Detergents that may be used are those that are hydrocarbyl (such as alkyl) substituted, such as those known in the art.
  • the ratio of (A) to (B), expressed as mmol of soap is in the range of 90:10 to 10:90.
  • the upper limit of the range there may be mentioned 80:20 and 75:25.
  • the lower limit of the range these may be mentioned 25:75. Said upper and lower limits may be independently combined to provide sub-ranges.
  • ADDITIVE e.g. Methylene - Bridged Alkyl Phenols ("MBAP's")
  • oxyalkylated hydrocarbylphenol condensates wherein oxyalkyl groups prepared from phenolic functional groups have the formula -(R'O) n -where R' is an ethylene, propylene or butylene group; and n is independently from 0 to 10; less than 45, preferably less than 30, mole % of the phenolic functional groups of the condensates are non-oxyalkylated; and more than 55 mole % of the phenolic functional groups of the condensates are mono-oxyalkylated.
  • EP-A-2 374 866 describes such condensates in more detail.
  • MBAP's constitute one embodiment thereof.
  • (C) is present in an amount in the range of 1 to 10, preferably 3 to 5, mass%.
  • 1 to 7 and 1 to 5 mass% there may also be mentioned 1 to 7 and 1 to 5 mass%.
  • an MBAP used in this invention may be capped or uncapped.
  • MDCL Marine Diesel Cylinder Lubricant
  • An MDCL may employ 10-35, preferably 13-30, most preferably 16-24, mass % of a concentrate or additive package, the remainder being base stock. It preferably includes at least 50, more preferably at least 60, even more preferably at least 70, mass % of oil of lubricating viscosity based on the total mass of MDCL.
  • the MDCL has a compositional TBN (using ASTM D2896) of 10-100, such as 70-100 or 40-100, preferably 60-90, more preferably 70-80.
  • Additive Mass% a.i. Broad
  • Mass % a.i. Preferred detergent(s) 1-20 3-15 dispersant(s) 0.5-5 1-3 anti-wear agent(s) 0.1-1.5 0.5-1.3
  • Trunk Piston Engine Oil (“TPEO)
  • a TPEO may employ 7-35, preferably 10-28, more preferably 12-24, mass % of a concentrate or additives package, the remainder being base stock.
  • the TPEO has a compositional TBN (using D2896) of 25-60, such as 25-55.
  • Additive Mass% a.i. Broad
  • Mass % a.i. Preferred detergent(s) 0.5-12 2-8 dispersant(s) 0.5-5 1-3 anti-wear agent(s) 0.1-1.5 0.5-1.3 oxidation inhibitor 0.2-2 0.5-1.5 rust inhibitor 0.03-0.15 0.05-0.1 pour point dispersant 0.03-1.15 0.05-0.1 base stock balance balance
  • 'oil-soluble' or 'oil-dispersible' do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • the lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
  • additive package(s) may be prepared, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby the additives can be added simultaneously to the oil of lubricating viscosity to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
  • the additives may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in the appropriate proportions, the remainder being base oil.
  • the final formulations may typically contain about 5 to 40 mass % of the additive packages(s), the remainder being base oil.
  • a calcium salicylate detergent (basicity index 1.35) and a calcium sulfonate detergent (basicity index 22.0) in various proportions were mixed in a single stage, assisted by stirrers and hotplates, at 75°C for 30 minutes with 1% diluent oil. This provided a set of mixes.
  • the stability tubes were visually inspected each week for, as evidence of additive instability, gel formation, phase separation, amount of sediment dropping to the bottom of the tube, and haziness.
  • RATIO (mmol/mmol): SALICYLATE/SULFONATE MBAP (mass %) 90/10 75/25 50/50 25/75 0 OK 12 gel/phase sep n 3 gel 1 gel >3 OK 12 gel/phase sep n 2 gel 1 gel 3 1 OK 12 OK 12 gel 1 gel >3 OK 12 gel/phase sep n 5 gel 1 gel 2 3 OK 12 OK 12 gel/phase sep n 3 gel >3 OK 12 gel/phase sep n 7 gel/phase sep n 6 gel >3 5 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 OK 12 Key: OK : no additive stability problems observed gel/phase sep n : additive instability (gel formation more severe than phase separation) numbers : number of weeks at which stability performance was observed and reported (first number at room temperature testing; second number at 60°C testing)

Claims (9)

  1. Additivpaket für eine Schmierölzusammensetzung für einen Zweitakt- oder Viertaktschiffsmotor, die weniger als 50% Öl mit Schmierviskosität, mehr als 50 Masse-% von (A) überbasischem Metallhydroxybenzoatdetergensadditiv und (B) überbasischem Metallsulfonatdetergensadditiv und (C) öllöslichem Kohlenwasserstoffphenol-Aldehyd-Kondensatadditiv in einer Menge im Bereich von 1 bis 10, vorzugsweise 3 bis 6 Masse-% umfasst, wobei das Verhältnis von (A) zu (B), ausgedückt als mmol Seife, im Bereich von 90:10 bis 10:90, vorzugsweise 80:20 bis 20:80 liegt.
  2. Schmierölzusammensetzung für einen Zweitaktschiffsmotor, die in einer größeren Menge Öl mit Schmierviskosität umfasst und mit einer geringeren Menge des Additivpakets gemäß Anspruch 1 gemischt ist, wobei die Zusammensetzung eine Gesamtbasenzahl (TBN) gemäß ASTM D2896 von 10 bis 120, vorzugsweise 40 bis 100 aufweist.
  3. Schmierölzusammensetzung für einen Viertaktschiffsmotor, die in einer größeren Menge Öl mit Schmierviskosität umfasst und mit einer geringeren Menge des Additivpakets gemäß Anspruch 1 gemischt ist, wobei die Zusammensetzung eine Gesamtbasenzahl (TBN) gemäß ASTM D2896 von 25 bis 60 aufweist.
  4. Additivpaket oder -zusammensetzung nach den Ansprüchen 1, 2 oder 3, wobei (A) ein überbasisches Calciumsalicylatdetergens ist.
  5. Additivpaket oder -zusammensetzung nach einem der vorhergehenden Ansprüche, wobei (B) ein überbasisches Calciumsulfonatdetergens ist.
  6. Additivpaket oder -zusammensetzung nach einem der vorhergehenden Ansprüche, wobei (C) Methylen-verbrücktes Alkylphenol ist, dessen Hydroxylgruppen entweder verkappt oder unverkappt sind.
  7. Zusammensetzung nach einem der Ansprüche 2 bis 6 in Form eines Schiffsmotorzylinderschmiermittels.
  8. Verwendung von 1 bis 10 Masse-% von Additiv (C) wie in Anspruch 1 oder Anspruch 6 definiert in einem Additivpaket für ein Schiffsdieselschmiermittel, das die Additive (A) und (B) enthält, wie in Anspruch 1 definiert und in dem Verhältnis gemäß Anspruch 1, zur Verbesserung der Stabilität der Additive (A) und (B) in dem Schmiermittel, wie mittels Gelbildung, Phasentrennung, Sediment oder Trübung durch visuelle Überprüfung über einen Zeitraum von 12 Wochen bei Raumtemperatur und bei 60°C bestimmt.
  9. Verfahren zum Schmieren eines Kreuzkopfschiffsdieselmotors, bei dem eine Zusammensetzung gemäß einem der Ansprüche 2 bis 7 während des Betriebs des Motors dem Kolben/Zylinder des Motors zugeführt wird.
EP16174815.7A 2015-06-30 2016-06-16 Additivpaket für die schmierung eines schiffsmotors Active EP3112447B1 (de)

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GB9621231D0 (en) * 1996-10-11 1996-11-27 Exxon Chemical Patents Inc Low sulfer fuels with lubricity additive
AU2003220205A1 (en) * 2002-03-14 2003-09-29 The Lubrizol Corporation Ethanol-diesel fuel composition and methods thereof
US7285516B2 (en) * 2002-11-25 2007-10-23 The Lubrizol Corporation Additive formulation for lubricating oils
US8618029B2 (en) * 2003-12-22 2013-12-31 Chevron Oronite S.A. Overbased detergents for lubricating oil applications
CA2509735C (en) * 2004-06-11 2012-09-25 Infineum International Limited Detergent additives for lubricating oil compositions
US20060046941A1 (en) * 2004-08-26 2006-03-02 Laurent Chambard Lubricating oil compositions
US7786060B2 (en) * 2004-11-16 2010-08-31 Infineum International Limited Lubricating oil additive concentrates
US20110239978A1 (en) 2010-04-06 2011-10-06 Dambacher Jesse D Lubricating Oil Composition
CN103857775A (zh) * 2011-07-07 2014-06-11 卢布里佐尔公司 提供给二冲程发动机改善的清洁度的润滑剂
SG11201400814PA (en) * 2011-10-20 2014-07-30 Lubrizol Corp Bridged alkylphenol compounds

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JP2017014505A (ja) 2017-01-19
EP3112447A1 (de) 2017-01-04
AU2016204471B2 (en) 2017-08-17
KR102633889B1 (ko) 2024-02-07
KR20170003437A (ko) 2017-01-09
JP6730107B2 (ja) 2020-07-29
SG10201605358SA (en) 2017-01-27
CA2934722C (en) 2023-10-03
CN106318540B (zh) 2021-03-16
CA2934722A1 (en) 2016-12-30

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