# US 11,111,453 B2 · Method for lubricating internal combustion engine > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,453 B2 - Document ID: US11111453B2 - Status: Granted - Kind: B2 - Application number: 16/341,195 - Filed: 2017-10-18 - Published: 2019-08-01 - Granted: 2021-09-07 - Earliest claimed: 2016-10-18 - Assignees: Eneos Corporation - Applicants: ENEOS Corporation - Inventors: Shigeki Takeshima - Web page: https://patentgrep.com/patent/US11111453B2 ## CPC - C10M 169/04: Mixtures of base-materials and additives - C10M 101/02: Petroleum fractions - C10M 129/26: Carboxylic acids; Salts thereof - C10M 129/54: containing hydroxy groups - C10M 133/12: having amino groups bound to a carbon atom of a six-membered aromatic ring - C10M 135/10: Sulfonic acids or derivatives thereof - C10M 137/02: having no phosphorus-to-carbon bond - C10M 139/00: Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 - C10M 159/20: Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products - C10M 159/24: containing sulfonic radicals - C10M 169/048: {the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds} - C10M 171/00: 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 (chemically defined ingredients C10M101/00 - C10M169/00; petroleum fractions C10M101/02, C10M121/02, C10M159/04) - C10M 2203/1006: used as base material - C10M 2203/1025: used as base material - C10M 2207/144: containing hydroxy groups - C10M 2207/26: Overbased carboxylic acid salts - C10M 2207/262: derived from hydroxy substituted aromatic acids, e.g. salicylates - C10M 2209/084: Acrylate; Methacrylate - C10M 2215/064: Di- and triaryl amines - C10M 2215/28: Amides; Imides - C10M 2219/044: Sulfonic acids, Derivatives thereof, e.g. neutral salts - C10M 2219/046: Overbased sulfonic acid salts - C10M 2219/068: Thiocarbamate metal salts - C10M 2219/089: Overbased salts - C10M 2223/02: having no phosphorus-to-carbon bonds - C10M 2223/045: Metal containing thio derivatives - C10M 2227/09: Complexes with metals - C10M 2229/041: containing aliphatic substituents - C10N 2010/02: Groups 1 or 11 - C10N 2010/04: Groups 2 or 12 - C10N 2020/02: Viscosity; Viscosity index - C10N 2030/04: Detergent property or dispersant property - C10N 2030/06: Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure - C10N 2030/10: Inhibition of oxidation, e.g. anti-oxidants - C10N 2040/10: Running-in-oil {; Grinding} - C10N 2040/252: {Diesel engines} - C10N 2040/255: {Gasoline engines} - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract A method for lubricating an internal combustion engine, the method including: supplying a lubricating oil composition to a cylinder of an internal combustion engine, wherein the internal combustion engine has a mean effective pressure of no less than 1.3 MPa, wherein an integrated intensity ratio of peaks of CaO in a X-ray diffraction spectrum of an ash is no more than 16.5%, the ash being obtained by incinerating the lubricating oil composition in an air at 950° C. ## Claims ### Claim 1 A cylinder lubricating oil composition for a premix combustion crosshead diesel engine, the lubricating oil composition comprising: a mineral base oil or a synthetic base oil or a mixture thereof, as a lubricant base oil; and (A) a metallic detergent, the component (A) comprising: (A1) a calcium borate-overbased metallic detergent in an amount of 0.35 to 1.70 mass % in terms of calcium on the basis of the total mass of the composition, the component (A1) comprising a calcium borate-overbased calcium salicylate detergent, or a calcium borate-overbased calcium sulfonate detergent, or any combination thereof; and (A2) a calcium carbonate-overbased metallic detergent in an amount of 0.35 to 1.30 mass % in terms of calcium on the basis of the total mass of the composition, the component (A2) comprising a calcium carbonate-overbased calcium salicylate detergent, or a calcium carbonate-overbased calcium sulfonate detergent, or any combination thereof, wherein an integrated intensity ratio of peaks of CaO in a X-ray diffraction spectrum of an ash is no more than 16.5%, the ash being obtained by incinerating the lubricating oil composition in an air at 950° C.; a molar ratio B/Ca of a boron content B (unit: mol) of the lubricating oil composition derived from the component (A) and a calcium content Ca (unit: mol) of the lubricating oil composition derived from the component (A) is no less than 0.52; and the lubricating oil composition is used to lubricate at least a cylinder in a premix combustion crosshead diesel engine, wherein the premix combustion crosshead diesel engine uses a main fuel having a flash point of no more than 15° C. ### Claim 2 (depends on 1) The lubricating oil composition according to claim 1, further comprising: one or more selected from the group consisting of: (B) an ashless dispersant, (C) a phosphorus-containing anti-wear agent, (D) an amine antioxidant, and (E) an oil-soluble organic molybdenum compound. ### Claim 3 (depends on 1) The lubricating oil composition according to claim 1, wherein the component (A1) consists of the calcium borate-overbased calcium salicylate detergent, or the calcium borate-overbased calcium sulfonate detergent, or any combination thereof; and the molar ratio B/Ca is 0.52 to 1.43. ### Claim 4 (depends on 1) The lubricating oil composition according to claim 1, wherein the lubricating oil composition has a kinematic viscosity at 100° C. of 16.3 to 21.9 mm2/s. ### Claim 5 (depends on 1) A method for lubricating a cylinder of a premix combustion crosshead diesel engine, comprising: a) supplying the lubricating oil composition as defined in claim 1 to a cylinder of a premix combustion crosshead diesel engine, wherein the premix combustion crosshead diesel engine has a mean effective pressure of no less than 1.3 MPa; and b) making a main fuel ignite in the cylinder, wherein the main fuel has a flash point of no more than 15° C. ### Claim 6 (depends on 5) The method according to claim 5, wherein the main fuel consists of a C1-4 hydrocarbon, or dimethyl ether, or any combination thereof. ### Claim 7 (depends on 6) The method according to claim 6, wherein the b) making a main fuel ignite in the cylinder comprises: i) compressing a fuel-air mixture of the main fuel and an air in the cylinder; and ii) injecting a pilot fuel into the cylinder, to ignite the fuel-air mixture, wherein the pilot fuel consists of a heavy fuel oil, a light fuel oil, or kerosene, or any combination thereof. ### Claim 8 A lubricating oil composition for a premix combustion middle-speed trunk piston diesel engine, the lubricating oil composition comprising: a mineral base oil or a synthetic base oil or a mixture thereof, as a lubricant base oil; and (A) a metallic detergent, the component (A) comprising: (A1) a calcium borate-overbased metallic detergent in an amount of 0.25 to 1.20 mass % in terms of calcium on the basis of the total mass of the composition, the component (A1) comprising a calcium borate-overbased calcium salicylate detergent, or a calcium borate-overbased calcium sulfonate detergent, or any combination thereof; and (A2) a calcium carbonate-overbased metallic detergent in an amount of 0.25 to 0.90 mass % in terms of calcium on the basis of the total mass of the composition, the component (A2) comprising a calcium carbonate-overbased calcium salicylate detergent, or a calcium carbonate-overbased calcium sulfonate detergent, or any combination thereof, wherein an integrated intensity ratio of peaks of CaO in a X-ray diffraction spectrum of an ash is no more than 16.5%, the ash being obtained by incinerating the lubricating oil composition in an air at 950° C.; a molar ratio B/Ca of a boron content B (unit: mol) of the lubricating oil composition derived from the component (A) and a calcium content Ca (unit: mol) of the lubricating oil composition derived from the component (A) is no less than 0.52; and the lubricating oil composition is used to lubricate at least a cylinder in a premix combustion middle-speed trunk piston diesel engine, wherein the premix combustion middle-speed trunk piston diesel engine uses a main fuel having a flash point of no more than 15° C. ### Claim 9 (depends on 8) The lubricating oil composition according to claim 8, further comprising: one or more selected from the group consisting of: (B) an ashless dispersant, (C) a phosphorus-containing anti-wear agent, (D) an amine antioxidant, and (E) an oil-soluble organic molybdenum compound. ### Claim 10 (depends on 8) The lubricating oil composition according to claim 8, wherein the component (A1) consists of the calcium borate-overbased calcium salicylate detergent, or the calcium borate-overbased calcium sulfonate detergent, or any combination thereof; and the molar ratio B/Ca is 0.52 to 1.43. ### Claim 11 (depends on 8) The lubricating oil composition according to claim 8, wherein the lubricating oil composition has a kinematic viscosity at 100° C. of no less than 9.3 mm2/s and less than 16.3 mm2/s. ### Claim 12 (depends on 8) A method for lubricating a premix combustion middle-speed trunk piston diesel engine, the method comprising: a) supplying the lubricating oil composition as defined in claim 8 to a cylinder of a premix combustion middle-speed trunk piston diesel engine, wherein the premix combustion middle-speed trunk piston diesel engine has a mean effective pressure of no less than 1.3 MPa; and b) making a main fuel ignite in the cylinder, wherein the main fuel has a flash point of no more than 15° C. ### Claim 13 (depends on 12) The method according to claim 12, wherein the main fuel consists of a C1-4 hydrocarbon, or dimethyl ether, or any combination thereof. ### Claim 14 (depends on 13) The method according to claim 13, wherein the b) making a main fuel ignite in the cylinder comprises: i) compressing a fuel-air mixture of the main fuel and an air in the cylinder; and ii) injecting a pilot fuel into the cylinder, to ignite the fuel-air mixture, wherein the pilot fuel consists of a heavy fuel oil, a light fuel oil, or kerosene, or any combination thereof. ### Claim 15 A lubricating oil composition for a turbocharged gasoline engine, the lubricating oil composition comprising: a mineral base oil or a synthetic base oil or a mixture thereof, as a lubricant base oil; and (A) a metallic detergent, the component (A) comprising: (A1) a calcium borate-overbased metallic detergent in an amount of 0.10 to 0.28 mass % in terms of calcium on the basis of the total mass of the composition, the component (A1) comprising a calcium borate-overbased calcium salicylate detergent, or a calcium borate-overbased calcium sulfonate detergent, or any combination thereof; and (A2) a calcium carbonate-overbased metallic detergent in an amount of 0.10 to 0.18 mass % in terms of calcium on the basis of the total mass of the composition, the component (A2) comprising a calcium carbonate-overbased calcium salicylate detergent, or a calcium carbonate-overbased calcium sulfonate detergent, or any combination thereof, wherein an integrated intensity ratio of peaks of CaO in a X-ray diffraction spectrum of an ash is no more than 16.5%, the ash being obtained by incinerating the lubricating oil composition in an air at 950° C.; a molar ratio B/Ca of a boron content B (unit: mol) of the lubricating oil composition derived from the component (A) and a calcium content Ca (unit: mol) of the lubricating oil composition derived from the component (A) is no less than 0.52; and the lubricating oil composition is used to lubricate at least a cylinder in a turbocharged gasoline engine. ### Claim 16 (depends on 15) The lubricating oil composition according to claim 15, further comprising: one or more selected from the group consisting of: (B) an ashless dispersant, (C) a phosphorus-containing anti-wear agent, (D) an amine antioxidant, and (E) an oil-soluble organic molybdenum compound. ### Claim 17 (depends on 15) The lubricating oil composition according to claim 15, wherein the component (A1) consists of the calcium borate-overbased calcium salicylate detergent, or the calcium borate-overbased calcium sulfonate detergent, or any combination thereof; and the molar ratio B/Ca is 0.52 to 1.43. ### Claim 18 (depends on 15) The lubricating oil composition according to claim 15, wherein the lubricating oil composition has a kinematic viscosity at 100° C. of no less than 4.0 mm2/s and less than 9.3 mm2/s. ### Claim 19 (depends on 15) A method for lubricating a premix combustion turbocharged gasoline engine, the method comprising: a) supplying the lubricating oil composition as defined in claim 15 to a cylinder of a turbocharged gasoline engine, wherein the turbocharged gasoline engine has a mean effective pressure of no less than 1.3 MPa; and b) making a fuel ignite in the cylinder, wherein the fuel consists of gasoline.