EP0447915A1 - Methode zur Schmierung von Alkoholbasiskraftstoffmotoren. - Google Patents

Methode zur Schmierung von Alkoholbasiskraftstoffmotoren. Download PDF

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Publication number
EP0447915A1
EP0447915A1 EP91103710A EP91103710A EP0447915A1 EP 0447915 A1 EP0447915 A1 EP 0447915A1 EP 91103710 A EP91103710 A EP 91103710A EP 91103710 A EP91103710 A EP 91103710A EP 0447915 A1 EP0447915 A1 EP 0447915A1
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Prior art keywords
oil
alkaline
earth metal
alcohol
composition
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EP91103710A
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English (en)
French (fr)
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EP0447915B1 (de
Inventor
Kiyoshi Inoue
Takashi Mito
Masakuni Hirata
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Eneos Corp
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Nippon Oil Corp
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2040/251—Alcohol fueled 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
    • 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
    • C10N2040/28—Rotary engines

Definitions

  • This invention relates to an engine oil composition for alcohol-based fuel engines, and more particularly to an engine oil composition for alcohol-based, such as methanol- or ethanol-based, fuel engines.
  • oxidation products of alcohol such as formic acid and water are easily formed.
  • a problem associated with the formation of such oxidation products has been the blowing of the products through the crankcase as a blow-by gas thus causing the cranckcase to corrode and rust .
  • these polar substances are the causes of wear of several parts of an engine. Therefore, it is necessary to neutralize the formic acid immediately after it enters into the engineoil to deactivate the acid.
  • an overbasic detergent prepared by use of calcium carbonate has been used in conventional engine oils.
  • the capacity of such a conventional overbasic detergent for neutralizing formic acid is insufficient, and said detergent has a tendency to become a coarse-grained particle during use.
  • its wear resistance is also unsatisfactory.
  • the present invention is based on a discovery whereby efficient results can be attained employing an alkaline-earth metal borate instead of the conventional overbasic detergents.
  • the present invention provides for an engine oil composition for alcohol-based fuel engines containing an overbasic detergent having improved capacity for neutralizing formic acid, improved wear resistance and no tendency to form coarse-grained particles during use.
  • the present invention provides an engine oil composition for alcohol-based fuel engines characterized by containing a major amount of mineral oil and/or synthetic oil as a lubricating base oil, and about 0.01 to 10 % by weight of an alkaline-earth metal borate on the basis of the total amount of the composition as an essential component.
  • Either mineral oils or synthetic oils may be used as the lubricatong base oils of the present invention.
  • Any paraffinic or naphthenic lubricating base oils may be acceptable wherein said base oils are manufactured by a process consisting mainly of topping of crude oil followed by vacuum distilation to give a lubricating oil fraction, and refining said lubricating fraction by a process selected from the group consisting of solvent deasphalting, solvent extraction, hydro-cracking, solvent dewaxing, catalytic dewaxing, hydro-refining, sulfuric acid treating, and clay treating.
  • the synthetic oils of the present invention include, for example, ⁇ -olefin polymers (polybutenes, octene-1 oligomers, decene-1 oligomers, and the like), alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-3-ethylhexyl sebacate, and the like), polyol esters (trimethylolpropane caprilate, trimethylolpropane pelargonate, pentaerythritol- 2-ethyl hexanoate, pentaerythritol pelargonate, and the like), polyoxyalkylene glycol, polyphenyl ether, silicon oils, perfluoroalkyl ethers, and mixture thereof.
  • Preferred kinematic viscosity of these lubricating base oils is in a range of about 3 to 20 cSt at 100°C.
  • Alkaline-earth metal borates of the present invention have a general formula of M O ⁇ x B2 O3 wherein M is an alkaline-earth metal atom, x is positive having a value of 0.5 to 3.0.
  • the alkaline-earth metals include magnesium, calcium, barium, with calcium being preffered.
  • the alkaline-earth metal borates have a particle size of less than about 0.1 ⁇ m, preferably less than about 0.05 ⁇ m.
  • alkaline-earth metal borate dispersions prepared by reacting oil-soluble metal salts with alkaline-earth metal borates may also be utilized in the present invention.
  • the alkaline-earth metal borate dispersions have a total base number (measured by the procedure prescribed by JIS K 2501 5.2.3) of more than 100, preferably more than 170.
  • the alkaline-earth metal borate dispersions are prepared by a reaction of an oil-soluble metal salt such as an oil-soluble alkaline-earth metal sulfonate, alkaline-earth metal saricylate, alkaline-earth metal pheneate, alkaline-earth metal phosphonate with an oxide or a hydroxide of an alkaline-earth metal in the presence of boric acid or boric acid anhydride.
  • an oil-soluble metal salt such as an oil-soluble alkaline-earth metal sulfonate, alkaline-earth metal saricylate, alkaline-earth metal pheneate, alkaline-earth metal phosphonate with an oxide or a hydroxide of an alkaline-earth metal in the presence of boric acid or boric acid anhydride.
  • oil-soluble metal salts alkaline-earth metal saricylates are most appropriate. Any methods for preparing the alkaline-earth metal borate dispers
  • a method which comprises reacting an oil-soluble metal salt aforesaid, a hydroxide or an oxide of alkaline-earth metal, and boric acid or boric acid anhydride in the presence of water, an alcohol such as methanol, ethanol, propanol, or butanol, and a diluent such as benzene, toluene or xylene at a temperature of about 20 to 200°C for about 2 to 8 hours, heating the mixture at about 100 to 200°C to remove water, followed by removing the alcohol and the diluent if necessary, to give a dispersion.
  • the reaction conditions may be employed suitably depending on the raw materials to be used, the amount of reactants and the like.
  • the alkaline-earth metal borate dispersions obtained by the above-mentioned procedures have a particle size of less than 0.1 ⁇ m and a total base number of more than about 100, and are appropriate for the present invention.
  • a content of the alkaline-earth metal borate in the present composition is in an amount of 0.01 to 10 % by weight, preferably 0.05 to 3 % by weight, more preferably about 0.05 to 1 % by weight on the basis of the total amount of the composition.
  • the following conventional lubricating oil additives can be additionally used to improve further the performance of the present composition if necessary, in so far as they do not deviate from the gist of the present invention.
  • these additives include oiliness improvers such as higher alcohols, higher fatty acids, esters and the like ; extreme pressure agents and friction modifiers such as tricresyl phosphate, triphenyl phosphate, zinc dithiophosphates, molibdenum disulfides, molibdenum dithiophosphates, molibdenum dithiocarbamates and the like; rust preventives such as petroleum sulfonates, dinonyl naphthalene sulfonates and the like; metal deactivating agents such as benzotriazole and the like; metal-based detergents such as alkaline-earth metal sulfonates, alkaline-earth metal salicylates, alkaline-earth metal pheneates, alkaline-earth metal phosphon
  • a content of the viscosity index improver is in an amount of about 1 to 30 % by weight
  • the deformer is in an amount of about 0.0005 to 1 % by weight
  • the metal deactivating agent is in an amount of about 0.005 to 1 % by weight
  • other additives is in an amount of about 0.1 to 15 % by weight respectively on the basis of the total amount of the composition.
  • the engine oil compositions for alcohol-based fuel engines of the present invention are suitable for spark-ignition or compression-ignition engines in which said alcohol-based fuel is selected from the group consisting mainly of methanol, ethanol, propanol, mixtures thereof, and the mixture of at least 10 % by volume of one of these alcohols with a petroleum-based fuel such as gasoline, kerosene, and gas oil.
  • a petroleum-based fuel such as gasoline, kerosene, and gas oil.
  • engine oil compositions were prepared by blending an overbasic oil-soluble metal salt prepared by use of calcium borate in an amount shown in Table 1 with a refined mineral oil (SAE 30, 10.0 cSt 100°C).
  • SAE 30, 10.0 cSt 100°C a refined mineral oil
  • Formic acid in an amount shown in Table 1 was added individually to these compositions and pH of these compositions after 30 Sec. were measured.
  • Table 1 gives the results.
  • the same procedures were repeated except that calcium carbonate was used to prepare the overbasic oil-souble metal salt, and the results are also shown in Table 1.
  • engine oil compositions were prepared by blending 2 % by weight, on the basis of the total amount of the composition, of overbasic oil-soluble metal salt prepared by use of calcium borate with a refined mineral oil (SAE 10, 4.3 cSt @ 100 °C).
  • SAE 10, 4.3 cSt @ 100 °C a refined mineral oil
  • Table 2 shows the test results. For reference, the same procedures were repeated except that calcium carbonate was used to prepare the overbasic oil-soluble metal salt, and the results are also shown in Table 2.
  • the engine oil compositions of the present invention were prepared by blending 15 % by weight, on the basis of the total amount of the composition, of an overbasic oil-soluble metal salt prepared by use of calcium borate with a refined mineral oil (SAE 10, 4.3 cSt @ 100 °C). The tests were carried out by the method prescribed by ASTM D 2619. Table 3 gives the test results. For reference, the same procedures were repeated except that calcium carbonate was used to prepare the overbasic oil-soluble metal salt, and the results are also shown in Table 3.
  • the engine oil compositions for alcohol-based fuel engines of the present invention are superior to the prior arts of compositions for alcohol-based fuel engines in capacity for neutralizing formic acid, wear resistance, and stability for hydrolysis.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
EP91103710A 1990-03-14 1991-03-11 Methode zur Schmierung von Alkoholbasiskraftstoffmotoren. Expired - Lifetime EP0447915B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2063741A JP2814131B2 (ja) 1990-03-14 1990-03-14 アルコール系燃料用エンジン油組成物
JP63741/90 1990-03-14

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EP0447915A1 true EP0447915A1 (de) 1991-09-25
EP0447915B1 EP0447915B1 (de) 1994-12-14

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Publication number Priority date Publication date Assignee Title
JP2007009123A (ja) * 2005-07-01 2007-01-18 Nippon Oil Corp 含酸素燃料エンジン用潤滑油組成物
JP5134270B2 (ja) * 2007-03-19 2013-01-30 Ｊｘ日鉱日石エネルギー株式会社 内燃機関用潤滑油組成物
US11680221B2 (en) 2017-05-19 2023-06-20 Eneos Corporation Lubricating oil composition for internal combustion engine

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3679584A (en) * 1970-06-01 1972-07-25 Texaco Inc Overbased alkaline earth metal sulfonate lube oil composition manufacture
WO1984003901A1 (en) * 1983-03-31 1984-10-11 Lubrizol Corp Alkyl phenol and amino phenol compositions and two-cycle engine oils and fuels containing same
FR2554825A1 (fr) * 1983-11-15 1985-05-17 Shell Int Research Sel metallique basique borate et composition d'huile lubrifiante le contenant
DE3607887A1 (de) * 1985-03-08 1986-09-11 Nippon Oil Co., Ltd., Tokio/Tokyo Verfahren zur herstellung von erdalkaliboratdispersionen
WO1988005810A1 (en) * 1987-01-30 1988-08-11 The Lubrizol Corporation Gear lubricant composition
WO1988007073A1 (fr) * 1987-03-17 1988-09-22 Elf France Procede de preparation d'un additif suralcanise renfermant un derive du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3679584A (en) * 1970-06-01 1972-07-25 Texaco Inc Overbased alkaline earth metal sulfonate lube oil composition manufacture
WO1984003901A1 (en) * 1983-03-31 1984-10-11 Lubrizol Corp Alkyl phenol and amino phenol compositions and two-cycle engine oils and fuels containing same
FR2554825A1 (fr) * 1983-11-15 1985-05-17 Shell Int Research Sel metallique basique borate et composition d'huile lubrifiante le contenant
DE3607887A1 (de) * 1985-03-08 1986-09-11 Nippon Oil Co., Ltd., Tokio/Tokyo Verfahren zur herstellung von erdalkaliboratdispersionen
WO1988005810A1 (en) * 1987-01-30 1988-08-11 The Lubrizol Corporation Gear lubricant composition
WO1988007073A1 (fr) * 1987-03-17 1988-09-22 Elf France Procede de preparation d'un additif suralcanise renfermant un derive du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif

Also Published As

Publication number Publication date
EP0447915B1 (de) 1994-12-14
JP2814131B2 (ja) 1998-10-22
DE69105788T2 (de) 1995-04-27
DE69105788D1 (de) 1995-01-26
JPH03263496A (ja) 1991-11-22

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