EP0447915B1 - Methode zur Schmierung von Alkoholbasiskraftstoffmotoren. - Google Patents

Methode zur Schmierung von Alkoholbasiskraftstoffmotoren. Download PDF

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Publication number
EP0447915B1
EP0447915B1 EP91103710A EP91103710A EP0447915B1 EP 0447915 B1 EP0447915 B1 EP 0447915B1 EP 91103710 A EP91103710 A EP 91103710A EP 91103710 A EP91103710 A EP 91103710A EP 0447915 B1 EP0447915 B1 EP 0447915B1
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EP
European Patent Office
Prior art keywords
alkaline
earth metal
alcohol
oil
overbasic
Prior art date
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Expired - Lifetime
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EP91103710A
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English (en)
French (fr)
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EP0447915A1 (de
Inventor
Kiyoshi Inoue
Takashi Mito
Masakuni Hirata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
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Nippon Oil Corp
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    • C10M2223/045—Metal containing thio derivatives
    • 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
    • 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-fuelled 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 a method for the lubrication of an alcohol-based fuel engine, and more particularly to a method for the lubrication of a methanol- or ethanol-based fuel engine.
  • the present invention is based on extensive research whereby the inventors unexpectedly have found that efficient results can be attained by employing an overbasic alkaline-earth metal borate, as defined in claim 1, instead of the conventional overbasic detergents for the lubrication of alcohol-based fuel engines.
  • FR-A1-2 554 825 discloses oil soluble reaction products prepared from alkaline-earth metal salts of an organic acid, having been made basic by a pre-reaction with CO2 , and a boron compound like boric acid. Since such reaction products do not comprise solid materials they can be easily compounded with luboils.
  • the present invention provides a method for the lubrication of alcohol-based fuel engines characterized by lubricating said engines with an engine oil composition containing a major amount of mineral oil and/or synthetic oil as lubricating base oil, and 0.01 to 10% by weight of an overbasic alkaline-earth metal borate as defined in claim 1, 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 lubricating base oils in the present invention.
  • Any paraffinic or naphthenic lubricating base oils may be acceptable, said base oils being manufactured by a process consisting mainly of topping a crude oil followed by vacuum distillation 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 used according to 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, perfluoralkyl ethers, and mixture thereof.
  • the preferred kinematic viscosity of these lubricating base oils is in the range of about 3 to 20.10 ⁇ 6 m2/s (cSt) at 100°C.
  • Alkaline-earth metal borates useful for the present invention have the general formula of M O .x B2 O3 wherein M is an alkaline-earth metal atom, x is a positive number having a value of 0.5 to 3.0.
  • the alkaline-earth metals include magnesium, calcium, barium, with calcium being preferred.
  • the alkaline-earth metal borates have a particle size of less than about 0.1 ⁇ m, preferably less than about 0.05 ⁇ m.
  • the overbasic alkaline-earth metal borates are hereinafter referred to as "alkaline-earth metal borate dispersions".
  • the overbasic alkaline-earth metal borate dispersions have a total base number (measured by the procedure presribed by JIS K 2501 5.2.3) of more than 100, preferably more than 170.
  • the overbasic alkaline-earth metal borate dispersions are prepared by the reaction of an oil-soluble alkaline-earth metal salicylate with an oxide or a hydroxide of an alkaline-earth metal in the presence of boric acid or boric acid anhydride. Any methods for preparing the overbasic alkaline-earth metal borate dispersions may be acceptable.
  • a method which comprises reacting an oil-soluble alkaline-earth metal salicylate, 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.
  • the alkaline-earth metal borate is present in the composition to be used according to the invention in an amount of 0.01 to 10% by weight, preferably 0.05 to 3% by weight, more preferably of 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.
  • 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, molybdenum disulfides, molybdenum dithiophosphates, molybdenum 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 phosphonates and the like; ashless dispersants such as succinimide
  • the viscosity index improver may be present in an amount of about 1 to 30% by weight, the defoamer in an amount of about 0.0005 to 1% by weight, the metal deactivating agent in an amount of about 0.005 to 1% by weight, and other additives 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 used for the lubrication of alcohol-based fuel engines according to 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.
  • 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.
  • engine oil compositions were prepared by blending an overbasic oil-soluble salt prepared by use of calcium borate in an amount shown in Table 1 with a refined mineral oil (SAE 30, 10.0 cSt (10.10 ⁇ 6m2/s) @ 100°C).
  • SAE 30, 10.0 cSt (10.10 ⁇ 6m2/s) @ 100°C a refined mineral oil
  • Formic acid in an amount shown in Table 1 was added individually to these compositions and the pH values of these compositions after 30 sec. were measured. Table 1 gives the 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 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 (4.3 x 10 ⁇ 6m2/s) at 100°C).
  • SAE 10, 4.3 cSt 4.3 x 10 ⁇ 6m2/s
  • the tests were carried out by the high-speed four point ball method.
  • the test conditions were as follows: Test load Engine speed Test duration 30 kg 1200 r.p.m. 30 min.
  • 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 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 (4.3 x 10 ⁇ 6 m2/s) at 100°C).
  • SAE 10, 4.3 cSt (4.3 x 10 ⁇ 6 m2/s) at 100°C a refined mineral oil
  • the tests were carried out by the method prescribed by ASTM D 2619. Table 3 gives the test results.
  • 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 used according to the present invention are superior to the prior art of compositions for alcohol-based fuel engines in respect of capacity for neutralizing formic acid, wear resistance, and stability against hydrolysis.

Landscapes

  • 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)

Claims (4)

  1. Ein Verfahren zum Schmieren eines Motors für einen Treibstoff auf Alkoholbasis, umfassend das Schmieren des besagten Motors mit einer Motorölzusammensetzung, umfassend eine größere Menge an Mineralöl und/oder synthetischem Öl als ein Basisschmieröl und als eine wesentliche Komponente 0,01 bis 10 Gew%, bezogen auf die Gesamtmenge der Zusammensetzung, eines überbasischen Erdalkalimetallborats, hergestellt durch eine Reaktion zwischen einem Erdalkalimetallsalicylat und einem Oxid oder einem Hydroxid eines Erdalkalimetalls in Gegenwart von Borsäure oder Borsäureanhydrid.
  2. Ein Verfahren nach Anspruch 1, in welchem das besagte Basisschmieröl eine Dispersion eines überbasischen Erdalkalimetallborats mit einer Gesamthasenzahl (gemessen nach JISK 2501 5.2.3) von mehr als 100, vorzugsweise von mehr als 170, umfaßt.
  3. Ein Verfahren nach Anspruch 1 und/oder 2, in welchem das besagte Erdalkalimetallborat eine Teilchengröße von weniger als 0,1 µm, vorzugsweise von weniger als 0,05 µm, aufweist.
  4. Ein Verfahren nach einem der Ansprüche 1 bis 3, in welchem der besagte Treibstoff auf Alkoholbasis mindestens 10 Vol% Alkohol umfaßt.
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 EP0447915A1 (de) 1991-09-25
EP0447915B1 true EP0447915B1 (de) 1994-12-14

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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
CN110662825A (zh) * 2017-05-19 2020-01-07 Jxtg能源株式会社 内燃机用润滑油组合物

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US3679584A (en) * 1970-06-01 1972-07-25 Texaco Inc Overbased alkaline earth metal sulfonate lube oil composition manufacture
US4724091A (en) * 1983-03-31 1988-02-09 The Lubrizol Corporation Alkyl phenol and amino phenol compositions and two-cycle engine oils and fuels containing same
GB2149810B (en) * 1983-11-15 1987-04-08 Shell Int Research Borated basic metal salt and oil composition containing it
JPS61204298A (ja) * 1985-03-08 1986-09-10 Nippon Oil Co Ltd アルカリ土類金属ホウ酸塩分散体の製造方法
ATE92094T1 (de) * 1987-01-30 1993-08-15 Lubrizol Corp Getriebeschmiermittelzusammensetzung.
FR2612526B1 (fr) * 1987-03-17 1990-02-02 Elf France Procede de preparation d'un additif suralcanise renfermant un derive du bore, l'additif ainsi obtenue et compositions lubrifiantes renfermant ledit additif

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DE69105788T2 (de) 1995-04-27
JP2814131B2 (ja) 1998-10-22
DE69105788D1 (de) 1995-01-26
JPH03263496A (ja) 1991-11-22
EP0447915A1 (de) 1991-09-25

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