EP0447915B1 - Methode pour lubrifier un moteur à carburant à base d'alcool - Google Patents

Methode pour lubrifier un moteur à carburant à base d'alcool 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
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91103710A
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German (de)
English (en)
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EP0447915A1 (fr
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
Original Assignee
Nippon Oil Corp
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    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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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. Méthode pour lubrifier un moteur à carburant à base d'alcool comprenant la lubrification dudit moteur avec une composition lubrifiante pour moteurs comprenant une quantité majoritaire d'huile minérale et/ou d'huile synthétique comme huile lubrifiante de base, et comme composant essentiel, de 0,01 à 10 % en masse, pourcentages calculés sur la base de la quantité totale de la composition, d'un borate de métal alcalino-terreux surbasique préparé en faisant réagir un salicylate de métal alcalino-terreux avec un oxyde ou un hydroxyde de métal alcalino-terreux en présence d'acide borique ou d'anhydride borique.
  2. Méthode selon la revendication 1 dans laquelle ladite huile lubrifiante de base comprend une dispersion de borate de métal alcalino-terreux surbasique avec un indice de base totale (mesuré selon la norme JISK 2501 5.2.3) de plus de 100, de préférence de plus de 170.
  3. Méthode selon la/les revendications 1 et/ou 2 dans laquelle ledit borate de métal alcalino-terreux a une grosseur de particule de moins de 0,1 µm, de préférence de moins de 0,05 µm.
  4. Méthode selon l'une quelconque des revendications 1 à 3 dans laquelle ledit carburant à base d'alcool comprend au moins 10 % en volume d'alcool.
EP91103710A 1990-03-14 1991-03-11 Methode pour lubrifier un moteur à carburant à base d'alcool Expired - Lifetime EP0447915B1 (fr)

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 (fr) 1991-09-25
EP0447915B1 true EP0447915B1 (fr) 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
WO2018212340A1 (fr) * 2017-05-19 2018-11-22 Ｊｘｔｇエネルギー株式会社 Composition d'huile lubrifiante pour machine à combustion interne

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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
JP2594347B2 (ja) * 1987-01-30 1997-03-26 ザ ルブリゾル コーポレーション ギア潤滑組成物
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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DE69105788D1 (de) 1995-01-26
JP2814131B2 (ja) 1998-10-22
EP0447915A1 (fr) 1991-09-25
JPH03263496A (ja) 1991-11-22
DE69105788T2 (de) 1995-04-27

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