EP2179011B1 - Lubricating composition for use in diesel engines compatible with biofuel - Google Patents
Lubricating composition for use in diesel engines compatible with biofuel Download PDFInfo
- Publication number
- EP2179011B1 EP2179011B1 EP08786285.0A EP08786285A EP2179011B1 EP 2179011 B1 EP2179011 B1 EP 2179011B1 EP 08786285 A EP08786285 A EP 08786285A EP 2179011 B1 EP2179011 B1 EP 2179011B1
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- EP
- European Patent Office
- Prior art keywords
- biofuel
- mass
- lubricating composition
- oil
- lubricating
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- 239000000203 mixture Substances 0.000 title claims description 27
- 239000002551 biofuel Substances 0.000 title claims description 13
- 230000001050 lubricating effect Effects 0.000 title claims description 12
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 38
- 239000002199 base oil Substances 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 13
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 12
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- -1 6-methylheptyl alcohol ester Chemical class 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 235000006708 antioxidants Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- 239000008186 active pharmaceutical agent Substances 0.000 claims 1
- 239000010687 lubricating oil Substances 0.000 description 23
- 239000003225 biodiesel Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
- C10M141/06—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 nitrogen-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
- 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
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/067—Polyaryl amine alkanes
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- 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
- C10N2020/081—Biodegradable compounds
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- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- 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
- C10N2030/78—Fuel contamination
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- 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
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- 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
- C10N2040/253—Small diesel engines
Definitions
- This invention relates to lubricating compositions for use in diesel engines that use biofuels.
- Biofuels for use in the diesel engines used in automotive vehicles have in some cases been produced by methyl esterification of plant oils, taking mainly rapeseed oil or sunflower oil as their raw material in France, German, and Italy within the EU, and mainly soybean oil as their raw material in the United States. In many cases, these fuels are used by mixing about 20% in a light oil.
- biodiesel fuels There are several points about these biodiesel fuels which must be borne in mind when using them. They have aspects which demand improvement simply in fuel terms in that their viscosities and pour points are rather high, and they are prone to oxidise because, being derived from plant oils, they contain many unsaturated fatty acids. Furthermore, these biodiesel fuels may compete directly with edible vegetable oils, and so they have not been studied as much as the above-mentioned alcohol fuels as alternatives to gasoline, and there have hardly been any attempts to improve lubricating oils in association with biodiesel fuels.
- EP0432089 describes a formulation containing A) a lubricant and a mixture of B) for example, at least one of the compounds O,O-bis-2-ethylhexylsodium dithiophosphate, O,O-bis-2-ethylhexylsodium thionophosphate, O,O-bis-2-methylpropylsodium dithiophosphate, O,O-bis-nonylphenylsodium dithiophosphate or S-[O,O-bis-2-ethyl-hexylthiophosphoryl]-potassium thioglycolate, C) at least one compound from the series of the aromatic amines, for example the diphenylamines or phenothiazines, and D) at least one compound from the series of the cyclic sterically hindered amines, the acyclic sterically hindered amines and the phenols substituted with alkyl radicals.
- lubricant formulations are said to have a high degree of stability towards oxidative degradation.
- WO2006/105267 discloses lubricating oil compositions with reduced phosphorus levels, for an internal combustion engine such as a diesel engine, providing superior oxidation control, and comprising a 4,4' methylenebis(2,6-di-tert-butylphenol), an alkylated diphenylamine, and in some alternatives an ester derived from 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid.
- the inventors have discovered that it is possible to inhibit ageing, and in particular degradation of the detergent performance of the lubricating oil, even after admixture with biodiesel fuel, by combining different types of anti-oxidant, a phenolic anti-oxidant and an amine-based anti-oxidant, in the lubricating oil composition.
- the present invention provides a lubricating composition for use in diesel engines compatible with biofuel, wherein the lubricating composition comprises a base oil belonging to Group III and/or Group II of the API base oil categories, from 0.5 to 5% by mass of a 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid and from 0.5 to 5% by mass of a diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene, the total content of the anti-oxidants being at least 2.5% by mass.
- a base oil belonging to Group III and/or Group II of the API base oil categories from 0.5 to 5% by mass of a 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid and from 0.5 to 5% by mass of a diphenylamine which is the reaction product of N-pheny
- this invention it is possible to inhibit rapid degradation of the detergent performance and accelerated ageing of the lubricating oil, even after admixture of biodiesel fuel in the lubricating oil, by using different types of anti-oxidant, a 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acid and a diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene, together, and thus it is possible to use the lubricating oil stably over a long period.
- biodiesel oils differ substantially from light oils is the content of constituent oxygen atoms. Also, it is believed that, since they contain double bonds derived from unsaturated fatty acids, the combustion reaction itself differs.
- the flash point is higher than in light oils and they are more prone to evaporate.
- the reaction may cease in the elementary process on the way to complete combustion, and the unreacted portion will often mix with the lubricating oil or the unburnt constituents themselves will be mixed with the lubricating oil, causing the formation of sludge in the lubricating oil and accelerating ageing of the lubricating oil through oxidation.
- the lubricating oils will be characterised by being used under more rigorous conditions even than when exposed to high temperatures when using only light oils as the fuel.
- base oils of this invention it is possible to use any suitable mineral oil or synthetic oil, and normally it is possible to use base oils, singly or in mixtures, that belong to Group III and Group II of the base oil categories of the API (American Petroleum Institute).
- Group III and Group II base oils include, for example, paraffinic mineral oils obtained by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by the Isodewax process which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins, base oils refined by the Mobil wax isomerisation process, and the so-called GTL (gas-to-liquid) base oils solvent dewaxed or catalyst dewaxed after synthesis by the Fischer-Tropsch method.
- GTL gas-to-liquid base oils solvent dewaxed or catalyst dewaxed after synthesis by the Fischer-Tropsch method.
- synthetic oils include also those that may be designated as "synthetic oils" according to the rulings of the NAD (National Advertising Division) which is responsible for advertising adjudications in America.
- a 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid and a diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene are blended together in these base oils.
- the amount of the above-mentioned 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acid is from 0.5 to 5.0% by mass based on the total amount of the lubricating oil composition, and preferably from 0.5 to 2% by mass.
- the amount of the above-mentioned diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene is from 0.5 to 5.0% by mass based on the total amount of the lubricating oil composition, and preferably from 0.5 to 2% by mass.
- the 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid and the diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene are used respectively in the above-mentioned amounts, but it is further required that the total amount of the two anti-oxidants at the same time is not less than 2.5% by mass. If the total amount of both is less than that, the expected effect will not be obtained.
- the present invention provides a method of operating a diesel engine comprising lubricating the diesel engine with a lubricating composition according to the present invention and using a biofuel, preferably derived from rapeseed oil, as fuel.
- the biodiesel fuel (BDF) was a methyl ester derived from rapeseed oil and was prepared so as to have the properties shown in Table 2.
- Table 2 Item Test method Units Characteristic (numeric value) Density: vibration method (15°C) JIS K-2249 g/cm 3 0.883 Flash point: PMCC method JIS K-2265 O C 155 Kinetic viscosity: 30°C JIS K-2283 mm 2 /s 5.51 Cetane value JIS K-2280 53.0
- Comparative Example 6 was a composition with a JASO (Engine Oil Standards Implementation Panel) DH-2 level diesel combustion engine oil for use in automotive vehicles.
- JASO Engine Oil Standards Implementation Panel
- Evaluation of the hot tube tests was from 0 to 10 in fractions of 0.5, and 7 and above was set as the pass mark.
- Example 1 is not according to the invention.
- Table 3 Example 1
- Example 2 Example 3
- Example 4 Base oil 86 85 85.5 82 Phenolic anti-oxidant 1.0 1.5 1.5 2.0 Amine-based antioxidant 1.0 1.5 1.0 4.0
- Additives package 12 12 12 12 Total 100 100 100 100 Admixed BDF 5 5 5 5 Hot tube score 7.0 7.0 7.0 7.5
- Table 4 Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3 Comp. Ex. 4 Comp. Ex. 5 Comp. Ex.
- Comparative Example 2 used 2.5% by mass of only the diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene, and although the total amount exceeded 2% by mass the hot tube score was poor at 2.0. More diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene was added to Comparative Example 3 than in Comparative Example 2, but the hot tube score rose only to 5.0.
- Comparative Example 4 used 2.5% by mass of only the 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acid, and although the total amount exceeded 2% by mass the hot tube score was poor at 3.0.
- Comparative Example 5 used both anti-oxidants together, but the total amount was less than 2% by mass and so the hot-tube score was poor at 2.5. A satisfactory effect was thus not obtained for any of Comparative Examples 1-5
- Comparative Example 6 had no admixture of biofuel, and even though no 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid or diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene was used, the hot tube score was 7.0 and it can be seen that a satisfactory effect was obtained.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2007190658A JP2009024123A (ja) | 2007-07-23 | 2007-07-23 | バイオ燃料対応ディーゼルエンジン用潤滑油組成物。 |
PCT/EP2008/059543 WO2009013275A1 (en) | 2007-07-23 | 2008-07-21 | Lubricating composition for use in diesel engines compatible with biofuel |
Publications (2)
Publication Number | Publication Date |
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EP2179011A1 EP2179011A1 (en) | 2010-04-28 |
EP2179011B1 true EP2179011B1 (en) | 2018-06-27 |
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EP08786285.0A Active EP2179011B1 (en) | 2007-07-23 | 2008-07-21 | Lubricating composition for use in diesel engines compatible with biofuel |
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US (2) | US20100269774A1 (ja) |
EP (1) | EP2179011B1 (ja) |
JP (1) | JP2009024123A (ja) |
CN (1) | CN101796171B (ja) |
AR (1) | AR068609A1 (ja) |
BR (1) | BRPI0814579B1 (ja) |
RU (1) | RU2456333C2 (ja) |
WO (1) | WO2009013275A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US7960322B2 (en) * | 2007-10-26 | 2011-06-14 | Chevron Oronite Company Llc | Lubricating oil compositions comprising a biodiesel fuel and an antioxidant |
CA2766063A1 (en) | 2009-06-26 | 2010-12-29 | The Lubrizol Corporation | Engine oil formulations for biodiesel fuels |
BR112012002608A2 (pt) * | 2009-08-05 | 2016-03-29 | Basf Se | composição lubrificante, e, método para melhorar o desempenho de uma composição lubrificante. |
EP2920282B1 (en) | 2012-11-19 | 2021-10-20 | The Lubrizol Corporation | Alkylene-coupled phenols for use in biodiesel engines |
JP2017039841A (ja) * | 2015-08-19 | 2017-02-23 | コスモ石油ルブリカンツ株式会社 | 内燃機関用潤滑油組成物 |
CA3047284A1 (en) | 2016-12-27 | 2018-07-05 | The Lubrizol Corporation | Lubricating composition with alkylated naphthylamine |
EP3562921B1 (en) | 2016-12-27 | 2022-04-27 | The Lubrizol Corporation | Lubricating composition including n-alkylated dianiline |
WO2018156304A1 (en) | 2017-02-21 | 2018-08-30 | Exxonmobil Research And Engineering Company | Lubricating oil compositions and methods of use thereof |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3652411A (en) * | 1969-12-04 | 1972-03-28 | Mobil Oil Corp | Polyglycol base lubricant |
ES2091236T3 (es) * | 1989-11-08 | 1996-11-01 | Ciba Geigy Ag | Composiciones de lubricantes. |
DE69004079D1 (de) * | 1990-05-14 | 1993-11-25 | Ethyl Petroleum Additives Ltd | Antioxidationszusammensetzungen. |
JPH04202398A (ja) * | 1990-11-30 | 1992-07-23 | Tonen Corp | 潤滑油組成物 |
ES2133363T3 (es) * | 1992-09-02 | 1999-09-16 | Lubrizol Corp | Antioxidantes para aceites vegetales altamente mono-insaturados. |
JPH08157853A (ja) * | 1994-12-08 | 1996-06-18 | Cosmo Sogo Kenkyusho:Kk | エステル系潤滑油組成物 |
US5672752A (en) * | 1995-09-13 | 1997-09-30 | The Bfgoodrich Company | Liquid alkylated diphenylamine antioxidant |
JP3935982B2 (ja) * | 1995-10-19 | 2007-06-27 | 出光興産株式会社 | 油圧作動油組成物 |
DE60029049T2 (de) * | 1999-05-19 | 2007-06-21 | Ciba Speciality Chemicals Holding Inc. | Stabilisierte hydroraffinierte und hydroentparaffinierte Schmiermittelzusammensetzungen |
RU2194742C2 (ru) * | 2001-03-16 | 2002-12-20 | ООО "Лаборатория Триботехнологии" | Противоизносная, антифрикционная присадка с модификатором трения, смазочный материал и способ получения модификатора трения |
US20050215441A1 (en) * | 2002-03-28 | 2005-09-29 | Mackney Derek W | Method of operating internal combustion engine by introducing detergent into combustion chamber |
WO2004081150A2 (en) * | 2003-03-14 | 2004-09-23 | Linnaeus Inc. | Methyl esters of hydroxyl-containing fatty acids as biofuels |
EP1471130A1 (en) * | 2003-04-23 | 2004-10-27 | Ethyl Petroleum Additives Ltd | Fuel composition containing molybdenum source and metal-containing detergent, and its use in two-stroke engines |
US20040266630A1 (en) * | 2003-06-25 | 2004-12-30 | The Lubrizol Corporation, A Corporation Of The State Of Ohio | Novel additive composition that reduces soot and/or emissions from engines |
US7667066B2 (en) * | 2004-02-27 | 2010-02-23 | Albemarle Corporation | Preparation of sterically hindered hydroxyphenylcarboxylic acid esters |
US20060223724A1 (en) * | 2005-03-29 | 2006-10-05 | Gatto Vincent J | Lubricating oil composition with reduced phosphorus levels |
-
2007
- 2007-07-23 JP JP2007190658A patent/JP2009024123A/ja active Pending
-
2008
- 2008-07-18 AR ARP080103099A patent/AR068609A1/es unknown
- 2008-07-21 BR BRPI0814579-2A patent/BRPI0814579B1/pt active IP Right Grant
- 2008-07-21 CN CN200880100097.6A patent/CN101796171B/zh active Active
- 2008-07-21 WO PCT/EP2008/059543 patent/WO2009013275A1/en active Application Filing
- 2008-07-21 EP EP08786285.0A patent/EP2179011B1/en active Active
- 2008-07-21 US US12/669,807 patent/US20100269774A1/en not_active Abandoned
- 2008-07-21 RU RU2010106057/04A patent/RU2456333C2/ru active
-
2012
- 2012-04-16 US US13/448,054 patent/US20130102509A1/en not_active Abandoned
Non-Patent Citations (1)
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Also Published As
Publication number | Publication date |
---|---|
BRPI0814579A2 (pt) | 2015-01-20 |
AR068609A1 (es) | 2009-11-25 |
JP2009024123A (ja) | 2009-02-05 |
EP2179011A1 (en) | 2010-04-28 |
US20130102509A1 (en) | 2013-04-25 |
BRPI0814579B1 (pt) | 2018-03-27 |
CN101796171A (zh) | 2010-08-04 |
CN101796171B (zh) | 2014-12-17 |
RU2010106057A (ru) | 2011-08-27 |
RU2456333C2 (ru) | 2012-07-20 |
WO2009013275A1 (en) | 2009-01-29 |
WO2009013275A9 (en) | 2009-03-12 |
US20100269774A1 (en) | 2010-10-28 |
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