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
- Authority
- EP
- European Patent Office
- Prior art keywords
- biofuel
- mass
- lubricating composition
- oil
- lubricating
- 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.)
- Active
Links
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
- This invention relates to lubricating compositions for use in diesel engines that use biofuels.
- In recent years, as a contribution to reducing CO2 in the global environment, there has been increasing momentum towards making positive use of fuels derived from plants and produced through biomass technologies. However, in composition they are not necessarily similar to existing fossil fuels and so various problems that can be generated by biofuels may be expected. Various investigations are being made of techniques to cope with these in the lubricating oils used in internal combustion engines.
- In the case of the alcohol fuels which are principally used in the field of gasoline engines, admixture with water cannot be avoided, and engine parts undergo a larger amount of wear than in the case of gasoline. Solutions for these problems have therefore been proposed. See Japanese Laid-open Patent
5-70786 (1993 - 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.
- 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.
- In the above-mentioned diesel engines, because a mixture of biodiesel fuel with light oil is used, a phenomenon is seen whereby an unburnt portion of the biodiesel fuel becomes mixed with the lubricating oil, promoting ageing thereof. This creates difficulties for using the lubricating oil stably over long periods.
-
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. Such 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.
- To this end, 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.
- According to 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.
- The light fuel oils and the biodiesel oils used in diesel engines of automotive vehicles, as already mentioned, have various obvious differences, and according to the literature ("New biomass liquid fuels for the 21st century", published by the Kagaku Kogyo Nippo [The Chemical Daily] on 2002-04-25) they can be summarised as being the differences shown in Table 1.
Table 1 Biodiesel oil Light oil Pour point (°C) -5.5 -11.5 Kinetic viscosity (mm2/s) 5.6 3.0 Flash point (°C) 135 ∼ 145 88 Sulphur content (%) 0.0001 0.2 Carbon (%) 77.1 ∼ 77.9 87.2 Hydrogen (%) 11.7 ∼ 11.8 12.8 Oxygen (%) 11.1 ∼ 11.2 0 - As is evident from Table 1, among the aspects where 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.
- Further, it may be mentioned that, in terms of physical properties, the flash point is higher than in light oils and they are more prone to evaporate. When supplied as fuel to engines, 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.
- Given these facts, 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.
- For the 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).
- These 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. They 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.
- For both the above-mentioned 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid and diphenylamine which is the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene, if the amount is less than 0.5% by mass the oxidative stability decreases, which is undesirable, and if it exceeds 5% by mass the piston detergency decreases, which is often undesirable.
- 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. - It is also possible to add to this lubricating oil composition, as required, suitable dispersants, extreme-pressure agents, detergents, viscosity index improvers and other additives.
- In another aspect 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/cm3 0.883 Flash point: PMCC method JIS K-2265 O C 155 Kinetic viscosity: 30°C JIS K-2283 mm2/s 5.51 Cetane value JIS K-2280 53.0 - The following constituent materials were used in preparation of the examples of embodiment and comparative examples.
- (1) Base oil: a mineral oil belonging to API Group III
- (2) Phenolic anti-oxidant: 6 methylheptyl alcohol ester of 3-(4-hydroxy-3,5-di-t-butyl-phenyl)propionic acid
- (3) Amine-based anti-oxidant: diphenylamine being a reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene
- (4) Additives package: additives containing dispersant, ZnDTP and detergent.
- Using the above-mentioned constituent materials, the lubricating oil compositions of Examples 1-4 and Comparative Examples 1-6 were prepared in accordance with Tables 3 and 4.
- The above-mentioned 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.
- The amounts of each constituent blended in are shown in each case as % by mass.
- In order to view the performance of the lubricating oil compositions of Examples 1-4 and Comparative Examples 1-6, hot tube tests (according to JPI-5S-55-99; a standard test from the Japanese Petroleum Institute for determining high temperature deposits) were carried out at 280°C under load conditions whereby 5% by mass of biodiesel fuel was added in respect of 100% by mass of each lubricating oil composition.
- 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.
- The results are shown in Tables 3 and 4. 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. 6 Base oil 88 85.5 84.5 85.5 86.5 88 Phenolic anti-oxidant 2.5 0.5 Amine-based antioxidant 2.5 3.5 1.0 Additives package 12 12 12 12 12 12 Total 100 100 100 100 100 100 Admixed BDF 5 5 5 5 5 Hot tube score 1.0 2.0 5.0 3.0 2.5 7.0 - When using 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 together, as shown in Examples 1-4, the amount of each being not less than 1% by mass and the total amount being not less than 2% by mass, an evaluation of 7 or higher was obtained in the hot tube test in all cases, and it was evident that these were lubricating oil compositions not prone to ageing after admixture of biofuel.
- Anti-oxidants were not added in the case of Comparative Example 1, and the hot tube score was poor, 1.0. 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.
Claims (4)
- 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 a 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 lubricating composition according to Claim 1 wherein the biofuel used in the diesel engine is derived from rapeseed oil.
- Use of the lubricating composition according to claim 1 or claim 2 in a diesel engine, and wherein a biofuel is used in the diesel engine, preferably a biofuel derived from rapeseed oil.
- A method of operating a diesel engine comprising lubricating the diesel engine with a lubricating composition according to any of claims 1 to 2 and using a biofuel, preferably derived from rapeseed oil, as fuel.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007190658A JP2009024123A (en) | 2007-07-23 | 2007-07-23 | Lubricating oil composition for diesel engine corresponding to biofuel |
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 |
---|---|
EP2179011A1 EP2179011A1 (en) | 2010-04-28 |
EP2179011B1 true EP2179011B1 (en) | 2018-06-27 |
Family
ID=39791277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08786285.0A Active EP2179011B1 (en) | 2007-07-23 | 2008-07-21 | Lubricating composition for use in diesel engines compatible with biofuel |
Country Status (8)
Country | Link |
---|---|
US (2) | US20100269774A1 (en) |
EP (1) | EP2179011B1 (en) |
JP (1) | JP2009024123A (en) |
CN (1) | CN101796171B (en) |
AR (1) | AR068609A1 (en) |
BR (1) | BRPI0814579B1 (en) |
RU (1) | RU2456333C2 (en) |
WO (1) | WO2009013275A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7960322B2 (en) * | 2007-10-26 | 2011-06-14 | Chevron Oronite Company Llc | Lubricating oil compositions comprising a biodiesel fuel and an antioxidant |
US9540586B2 (en) | 2009-06-26 | 2017-01-10 | The Lubrizol Corporation | Engine oil formulations for biodiesel fuels |
WO2011017555A1 (en) * | 2009-08-05 | 2011-02-10 | Basf Se | Lubricant composition |
DK2920282T3 (en) | 2012-11-19 | 2021-11-08 | Lubrizol Corp | ALKYLEN-COUPLED PHENOLES FOR USE IN BIODIESEL ENGINES |
JP2017039841A (en) * | 2015-08-19 | 2017-02-23 | コスモ石油ルブリカンツ株式会社 | Lubricant composition for internal combustion engine |
US11162048B2 (en) | 2016-12-27 | 2021-11-02 | The Lubrizol Corporation | Lubricating composition with alkylated naphthylamine |
ES2914785T3 (en) | 2016-12-27 | 2022-06-16 | Lubrizol Corp | Lubricant composition including N-alkylated dianiline |
US10487289B2 (en) | 2017-02-21 | 2019-11-26 | 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 |
DE59010484D1 (en) * | 1989-11-08 | 1996-10-10 | Ciba Geigy Ag | Lubricant compositions |
EP0456925B1 (en) * | 1990-05-14 | 1993-10-20 | Ethyl Petroleum Additives Limited | Antioxidant compositions |
JPH04202398A (en) * | 1990-11-30 | 1992-07-23 | Tonen Corp | Lubricating oil composition |
DE69324746T2 (en) * | 1992-09-02 | 1999-10-21 | The Lubrizol Corp., Wickliffe | Antioxidants for highly monounsaturated vegetable oils |
JPH08157853A (en) * | 1994-12-08 | 1996-06-18 | Cosmo Sogo Kenkyusho:Kk | Ester-based lubricating oil composition |
US5672752A (en) * | 1995-09-13 | 1997-09-30 | The Bfgoodrich Company | Liquid alkylated diphenylamine antioxidant |
JP3935982B2 (en) * | 1995-10-19 | 2007-06-27 | 出光興産株式会社 | Hydraulic fluid composition |
DE60029049T2 (en) * | 1999-05-19 | 2007-06-21 | Ciba Speciality Chemicals Holding Inc. | Stabilized hydrorefined and hydrodewaxed lubricant compositions |
RU2194742C2 (en) * | 2001-03-16 | 2002-12-20 | ООО "Лаборатория Триботехнологии" | Antiwear and antifriction additive with friction modifier, lubricating material, and method of preparing friction modifier |
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/en active Pending
-
2008
- 2008-07-18 AR ARP080103099A patent/AR068609A1/en unknown
- 2008-07-21 RU RU2010106057/04A patent/RU2456333C2/en active
- 2008-07-21 US US12/669,807 patent/US20100269774A1/en not_active Abandoned
- 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 BR BRPI0814579-2A patent/BRPI0814579B1/en active IP Right Grant
- 2008-07-21 CN CN200880100097.6A patent/CN101796171B/en active Active
-
2012
- 2012-04-16 US US13/448,054 patent/US20130102509A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
CN101796171B (en) | 2014-12-17 |
US20100269774A1 (en) | 2010-10-28 |
US20130102509A1 (en) | 2013-04-25 |
EP2179011A1 (en) | 2010-04-28 |
BRPI0814579A2 (en) | 2015-01-20 |
CN101796171A (en) | 2010-08-04 |
WO2009013275A9 (en) | 2009-03-12 |
RU2010106057A (en) | 2011-08-27 |
WO2009013275A1 (en) | 2009-01-29 |
JP2009024123A (en) | 2009-02-05 |
RU2456333C2 (en) | 2012-07-20 |
BRPI0814579B1 (en) | 2018-03-27 |
AR068609A1 (en) | 2009-11-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2179011B1 (en) | Lubricating composition for use in diesel engines compatible with biofuel | |
CN102300966B (en) | Polyol Ester Lubricating Oil | |
US20100105583A1 (en) | High temperature biobased lubricant compositions from boron nitride | |
JP5638256B2 (en) | Lubricating oil composition | |
KR970707264A (en) | LUBRICANT ADDITIVE FORMULATION | |
TW200930805A (en) | Lubricating oil composition | |
CN107892978B (en) | Long-life energy-saving diesel engine oil composition and preparation method thereof | |
CN104919028A (en) | Coupled phenols for use in biodiesel engines | |
CN100344740C (en) | Lubricating oil composition | |
TW408172B (en) | Biodegradable grease compositions | |
CN101362970A (en) | Novel synthetic fuel and method of preparation thereof | |
CN108779413A (en) | Lubricant for two-stroke marine engine | |
CN107699320A (en) | A kind of gas engine Special lubricating fluid composition | |
PL204130B1 (en) | Diesel fuel compositions | |
WO2011007643A1 (en) | Fuel-efficient engine oil composition | |
JP5349223B2 (en) | Engine oil composition | |
KR20080014789A (en) | High temperature biobased lubricant compositions comprising boron nitride | |
RU2683646C2 (en) | Lubricating oil composition | |
CN102037109B (en) | Lubricant additive composition suitable for lubricating two-stroke engines fueled with heavy fuels | |
JP2016520693A (en) | Diester base oil blends with improved cold flow and low Noack | |
RU2738610C1 (en) | Composition of environmentally safe diesel fuel | |
RU2786216C1 (en) | Composition of environmentally friendly diesel fuel with improved lubrication properties | |
RU2476587C2 (en) | Lubricant composition of high-temperature oil for heat-stressed gas-turbine engines of supersonic aircraft | |
JP6699841B2 (en) | Antioxidant for light oil and light oil fuel composition | |
JP5525708B2 (en) | Light oil composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20100216 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20161201 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20180219 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1012346 Country of ref document: AT Kind code of ref document: T Effective date: 20180715 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602008055769 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180927 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180927 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20180627 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180928 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1012346 Country of ref document: AT Kind code of ref document: T Effective date: 20180627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181027 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602008055769 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180721 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180731 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180731 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180721 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180731 |
|
26N | No opposition filed |
Effective date: 20190328 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180721 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20080721 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180627 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240530 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240611 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240604 Year of fee payment: 17 |