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
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • 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
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
• • 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
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • 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
  • C10M2215/28—Amides; Imides
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • 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
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • 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
  • C10N2030/52—Base number [TBN]
• • 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

Definitions

• the present invention relates to a lubricating oil composition, particularly a lubricating oil composition for use in diesel engines (i.e. compression-ignition engines), more especially diesel engines of the type referred to as heavy duty diesel engines, herein abbreviated to "HDD”.
• diesel engines i.e. compression-ignition engines
• HDD heavy duty diesel engines
• Diesel engines comprise one or more bores in each of which a piston reciprocates.
• the piston has piston rings around its periphery to provide a seal between the combustion chamber and the crankcase.
• the reciprocating movement of the piston causes the piston rings to bear towards the wall of the bore with the potential to cause wear of the bore wall and the piston rings. Wear of the bore wall and the piston rings is ameliorated by ensuring, as far as possible, that a film of lubricating oil is maintained on the bore wall to avoid or reduce any direct contact between the piston rings and the bore wall.
• the wall of the bore is formed with arrays of grooves which act to retain lubricating oil so that the formation and maintenance of a film of lubricating oil over the wall of the bore is facilitated.
• the grooves are often formed as spiral grooves or recesses in the bore wall, and these are usually formed as two sets of grooves spiralling in opposite senses in the bore wall so that the grooves of each set overlap each other, whereby the formation and maintenance of a film of lubricating oil on the bore wall is facilitated.
• One objective of the present invention to reduce or eliminate bore polishing by the use of certain types of lubricant, as specified below.
• EP 1167497A claims and describes a lubricating oil composition having a sulfur content of 0.01 to 0.3 wt. % and a phosphorus content of 0.01 to 0.1 wt. %, and giving a sulphated ash in the range of 0.1 to 1 wt. %, which comprises
• the composition of EP 1167497A is intended to provide lubrication for all types of internal combustion engines, including diesel engines, without adversely affecting the functioning of exhaust gas particulate traps, oxidizing catalysts and/or NO x -reducing catalysts.
• Example 3 of this patent document describes a lubricating oil composition comprising, as a metal-containing detergent, 1.7 wt. % magnesium salicylate which contains 6.0 wt. % Mg, 0.22 wt. % S; TBN 280 mg KOH/g, available as "SAP 008" from Shell Japan Co. Ltd.
• EP1167497A does not appear to relate to heavy duty diesel engines, and is not concerned with bore polishing issues. It does not provide any disclosure or teaching having a bearing on bore polishing.
• US patent US 6423670 B2 claims and discloses a diesel engine lubricating oil composition
• a diesel engine lubricating oil composition comprising a major amount of oil of lubricating viscosity to which has been added: (a) a lubricating oil ashless dispersant which has not more than 0.2 mass % boron; (b) an oil-soluble neutral calcium phenate detergent; (c) an oil-soluble overbased calcium or magnesium sulfonate or mixture thereof present in an amount such that not more than 0.05 magnesium is present in the composition; (d) a metal dihydrocarbyldithiophosphate present in an amount such that the phosphorus content of the composition is from 0.025 to 0.10 mass %; and (e) a phenolic or aminic antioxidant in a minor amount the composition being free of neutral metal detergent, other than the phenate (b).
• Example 2 of US 6423670 describes two lubricating oils, both comprising 0.256 mass % overbased Mg sulfonate, a borated dispersant, a neutral calcium phenate, a phenol antioxidant, a zinc dihydrocarbyldithiophosphate, and an overbased calcium sulfonate, and one of the oils comprising, in addition, a neutral calcium sulfonate.
• the oils were evaluated according the procedure of the Daimler Chrysler Sequence IIIE, OM364LA diesel engine test for several characteristics, including bore polish. The oil comprising the neutral calcium sulphonate gave a poor result (5-6%) in terms of Bore Polish results. Similar oils without the neutral calcium sulfonate gave better results even when the overbased Mg sulfonate content was reduced, other factors being equal.
• compositions of US 5320765A are claimed to reduce engine carbon deposits and to reduce rates of lubricating oil consumption.
• the compositions according to US 5320765 A have low ash contents (less than 0.6 weight percent) in order to meet mandatory limitations on ash in engine exhaust gas.
• Lubricating oils for diesel engines are usually formulated to have relatively high basicity (e.g. high total base number, TBN) in order to neutralize acidic moieties and thus reduce corrosion due to acidic moieties.
• High basicity is usually attained by incorporating basic metal-containing detergents in the lubricating oils.
• Common basic metal-containing detergents include calcium-based detergents, such as calcium sulfonates. The basicity of metal-containing detergents is often increased by employing overbased detergents, which are well-known to skilled persons and which contain more basic metal moiety than non-overbased detergents.
• the amount of basic metal detergent which can be incorporated in a lubricating oil is restricted because the metal of the detergent gives rise to ash materials which adversely affect the operation of engine equipment such as exhaust gas filters and exhaust gas purification catalysts.
• Ash materials are assessed by mass. Thus, the mass of ash which is tolerable for an engine and its associated equipment restricts the TBN of the engine oil arising from the basic metal-containing detergents therein.
• magnesium detergents produce a lower mass of ash than calcium detergents due to the fact that magnesium is lighter than calcium and gives rise to lighter ash.
• Engine oil compositions for diesel engines, including HDDs have been formulated with magnesium detergents.
• a well-known drawback of lubricant compositions comprising magnesium-containing detergents is that they tend to cause bore polishing, particularly (but not exclusively) in contemporary European-style HDDs. Accordingly, the concentration of magnesium in engine oils has tended to be restricted to relatively low values.
• lubricating oils containing relatively high concentrations of magnesium from magnesium-containing detergents can be formulated without giving rise to unacceptable levels of bore polishing or unacceptable levels of ash in diesel engines, including HDDs.
• magnesium-containing lubricating compositions gives rise to certain benefits and advantages.
• the detergent component of the claimed lubricating oil compositions may comprise at least one salicylate detergent.
• a first aspect of the present invention provides, a lubricating composition for a diesel engine, particularly a heavy duty diesel engine (“HDD”), comprising the following components:
• a second aspect of the present invention provides a method of operating a heavy duty diesel engine which comprises lubricating the engine with a lubricating oil composition according to the first aspect.
• a third aspect of the invention provides a method of reducing bore polishing in a heavy duty diesel engine, which method comprises lubricating the engine with a lubricating oil composition according to the first aspect.
• the base oil is an oil of lubricating viscosity and may have characteristics in the following ranges:
• the base oil contains one or more of Groups I, II, III or IV base stocks as defined in API Engine Oil Licensing and Certification System (EOLCS), Industry Services Department, 14 th edition, December 1996, Addendum 1, December 1998 and ATIEL code.
• the base oil sulphur content may be between 0.00 and 1.00 wt.% and the KV @100°C may be from 3.8 mm 2 /s to 21.9 mm 2 /s. More preferably the base oil sulphur content may be from 0.00 to 0.80 wt.% and the KV @100°C may be from 3.8 mm 2 /s to 8.0 mm 2 /s.
• the antioxidant component may be one or more of an amine or an aminic compound and/or a sulfur-free phenol or a sulfur-free phenolic compound.
• Suitable amines include (but are not restricted to) Irganox L67 and Irganox L57 available from Ciba and Naugalube 438L available from Chemtura.
• Suitable sulfur-free phenols include (but are not restricted to) Irganox L135 available from Ciba and HITEC 4782 and 4727 available from Afton Chemicals. "Irganox", “Naugalube” and “HITEC” are trade-names.
• the one or more antioxidant component comprise at least 0.6 mass % of the lubricating oil composition, based on the total mass of the lubricating oil composition.
• the one or more antioxidant components provide at least 0.75 mass % of the lubricating oil compositions based upon the total mass of the lubricating oil composition.
• the one or more antioxidant components comprise up to 3.0 mass % of the lubricating oil composition based upon the total mass of the lubricating oil composition.
• the one or more antioxidant components suitably provide up to 2.75 mass % of the lubricating oil composition, based upon the total mass of the lubricating oil composition.
• the lubricating oil composition comprises only ash-free antioxidant components.
• the overbased magnesium compound provides the composition with greater than 0.05 mass % Mg, based upon the mass of the composition.
• the magnesium compound provides the composition with at least 0.06 mass % Mg, based on the mass of the composition.
• the magnesium compound may provide the composition with at least 0.063 mass % Mg, based upon the mass of the composition.
• the overbased magnesium compound provides the composition with no more than 0.3 mass % Mg, based upon the mass of the composition.
• the Mg content of the composition is suitably up to 0.15 mass %, based upon the mass of the composition.
• the composition suitably comprises up to 0.14 mass % Mg from the magnesium compound, based upon the total mass of the composition.
• Lubricating compositions according to the invention may have a TBN (total base number as determined by ASTM D2896) of at least 8.0, preferably 9.0 or higher.
• TBN total base number as determined by ASTM D2896
• the maximum TBN is not likely to exceed 20.0, and 15.0 may be regarded as a practical maximum TBN for many compositions.
• Lubricating compositions according to the invention may comprise phosphorus moieties.
• the phosphorus moieties may be antiwear components such as one or more salts of one or more dihydrocarbyldithiophosphoric acids.
• a typical salt of a dihydrocarbyldithiophosphoric acid employed as an antiwear component is zinc dihydrocarblydithiophosphate, ZDDP.
• the lubricating compositions may comprise phosphorus moieties from other components, such as certain phosphites which may be employed as antiwear components.
• Phosphorus may be present in the lubricating compositions (e.g. from ZDDP) in amounts up to 2000 ppm by mass.
• the maximum phosphorus level is preferably lower, e.g.
• the amount of phosphorous provided by the metal hydrocarbyl dithiophosphate is in the range of 0.05 to 0.20 mass %, based on the mass of the composition.
• Lubricating compositions according to the present invention may optionally comprise additional additives, including one or more dispersants.
• the one or more dispersants are suitably nitrogen containing dispersants.
• the one or more dispersants may provide the lubricating composition with at least 0.07 mass % nitrogen, based upon the mass of the composition.
• the one or more optional dispersants suitably provide the lubricating oil composition with between 0.07 to 0.25 mass % nitrogen, based upon the mass of the lubricating oil composition.
• the sulphated ash content of the lubricating oil composition is at least 0.6 mass %, based upon the mass of the composition.
• the lubricating oil composition suitably has a sulphated ash content of at least 0.8 mass %, based on the mass of the composition.
• a lubricating oil composition according to the present invention suitably has a sulphated ash content of no lower than 1.0 mass %.
• a lubricating oil composition according to the present invention has a sulphated ash content of not more than 2.0 mass % based on the total mass of the composition.
• a lubricating oil composition according to the present invention may have a sulphated ash content no greater than 1.6 mass %, preferably no greater than 1.5 mass %, and more preferably no greater than 1.2 mass % based on the mass of the composition.
• compositions were formulated, all suitable for lubricating a heavy duty diesel engine.
• the compositions contained, inter alia, the following components:
• compositions also included components which are usually included in HDD lubricant compositions, such as one or more of the following: friction modifier, viscosity modifier, antifoamant, demulsifier, pour point depressant (inter alia ). Since these components are well-known and are not believed to be significant in relation to the bore-polishing benefits of the lubricating compositions of the invention, they will not be further discussed herein.
• Lubricant oil compositions suitable for use with HDDs were formulated from the components (i) to (v) mentioned above, together with other well-known lubricant oil components.
• the oils were formulated in the well-known manner to have viscosity characteristics of 10W-40 or 15W-40.
• the lubricant viscosity was SAE 40 grade and all samples had an approximately equal kinematic viscosity at 100°C, thereby factoring out base stock effects and giving a robust comparison between the samples.
• the compositions had varied concentrations of the following components: the calcium and magnesium detergents, the dispersant, the antioxidant, and the ZDDP antiwear component.
• compositions were evaluated for bore polish characteristics in accordance with the well-known test: CEC-L-52-T-97 (OM441LA).
• the test method is available from the CEC (Coordinating European Council).
• Table 1 Bore Polish Test Results - (Test Procedure according to CEC-L-52-T-97) Low %Mg, Low AO** PASSING Oil Bore Polish High %Mg, Low AO** Fail on Bore Polish High %Mg Oil, High AO** Pass on Bore Polish Sample No.
• oil samples 1, 2 and 3 are illustrative of compositions having low magnesium contents and low antioxidant contents.
• the magnesium contents are in the range of 0.26 to 0.29 mass %.
• the antioxidant contents are in the range of 0.30 to 0.42 mass %.
• the other components of these three samples are in concentrations which do not significantly affect the Bore Polish test results. A skilled person would know how to adjust the concentrations of the other components to achieve this effect. It is seen that the compositions all have bore polish results below the maximum limit (2.0) and that therefore, all of the samples 1, 2 and 3 pass the Bore Polish test.
• Oil samples 4 to 8 are illustrative of compositions having high magnesium contents and low antioxidant concentrations.
• the samples have Mg concentrations in the range of 0.053 to 0.102 mass %, and antioxidant concentrations in the range 0.17 to 0.42 mass% (overlapping those of Samples 1 to 3).
• the other components of these five Samples are present in concentrations which do not significantly affect the Bore Polish results. A skilled person would know how to adjust the concentrations of these other components to achieve this effect. It is apparent from the Test Results for Samples 4 to 8 that high Mg concentrations and low antioxidant concentrations produce Bore Polish "Fail” results above the maximum limit (2.0), in the range of 2.4 to 3.6. It is also apparent that "Fail” results were still obtained in the range despite varying the principal anti-wear additive (ZDDP- A) from 0.08 to 0.12 wt.% P.
• ZDDP- A principal anti-wear additive
• Sample 13 comprising 0.170 mass % Ca and 0.138 mass % Mg, gave rise to 1.4 mass % sulphated ash, no higher than the ash obtained with low Mg Samples 1 and 3 and high Mg Samples 4 and 5, which all contain relatively higher levels of calcium that Samples 13.
• oil compositions according to the invention provide excellent performance in terms of bore polishing results without giving rise to unacceptable levels of sulphated ash.

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• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
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• Lubricants (AREA)

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• 2007
  • 2007-05-03 EP EP07107472.8A patent/EP1884557B1/de active Active

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