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WO2006066767A1 - Systemes de lubrification - Google Patents

Systemes de lubrification Download PDF

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Publication number
WO2006066767A1
WO2006066767A1 PCT/EP2005/013421 EP2005013421W WO2006066767A1 WO 2006066767 A1 WO2006066767 A1 WO 2006066767A1 EP 2005013421 W EP2005013421 W EP 2005013421W WO 2006066767 A1 WO2006066767 A1 WO 2006066767A1
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WO
WIPO (PCT)
Prior art keywords
base
lubricant
engine
lubricating
dispersant
Prior art date
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Ceased
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PCT/EP2005/013421
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English (en)
Inventor
Brian Lawrence
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Infineum International Ltd
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Infineum International Ltd
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Publication of WO2006066767A1 publication Critical patent/WO2006066767A1/fr
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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M26/00—Engine-pertinent apparatus for adding exhaust gases to combustion-air, main fuel or fuel-air mixture, e.g. by exhaust gas recirculation [EGR] systems
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—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
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0091—Treatment of oils in a continuous lubricating circuit (e.g. motor oil system)
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • C10N2030/041—Soot induced viscosity control
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • 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

  • This invention relates to lubrication of or for internal combustion engines, such as compression-ignited, e.g. diesel, engines and spark-ignited, e.g. gasoline, engines.
  • internal combustion engines such as compression-ignited, e.g. diesel, engines and spark-ignited, e.g. gasoline, engines.
  • Exhaust Gas Recirculation (commonly abbreviated to EGR) is a known system for use in or with internal combustion engines that recirculates exhaust gases back through the engine, via the air inlet manifold of a normally aspirated engine or to the compressor inlet or outlet of a turbocharged engine.
  • EGR is used to reduce emission of oxides of nitrogen (NOx) from diesel engines by reducing peak combustion temperatures.
  • NOx oxides of nitrogen
  • Coupled EGR exhaust gases
  • EGR including Cooled EGR
  • the present invention provides a way of enhancing and/or extending lubricant life that does not require use of a chemical filter in the EGR or chemical filtration of the EGR stream. This is done by employing an immobilised strong base in the lubricating system of the engine.
  • this invention provides a lubricating system of or for an internal combustion engine equipped with an exhaust gas recirculation (EGR) system having means for cooling gas in the EGR system comprising: a. a lubricant containing, in a minor amount, a first base in the form of a dispersant; b. means for circulating the lubricant; and c. a second base, stronger than the first base, immobilised in the lubricating system; wherein the exhaust gas circulation system does not include a chemical filter.
  • EGR exhaust gas recirculation
  • this invention provides a method of lubricating an internal combustion engine, said method comprising: a. lubricating the engine with a circulating lubricant that contains, in a minor amount, a first base in the form of a dispersant; b. contacting the lubricant from step a. with second base, stronger than the first base, that is immobilised; c. re-circulating lubricant from step b.; and d. recirculating and cooling exhaust combustion gases from operation of the engine to the air intake stream for the engine, without chemically filtering the re-circulating gases.
  • this invention provides the use, in a lubricating system of or for an internal combustion engine, to inhibit viscosity increase, and/or maintain particulate combustion products, especially soot, in suspension and/or improve soot-handling characteristics; and/or control sludge deposits in the engine and/or moderate the rate of TBN depletion and inhibit the rate of TAN increase, in the crankcase lubricant of the engine, of a combination of an immobilised second base to displace a first base weaker than the second base, first base:acid salts in circulating lubricant, and of recirculated, cooled, chemically unfiltered exhaust gas.
  • this invention provides the use to inhibit viscosity increase in a lubricant, and/or to maintain particulate combustion products, especially soot, in suspension in a lubricant, and/or to improved the soot-handling characteristics of the lubricant, and/or to control sludge deposits in an internal combustion engine, and/or moderate the rate of lubricant TBN depletion and inhibit the rate of TAN increase, of an immobilised second base to displace a first base, weaker than the second base, from first base:acid salts in circulating lubricant in a lubricating system, the system being of or for an internal combustion engine in which the exhaust gas is recirculated, cooled and chemically unfiltered.
  • a chemical filter is not provided in the EGR system and recirculating exhaust gases are not chemically filtered.
  • the EGR system and stream include all parts thereof positioned before the intake manifold of the engine and include those parts or operations positioned or occurring, as appropriate, both before and after the recirculating gases are mixed with intake air.
  • active ingredient or "(a.i.)” refers to additive material that is not diluent or solvent; "comprising” or any cognate word specifies the presence of stated features, steps, or integers or components, but does not preclude the presence or addition of one or more other features, steps, integers, components or groups thereof; the expressions "consists of or “consists essentially of or cognates may be embraced within “comprises” or cognates, wherein "consists essentially of permits inclusion of substances not materially affecting the characteristics of the composition to which it applies;
  • major amount means in excess of 50 mass % of a composition
  • minor amount means less than 50 mass % of a composition
  • TAN means total acid number as measured by ASTM D664;
  • TBN total base number as measured by ASTM D4739.
  • the lubricant contains a major proportion of an oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) as the primary liquid constituent of the lubricant into which additives and possibly other oils are blended.
  • base stock sometimes referred to as "base stock” or “base oil”
  • a base oil may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil and heavy duty diesel oil. Generally the viscosity of the oil ranges from 2 to 30, especially 5 to 20, mmV at 100 0 C.
  • Natural oils include animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffmic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes), poly (1- decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl)benzenes); polyphenols (e.g.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g.
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Unrefined, refined and re-refined oils can be used in the lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.
  • base oil examples include gas-to-liquid (“GTL”) base oils, i.e. the base oil may be an oil derived from Fischer-Tropsch-synthesised hydrocarbons made from synthesis gas containing hydrogen and carbon monoxide using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • GTL gas-to-liquid
  • Base oil may be categorised in Groups 1 to V according to the API EOLCS 1509 definition.
  • the oil of lubricating viscosity is provided in a major amount, in combination with a minor amount of at least one additive and, if necessary, one or more co-additives such as described hereinafter, constituting the lubricant.
  • This preparation may be accomplished by adding the additive directly to the oil or by adding it in the form of a concentrate thereof to disperse or dissolve the additive.
  • Additives may be added to the oil by any method known to those skilled in the art, either prior to, contemporaneously with, or subsequent to, addition of other additives.
  • the terms "oil-soluble” or “dispersible”, or cognate terms, used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or are capable or being suspended in the oil in all proportions.
  • the lubricant contains, in a minor amount, a first base comprising a dispersant.
  • a dispersant is an additive for a lubricant whose primary function is to hold solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge fiocculation and precipitation or deposition on metal parts of the engine.
  • Dispersants may be "ashless", i.e. non-metallic organic materials that form substantially no ash on combustion, in contrast to metal-containing, and hence ash-forming, materials. They comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an O, P or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
  • Ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of a long chain of hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto, and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and alkylene polyamine, such as described in US-A-3, 442, 808.
  • the oil-soluble polymeric hydrocarbon backbone is typically an olefin polymer or polyene, especially a polymer comprising a major molar amount (i.e. greater than 50 mole %) of a C 2 to C 18 olefin (e.g. ethylene, propylene, butylenes, isobutylene, pentene, octane- 1, styrene), and typically a C 2 to C 5 olefin.
  • the oil-soluble polymeric hydrocarbon backbone may be homopolymeric (e.g. comprising a copolymer of ethylene and an alpha-olefm such as propylene or butylenes, or a copolymer of two different alpha-olefins).
  • a preferred class of olefin polymers comprises polybutenes, specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • Other classes of olefin polymers include ethylene alpha-olefm (EAO) copolymers and alpha-olefm homo- and copolymers.
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl- substituted succinic acid.
  • a noteworthy group of dispersants are hydrocarbon- substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as polyethylene polyamine.
  • reaction products of polyalkylene polyamines with alkenyl succinic anhydrides such as described in US-A-3, 202, 678; -3, 154, 560; -3, 172,892; -3, 024, 195, -3, 024, 237; -3,219,666; and - 3,216,936; and BE-A-66,875 that may be post-treated to improve their properties, such as borated (as described in US-A-3,087,936 and -3,254,025) fluorinated and oxylated.
  • boration may be accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
  • Dispersants may also include metal-containing materials such as molybdenum- containing materials known in the art.
  • Preferred dispersants are p ⁇ lyalkene-substituted succinimides wherein the polyalkene group has a number-average molecular weight in the range of 900 to 5,000.
  • the number-average molecular weight is measured by gel permeation chromatography (GPC).
  • the polyalkene group may comprise a major molar amount (i.e. greater than 50 mole %) of a C 2 to C 18 alkene, e.g. ethene, propene, butene, isobutene, pentene, octane-1 and styrene.
  • the alkene is a C 2 to C 5 alkene; more preferably it is butene or isobutene, such as may be prepared by polymerisation of a C 4 refinery stream.
  • the number average molecular weight of the polyalkene group is in the range of 1,800 to 2,800, such as 2,000 to 2,500.
  • the polyalkene-substituted succinimides wherein the polyalkene group has a number- average molecular weight in the range of 900 to 5,000 and more especially the latter, most preferred, dispersant may be used in a lubricant having a phosphorus content, expressed as atoms of phosphorus, of less than 0.1 mass %, an ash content, expressed as sulphated ash, of less than 1.0 mass %, and optionally a sulphur content, expressed as atoms of sulphur, of less than 0.4 mass %.
  • the first base will normally be added to the lubricant during its formulation or manufacture.
  • the first base must be strong enough to neutralize at least a portion of the combustion acids (i.e. form a salt or salts).
  • a suitable first base will typically have a pKa from 4 to 12 and in many cases may be termed a "weak base".
  • the first base should be sufficiently soluble for the salt or salts formed to remain soluble in the lubricant and not to precipitate.
  • the amount of first base in the lubricant will vary depending upon the amount of combustion acids present, the degree of neutralization desired, and the specific applications of the lubricant. In general, the amount need only be that which is effective or sufficient to neutralize at least a portion of the combustion acids.
  • the amount of first base, as active ingredient will range from 0.01 to 3 wt % or more such as up to 4 wt%, preferably from 0.1 to 1.0 wt %. This range is particularly advantageous for polyalkene-substituted succinimides wherein the polyalkene group has a number-average molecular weight in the range of 900 to 5,000, and more especially the most preferred dispersant defined above.
  • lubricating oil additives may include other dispersants, antiwear agents, antioxidants, corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers and friction modifiers.
  • the lubricant is not restricted to a conventionally-formulated lubricant, but may be any lubricant specifically or otherwise designed for the purposes described in this specification regardless of SAE viscosity grade; API, ILSEC, ACEA, JAMA, JASO or other performance credentials; base oil compositions as described below; and additive compositions whether for heavy duty (HD) passenger car motor oil (PCMO), conventional, or low or ultra-low sulphated ash-phosphorus-sulphur (SAPS).
  • HD heavy duty
  • PCMO passenger car motor oil
  • SAPS ultra-low sulphated ash-phosphorus-sulphur
  • the second base is a base that will displace at least a portion of the first base from the neutral salts and return that portion of the first base to the lubricant for recirculation to the piston ring zone where the first base is reused to neutralize combustion acids.
  • suitable second bases include, but are not limited to, barium oxide, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, sodium aluminate, sodium carbonate, sodium hydroxide, zinc oxide, or their mixtures; magnesium oxide is particularly preferred. In many cases the second bases may be termed "strong bases".
  • the second base may be adhered to or incorporated (e.g. impregnated) on or with a substrate immobilized in the lubricating system of the engine.
  • the substrate can be located on the engine block or near the sump.
  • the substrate if used, will be part of the filter system for filtering lubricant, although it could be separate therefrom.
  • Preferred substrates include paper, fabric, felt, glass, plastic, microglass and both woven and non-woven polymeric fibre.
  • Other useful substrates include, but are not limited to, alumina, activated clay, cellulose, cement binder, silica-alumina, and activated carbon.
  • the substrate may be inert or not inactive.
  • the second base may be incorporated into or adhered onto the substrate by methods known to those skilled in the art.
  • the substrate is alumina
  • the second base can be deposited by using the following technique.
  • a highly porous alumina is selected. The porosity of the alumina is determined by weighing dried alumina and then immersing it in water. The alumina is removed from the water and the surface water removed by blowing with dry air. The alumina is then reweighed and compared with the dry alumina weight. The difference in weight is expressed as grams of water per gram of dry alumina.
  • a saturated solution of calcium oxide in water is prepared and added to the dry alumina in an amount equal to the difference between the weight of the wet and dry alumina. The water is removed from the alumina by heating, leaving calcium oxide deposited on the alumina as the product. This preparation can be carried out under ambient conditions, except that the water removal step is performed at about 100 0 C.
  • the amount of second base required will vary with the amount of first base in the lubricant and the amount of combustion acids formed during engine operation. However, since the second base is not being continuously regenerated for reuse (unlike the first base), the amount of second base must be at least equal to (and preferably be a multiple of) the equivalent weight of the first base in the lubricant. Therefore, the amount of second base should be from 1 to 15 times, preferably from 1 to 5 times, the equivalent weight of the first base in the lubricant.
  • the second base combustion acid salts thus formed will be immobilized as deposits with the second base, for example on the substrate, if used. Thus, deposits which would normally be formed in the piston ring zone are not formed until the soluble salts contact the second base.
  • the second base will be located such that it can be easily removed from the lubricating system, e.g. by including it as part of the oil filter system.
  • the invention is applicable to a wide range of internal combustion engines equipped with a Cooled EGR such as compression-ignited and spark-ignited engines.
  • Examples include engines for power generation, locomotive and marine equipment and heavy duty on-highway trucks; heavy duty off-highway engines such as may be used for agriculture, construction and mining and engines for light duty commercial and passenger car applications.
  • a particularly preferred embodiment of the first aspect of the invention is a lubricating system of or for an internal combustion engine equipped with an exhaust gas recirculation (EGR) system having means for cooling gas in the EGR system
  • EGR exhaust gas recirculation
  • a lubricant containing, in a minor amount, a first base in the form of a dispersant, being a polyalkene-substituted succinimide wherein the polyalkene group has a number-average molecular weight in the range of 900 to 5,000 (wherein the number-average molecular weight is measured by gel permeation chromatography (GPC)), wherein the polyalkene group may preferably comprise a major molar amount (i.e.
  • GPC gel permeation chromatography
  • the first base typically being present in an amount range from 0.01 to 3 wt % or more, preferably from 0.1 to 1.0 wt %; b. means for circulating the lubricant; and c. a second base, stronger than the first base and immobilised in the lubricating system, the second base consisting essentially of magnesium oxide; the lubricant in a.
  • a total phosphorus content expressed as atoms of phosphorus, of less than 0.1 mass %, an ash content, expressed as sulphated ash, of less than 1.0 mass %, and optionally a sulphur content, expressed as atoms of sulphur, of less than 0.4 mass %; and wherein the exhaust gas circulation system does not include a chemical filter.
  • a particularly well-preferred second aspect of the invention is a method of lubricating an internal combustion engine, said method comprising: a. lubricating the engine with a circulating lubricant that contains, in a minor amount, a first base in the form of a dispersant, being a polyalkene-substituted succinimide wherein the polyalkene group has a number-average molecular weight in the range of 900 to 5,000 (wherein the number-average molecular weight is measured by gel permeation chromatography (GPC)), wherein the polyalkene group may preferably comprise a major molar amount (i.e.
  • GPC gel permeation chromatography
  • the number average molecular weight of the polyalkene group is in the range of 1,800 to 2,800, such as 2,000 to 2,500, the first base typically being present in an amount range from 0.01 to 3 wt % or more, preferably from 0.1 to 1.0 wt %; b. contacting the lubricant from step a. with second base, stronger than the first base, that is immobilised, the second base consisting essentially of magnesium oxide; c. re-circulating lubricant from step b.; and d.
  • the lubricant in step a has (after addition of the first base and any other additives) a total phosphorus content, expressed as atoms of phosphorus, of less than 0.1 mass %, an ash content, expressed as sulphated ash, of less than 1.0 mass %, and optionally a sulphur content, expressed as atoms of sulphur, of less than 0.4 mass %.
  • Particularly-preferred embodiments of the third and fourth aspects of the invention concern the uses of the particularly-preferred combination of first and second bases described in the two immediately-preceding paragraphs, in the lubricant composition defined therein, to inhibit viscosity increase in said lubricant; or to maintain particulate combustion products, especially soot, in suspension in said lubricant; or to control sludge deposits in a diesel engine employing said lubricant; or to moderate the rate of lubricant TBN depletion and inhibit the rate of TAN increase; the use being in a lubricating system of or for a diesel engine in which the exhaust gas is recirculated, cooled and chemically filtered.
  • a lubricant was blended, as an SAE 15W40 viscosity grade lubricant, with an all-Group I mineral base oil, a commercial viscosity modifer and commercial additive package for providing heavy duty performance according to the American Petroleum Institute (API) CI-4 category.
  • the lubricant contained a "first" (weak) base in the form of a polyisobutene succinimide dispersant (3.8 mass %) in which the polyisobutene had a number average molecular weight of 2225.
  • the lubricant was tested in a Herbston (RTM) (TDi) engine (1.9L), modified to replicate the operation of a heavy duty diesel engine provided with a Cooled EGR.
  • An external supercharger was added to compensate for power loss due to use of EGR.
  • the tests were carried out under identical high load conditions for a nominal duration of 100 hours with a wide open throttle at 1900 rpm giving rise to an increase of the average EGR rate to 14.8% by volume (being the ratio of the volume of exhaust gas in the intake stream to the volume flow of fresh air in the intake stream, determined by measuring the carbon dioxide (vol. %) in the intake manifold and in the exhaust gas after correction for "background" carbon dioxide in the ambient air, typically about 0.09 vol. %) and an average inlet manifold temperature of 4O 0 C.
  • Test 1 was satisfactorily completed to its intended 100 hour duration, and inspection of the engine showed acceptable cleanliness.
  • Test A was aborted after about 94 hours because it became impossible to control the engine operating temperature within defined limits. Inspection of the engine showed this to be due to severe sludge deposit formations on the engine temperature control probe and on most or all other internal engine surfaces thereby significantly reducing the volume of circulating lubricant.
  • Test A ⁇ Plots are made based on the results and extrapolated.
  • the need for oil change may be regarded as being related to the point of intersection between the TBN and TAN lines or curves. It is seen from Figure 1 that the extrapolated intersect for reference Test A is at about 100 hours whereas the extrapolated intersect for Test 1 (of the invention) is at about 160 hours. Figure 1 therefore demonstrates that useful engine life (or oil drain interval) is significantly enhanced or extended.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

Dans la lubrification d'un moteur à combustion interne équipé d'un système de recirculation des gaz d'échappement refroidis (EGR), un lubrifiant contenant une quantité mineure d'un dispersant est mis en circulation dans un système de lubrification, de sorte que le dispersant forme des sels contenant des acides de combustion, après quoi le lubrifiant est mis en contact avec une base immobilisée plus fortement basique que le dispersant, qui déplace le dispersant des sels pour former un ensemble base: sels d'acide de combustion et libérer le dispersant dans le lubrifiant. Le système EGR ne comprend pas de filtre chimique et des gaz de combustion sont filtrés chimiquement.
PCT/EP2005/013421 2004-12-24 2005-12-13 Systemes de lubrification Ceased WO2006066767A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0428309.9 2004-12-24
GB0428309A GB2421511B (en) 2004-12-24 2004-12-24 Lubricating systems

Publications (1)

Publication Number Publication Date
WO2006066767A1 true WO2006066767A1 (fr) 2006-06-29

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PCT/EP2005/013421 Ceased WO2006066767A1 (fr) 2004-12-24 2005-12-13 Systemes de lubrification

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GB (1) GB2421511B (fr)
WO (1) WO2006066767A1 (fr)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2008112998A1 (fr) 2007-03-15 2008-09-18 Honeywell International Inc. Procédé de régénération d'un dispersant huileux de graissage
US8022021B2 (en) 2007-02-05 2011-09-20 The Lubrizol Corporation Low ash controlled release gels
US8691096B2 (en) 2008-02-01 2014-04-08 Lutek, Llc Oil filters containing strong base and methods of their use

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GB476422A (en) * 1935-03-04 1937-12-06 John Kay Russell Improvements in or relating to liquid refiners and method for refining liquids
US5164101A (en) * 1988-11-09 1992-11-17 Exxon Research And Engineering Co. Method for reducing piston deposits
US20030111398A1 (en) * 2001-05-30 2003-06-19 Derek Eilers Additive dispensing cartridge for an oil filter, and oil filter incorporating same
US20030148899A1 (en) * 1999-04-08 2003-08-07 Toshiaki Kuribayashi Lubricant oil composition for diesel engines (LAW964)

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JP3491797B2 (ja) * 1995-12-05 2004-01-26 株式会社デンソー 車両用発電装置
JP2000319682A (ja) * 1999-05-10 2000-11-21 Tonen Corp 内燃機関用潤滑油組成物
GB0121084D0 (en) * 2001-08-31 2001-10-24 Univ Leeds Improved productivity of heterologous gene expression
US6851414B2 (en) * 2002-07-30 2005-02-08 Exxonmobil Research And Engineering Company Method and system to extend lubricant life in internal combustion EGR systems
US6869919B2 (en) * 2002-09-10 2005-03-22 Infineum International Ltd. Lubricating oil compositions
US20040168215A1 (en) * 2003-02-21 2004-08-26 Liwen Jiang Plant gene expression system for processing, targeting and accumulating foreign proteins in transgenic seeds

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Publication number Priority date Publication date Assignee Title
GB476422A (en) * 1935-03-04 1937-12-06 John Kay Russell Improvements in or relating to liquid refiners and method for refining liquids
US5164101A (en) * 1988-11-09 1992-11-17 Exxon Research And Engineering Co. Method for reducing piston deposits
US20030148899A1 (en) * 1999-04-08 2003-08-07 Toshiaki Kuribayashi Lubricant oil composition for diesel engines (LAW964)
US20030111398A1 (en) * 2001-05-30 2003-06-19 Derek Eilers Additive dispensing cartridge for an oil filter, and oil filter incorporating same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8022021B2 (en) 2007-02-05 2011-09-20 The Lubrizol Corporation Low ash controlled release gels
WO2008112998A1 (fr) 2007-03-15 2008-09-18 Honeywell International Inc. Procédé de régénération d'un dispersant huileux de graissage
EP2121883A4 (fr) * 2007-03-15 2011-05-04 Honeywell Int Inc Procédé de régénération d'un dispersant huileux de graissage
US8691096B2 (en) 2008-02-01 2014-04-08 Lutek, Llc Oil filters containing strong base and methods of their use

Also Published As

Publication number Publication date
GB0428309D0 (en) 2005-01-26
GB2421511B (en) 2008-01-02
GB2421511A (en) 2006-06-28

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