EP1195426B1 - Schmierölzusammensetzung für flüssiggasbetriebene Brennkraftmaschine - Google Patents

Schmierölzusammensetzung für flüssiggasbetriebene Brennkraftmaschine Download PDF

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Publication number
EP1195426B1
EP1195426B1 EP01203645A EP01203645A EP1195426B1 EP 1195426 B1 EP1195426 B1 EP 1195426B1 EP 01203645 A EP01203645 A EP 01203645A EP 01203645 A EP01203645 A EP 01203645A EP 1195426 B1 EP1195426 B1 EP 1195426B1
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EP
European Patent Office
Prior art keywords
composition
tbn
gas
lubricating oil
salicylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01203645A
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English (en)
French (fr)
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EP1195426A1 (de
Inventor
Mr. Terence Garner
Mr. Laurent Chambard
Mr. Adrian Dunn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Infineum International Ltd
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Infineum International Ltd
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Publication date
Priority claimed from EP00121752A external-priority patent/EP1195425A1/de
Application filed by Infineum International Ltd filed Critical Infineum International Ltd
Priority to EP01203645A priority Critical patent/EP1195426B1/de
Publication of EP1195426A1 publication Critical patent/EP1195426A1/de
Application granted granted Critical
Publication of EP1195426B1 publication Critical patent/EP1195426B1/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/14—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 hydroxy groups
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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    • 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
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104—Aromatic fractions
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
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    • 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
    • C10M2215/12—Partial amides of polycarboxylic acids
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    • C10M2215/122—Phtalamic acid
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    • 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
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    • C10M2215/26—Amines
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    • C10M2215/28—Amides; Imides
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
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    • C10M2219/089—Overbased salts
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • 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
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    • 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
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • This invention relates to gas-fuelled engine lubrication.
  • Gas-fuelled engines sometimes referred to as gas-fired engines or merely gas engines, are known and may be used in the oil and gas industry, for example, to drive pumping stations of natural gas pipelines, blowers and generators in purification plants and on gas tankers, to compress natural gas at well heads and along pipe lines and to produce electric power in fit-for-purpose plants.
  • Their design may be two- or four-stroke, spark-ignited or compression-ignited, though four-stroke compression-ignited designs constitute a large percentage.
  • Natural gas constitutes a typical fuel.
  • US-A-5 726 133 describes a way of meeting the above problems by using, in a natural gas engine oil, an additive mixture comprising a mixture of detergents comprising at least one first alkali or alkaline earth metal salt or mixture thereof of TBN of 250 and less, and at least one second alkali or alkaline earth metal salt or mixture thereof which is more neutral than the first salt.
  • EP-A-0 860 495 describes a lubricating oil composition stated to be excellent for NOx oxidation resistance and thermal oxidation resistance and suitable as a long-life engine oil for gas engine heat pumps.
  • the composition includes a metal salicylate having a TBN of from 100 to 195, and optionally includes a metal phenate having a TBN of from 100 to 300.
  • the present invention meets this desire, as evidenced by and in the examples hereof, by using, as a first detergent, a salicylate having a TBN of 95 or less and a second detergent having a TBN of greater than 250.
  • US 5,906,969 discloses lubricating oils for improving the fuel economy of internal combustion engines.
  • a first aspect of the present invention is a gas-fuelled engine lubricating oil composition having a TBN in the range of 2 to 20 comprising:
  • a second aspect of the present invention is a method of lubricating a gas-fuelled internal combustion engine, the method comprising operating the engine and lubricating it with the composition defined above according to the first aspect of the invention.
  • a third aspect of the present invention is a method for enhancing the resistance of a gas-fuelled lubricating oil composition to oxidation and nitration, the method comprising the step of adding additives (B) to (E) as defined in the first aspect of the invention to the gas-fuelled lubricating oil composition.
  • Major amount means in excess of 50 mass % of the composition.
  • Minor amount means less than 50 mass % of the composition, both in respect of the stated additive and in respect of the total mass % of all the additives present in composition, reckoned as active ingredient of the additive or additives.
  • TBN Total Base Number
  • the TBN of the lubricant composition is in the range of from 2 to 20, such as from 2.5 to 20, preferably from 6.5 to 20, more preferably from 6.5 to 15.
  • the oil of lubricating viscosity may be any oil suitable for the lubrication of a gas-fuelled engine.
  • the lubricating oil may suitably be an animal, a vegetable or a mineral oil.
  • the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil.
  • the lubricating oil may be a synthetic lubricating oil.
  • Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed.
  • the lubricating oil may generally comprise greater than 60, typically greater than 70, mass % of the composition, and typically have a kinematic viscosity at 100°C of from 2 to 40, for example for 3 to 15, mm 2 s -1 and a viscosity index of from 80 to 100, for example from 90 to 95.
  • hydrocracked oils Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures.
  • Hydrocracked oils typically have a kinematic viscosity at 100°C of from 2 to 40, for example from 3 to 15, mm 2 s -1 and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
  • the oil may include 'brightstock' which refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C of from 28 to 36 mm 2 s -1 and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5, mass %, based on the mass of the composition.
  • 'brightstock' refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C of from 28 to 36 mm 2 s -1 and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5, mass %, based on the mass of the composition.
  • a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants, which, in respect of (B), is salicylic acid.
  • the detergent comprises a polar head with a long hydrophobic tail, the polar head comprises a metal salt of the salicylic acid.
  • Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • the metal may be an alkali or alkaline earth metal, e.g., sodium, potassium, lithium, calcium, and magnesium. Calcium is preferred.
  • Surfactants for the surfactant system of the overbased metal detergents contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
  • hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impact the desired oil-solubility.
  • the salicylates may be non-sulfurized or sulfurized, and may be chemically modified and/or contain additional substitutents.
  • Processes for sulfurizing a hydrocarbyl-substituted salicylic acid are well known to those skilled in the art.
  • Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained, normally in a diluent, in admixture with uncarboxylated phenol.
  • Preferred substituents in oil-soluble salicylic acids from which the salicylates may be derived are alkyl substituents.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there are more than one alkyl groups, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil-solubility.
  • the gas-fuelled engine lubricating oil composition preferably includes only one metal hydrocarbyl-substituted salicylate detergent having a TBN of 95 or less, component (B).
  • the salicylate may be used in a proportion in the range of 0.5 to 30, preferably 2 to 15 or to 20, mass % based on the mass of the lubricating oil composition.
  • Component (C) is one or more calcium salicylate, phenate or complex detergents having a TBN of greater than 250.
  • Complex detergents comprise an overbased mixture of at least two calcium surfactants, such as a calcium alkyl phenate and a calcium alkyl salicylate.
  • a complex detergent is a hybrid material in which the surfactant groups, e.g. phenate and salicylate, are incorporated during the overbasing process. Examples of complex detergents are described in the art.
  • Another example of a detergent that may be used comprises a sulfurized and then overbased mixture of a calcium alkyl phenate and a calcium alkyl salicylate such as described in EP-A-750,659 , for example as:
  • the calcium detergents (C) have a TBN in the range of 250 to 500, more preferably 260 to 400.
  • a dispersant is an additive for a lubricating composition 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 lubricating oil, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Ashless dispersants 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.
  • ashless dispersants are succinimides, e.g. polyisobutene succinic anhydride; and polyamine condensation products that may be borated or unborated.
  • the antiwear additives may be metallic or non-metallic, preferably the former.
  • Dihydrocarbly dithiophosphate metal salts are examples of the anti-wear additives used in the present invention.
  • the metal in the dihydrocarbyl dithiophosphate metal may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.
  • Zinc salts are preferred, preferably in the range of 0.1 to 1.5, preferably 0.5 to 1.3, mass %, based upon the total mass of the lubricating oil composition.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary.
  • any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
  • the preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: [(RO) (R'O) P(S)S] 2 Zn where R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, I-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. in R and R 1 ) in the dithiophoshoric acid will generally be 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • composition of the present invention may, optionally, have further added there-to in a minor amount (F) one or more antioxidants as discussed in further detail below.
  • amines or phenolic may be amines or phenolic.
  • secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms.
  • anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
  • the anti-oxidant if present, is provided in the composition in an amount of up to 3 mass %.
  • additives such as pour point depressants, anti-foamants, and/or demulsifiers may be provided, if necessary.
  • additives (B) to (E), and (F) if provided can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
  • additives (B) to (E), and (F) if provided, in accordance with the present invention may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in the appropriate proportions, the remainder being base oil.
  • the final formulations may typically contain about 5 to 40 mass % of the additive packages(s), the remainder being base oil.
  • 'active ingredient' refers to the additive material that is not diluent.
  • 'oil-soluble' or 'oil-dispersable' do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • the lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
  • Gas-fuelled engine lubricating oil compositions of the invention were prepared by blending methods known in the art. Their compositions were as follows: COMPONENTS Example 1 Example 2 (B) Ca salicylate, TBN 65 3.46 3.85 (C) Ca salicylate, TBN 281 0.35 0.39 (D) Borated succinimide dispersant 3.41 3.80 Unborated succinimide dispersant 2.58 2.88 (E) ZDDP anti-wear additive 0.26 0.29 (F) Diphenylamine anti-oxidant 0.35 0.39 (A) Base Oil Balance Balance TBN 7.1 8 Ash (sulfated) (%) 0.45 0.50 (Antifoams were also present)
  • Example A As comparison gas-fuelled engine lubricating oil compositions (Examples A and B), there were used commercially available lubricating oils, the detergency of each of which was phenate-based and was salicylate-free.
  • Example A had a TBN of 5.2 and 0.45% sulfated ash and Example B had a TBN of 8.8 and 0.80% sulfated ash.

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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)
  • Lubricants (AREA)

Claims (8)

  1. Schmierölzusammensetzung für einen gasbetriebenen Motor mit einer TBN im Bereich von 2 bis 20, die:
    (A) in einer größeren Menge Öl von Schmierviskosität und dazu hinzugefügt jeweils in kleineren Mengen:
    (B) ein oder mehrere mit Kohlenwasserstoffrest substituierte Metallsalicylatdetergenzien mit einer TBN von 95 oder weniger,
    (C) ein oder mehrere Calciumsalicylat-, Phenat- oder Komplexdetergenzien mit einer TBN von größer als 250,
    (D) ein oder mehrere Dispergiermittel, wie ein aschefreies Dispergiermittel, und
    (E) vorzugsweise ein oder mehrere Antiverschleißadditive umfasst.
  2. Zusammensetzung nach Anspruch 1, der ferner in einer kleineren Menge als (F) ein oder mehrere Antioxidanzien, wie Amin oder phenolische Antioxidanzien, zugesetzt sind.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, wobei das Metall des mit Kohlenwasserstoffrest substituierten Salicylats (B) Calcium ist.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei das Calciumdetergens (C) ein mit Kohlenwasserstoffrest substituiertes Calciumsalicylat oder ein Calciumkomplexdetergens ist, das ein Salicylattensid mit einer TBN im Bereich von 250 bis 500, vorzugsweise 260 bis 400 enthält.
  5. Zusammensetzung nach einem der Ansprüche 2 bis 4, wobei das Antioxidanz (F) in der Zusammensetzung in einer Menge von bis zu 3 Masse-% vorliegt.
  6. Verfahren zum Schmieren eines mit Gas betriebenen Verbrennungsmotors, bei dem der Motor betrieben wird und er mit einer Zusammensetzung gemäß einem der Ansprüche 1 bis 5 geschmiert wird.
  7. Verfahren zur Erhöhung der Widerstandsfähigkeit einer Schmierölzusammensetzung für einen mit Gas betriebenen Motor gegenüber Oxidation und Nitrierung, bei dem die Zusammensetzung mit den Additiven (B) bis (F) wie in einem der Ansprüche 1 bis 5 definiert zu der Schmierölzusammensetzung für den mit Gas betriebenen Motor gegeben wird.
  8. Additivpaket oder -konzentrat für eine Schmierölzusammensetzung für einen mit Gas betriebenen Motor, das:
    (B) ein oder mehrere mit Kohlenwasserstoffrest substituierte Metallsalicylatdetergenzien mit einer TBN von 95 oder weniger,
    (C) ein oder mehrere Calciumsalicylat-, Phenat- oder Komplexdetergenzien mit einer TBN von größer als 250,
    (D) ein oder mehrere Dispergiermittel, wie ein aschefreies Dispergiermittel, und
    (E) vorzugsweise ein oder mehrere Antiverschleißadditive umfasst.
EP01203645A 2000-10-05 2001-09-24 Schmierölzusammensetzung für flüssiggasbetriebene Brennkraftmaschine Expired - Lifetime EP1195426B1 (de)

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EP00121752A EP1195425A1 (de) 2000-10-05 2000-10-05 Schmierölzusammensetzung für flüssiggasbetriebene Brennkraftmaschine
EP00121752 2000-10-05
EP01203645A EP1195426B1 (de) 2000-10-05 2001-09-24 Schmierölzusammensetzung für flüssiggasbetriebene Brennkraftmaschine

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EP1195426B1 true EP1195426B1 (de) 2007-08-15

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US20030191032A1 (en) * 2002-01-31 2003-10-09 Deckman Douglas E. Mixed TBN detergents and lubricating oil compositions containing such detergents
US7772169B2 (en) 2002-05-24 2010-08-10 The Lubrizol Corporation Low ash stationary gas engine lubricant
US20050070447A1 (en) * 2003-09-25 2005-03-31 The Lubrizol Corporation Ashless stationary gas engine lubricant
US20070105729A1 (en) * 2005-11-09 2007-05-10 Chip Hewette Gear additive composition
US8299003B2 (en) 2005-11-09 2012-10-30 Afton Chemical Corporation Composition comprising a sulfur-containing, phosphorus-containing compound, and/or its salt, and uses thereof
US20070142660A1 (en) 2005-11-09 2007-06-21 Degonia David J Salt of a sulfur-containing, phosphorus-containing compound, and methods thereof
US8680030B2 (en) 2005-11-18 2014-03-25 Exxonmobil Research And Engineering Company Enhanced deposit control for lubricating oils used under sustained high load conditions employing glycerine derivative with a grafted hindered phenolic and/or a hindered phenolic containing a thioether group
WO2010086365A1 (en) * 2009-01-28 2010-08-05 Shell Internationale Research Maatschappij B.V. Lubricating composition
US20130157910A1 (en) * 2011-12-16 2013-06-20 Chevron Oronite Company Llc Diesel engine oils

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JP3613530B2 (ja) * 1993-05-27 2005-01-26 東燃ゼネラル石油株式会社 潤滑油組成物
GB9400417D0 (en) * 1994-01-11 1994-03-09 Bp Chemicals Additives Lubricating oil composition
US5726133A (en) * 1996-02-27 1998-03-10 Exxon Research And Engineering Company Low ash natural gas engine oil and additive system
GB9611428D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
EP0963429B1 (de) * 1997-11-28 2012-03-07 Infineum USA L.P. Schmierölzusammensetzungen
US5906969A (en) * 1998-05-01 1999-05-25 Exxon Research And Engineering Company High fuel economy passenger car engine oil

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