EP1085076B1 - Eine Methode zum Schmieren für Zweitakt-Schiffsdieselmotoren - Google Patents

Eine Methode zum Schmieren für Zweitakt-Schiffsdieselmotoren Download PDF

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EP1085076B1
EP1085076B1 EP00202994A EP00202994A EP1085076B1 EP 1085076 B1 EP1085076 B1 EP 1085076B1 EP 00202994 A EP00202994 A EP 00202994A EP 00202994 A EP00202994 A EP 00202994A EP 1085076 B1 EP1085076 B1 EP 1085076B1
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Prior art keywords
oil
mass
lubricant
cylinder
acids
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French (fr)
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EP1085076A1 (de
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Charles Herbert Bovington
Terence Garner
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives 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
    • 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
    • C10M137/105—Thio derivatives not containing metal
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • 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
    • 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
    • C10M2219/08—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
    • C10M2219/088—Neutral 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
    • 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
    • C10M2219/089—Overbased 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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

Definitions

  • This invention relates to the lubrication of the cylinder or cylinders of a cross-head marine diesel (compression-ignited) engine for raising the temperature of the onset of scuffing-type mechanical wear of the cylinder walls of the engine during its operation.
  • One type of marine diesel propulsion engine is characterised as a slow speed, two-stroke engine which is frequently referred to as a cross-head engine because of its construction.
  • the firing cylinder and crankcase are lubricated separately by cylinder and system oils respectively.
  • the cylinder oil sometimes referred to as a marine diesel cylinder lubricant (MDCL)
  • MDCL marine diesel cylinder lubricant
  • WO 99/35218 discloses the use of a sulfur-containing borate ester or a diaryldithiophosphate derivative as an ashless anti-wear additive at 250°C.
  • EP 369 804A discloses the use of the following anti-wear additives at 200°C: tritolylphosphate, triphenylphosphorothionate and trixylylphosphate.
  • the present invention ameliorates the above problem, as evidenced by test results described in this specification, by lubricating the cylinder with an MDCL that includes a specific auxiliary additive.
  • the invention is method of lubricating a cylinder of a two-stroke cross-head marine diesel engine which comprises supplying to the walls of the cylinder, a cylinder lubricant comprising, or made by admixing,
  • a second aspect of the invention is a method of raising the temperature of the onset of scuffing-type mechanical wear of the walls of a cylinder of a two-stroke cross-head marine diesel engine by lubricating the walls with the cylinder lubricant as defined above.
  • the engines of this invention may, for example, have from 6 to 12 cylinders and their engine speed may, for example, be in the range of from 40 to 200, preferably 60 to 120, rpm. Their total output may, for example, be in the range of 18,000 to 70,000 kW.
  • the lubricant may, for example have a TBN of 15 or greater, preferably, 40 or greater, for example in the range of from 60 to 100.
  • the viscosity index of the lubricant is at least 80, such as at least 90, for example at least 100.
  • the lubricant may, for example, have a kinematic viscosity at 100°C (as measured by ASTM D445) of at least 14, preferably at least 15, more preferably in the range from 17 to 30, for example from 17 to 25, mm 2 s -1 .
  • the base stock is an oil of lubricating viscosity (sometimes referred to as base oil) and may be any oil suitable for the lubrication of a cross-head engine.
  • the lubricating oil may suitably be an animal, 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 tri-decyl 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 that 60, typically greater than 70%, by mass of the lubricant and 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 from 80 to 100, for example from 90 to 95.
  • Hydrocracked oils Another class of lubricating oil 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 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.
  • 'brightstock' refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C from 28 to 36 mm 2 s -1 and are typically used in a proportion of less that 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 lubricant.
  • Overbased metal compounds suitable for use in the lubricant of the present invention include alkali metal and alkaline earth metal additives such as overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salts of a surfactant selected from phenol, sulfonic acid, carboxylic acid, salicylic acid and naphthenic acid, wherein the overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilised by the oil-soluble salt of the surfactant.
  • the metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt.
  • the metal, whether the metal of the oil-soluble or oil-insoluble salt is calcium.
  • the TBN of one or each of the overbased metal compounds is at least 250, such as up to 500.
  • Surfactants for the surfactant system of the overbased metal compounds preferably 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 impart the desired oil-solubility.
  • Phenols for use in this invention, may be non-sulfurized or, preferably, sulfurized.
  • phenol as used herein includes phenols containing more than one hydroxyl group (for example, alkyl catechols) or fused aromatic rings (for example, alkyl naphthols) and phenols which have been modified by chemical reaction, for example, alkylene-bridged phenols and Mannich base-condensed phenols; and saligenin-type phenols (produced by the reaction of a phenol and an aldehyde under basic conditions).
  • Preferred phenols may be derived from the formula where R represents a hydrocarbyl group and y represents 1 to 4. Where y is greater than 1, the hydrocarbyl groups may be the same or different.
  • Sulfurized hydrocarbyl phenols may typically be represented by the formula: where x is generally from 1 to 4. In some cases, more than two phenol molecules may be linked by S x bridges.
  • hydrocarbyl groups represented by R are advantageously alkyl groups, which advantageously contain 5 to 100, preferably 5 to 40, especially 9 to 12, carbon atoms, the average number of carbon atoms in all of the R groups being at least 9 in order to ensure adequate solubility in oil.
  • Preferred alkyl groups are nonyl (tripropylene) groups.
  • hydrocarbyl-substituted phenols will for convenience be referred to as alkyl phenols.
  • a sulfurizing agent for use in preparing a sulfurized phenol or phenate may be any compound or element which introduces -(S) x - bridging groups between the alkyl phenol monomer groups, wherein x is generally from 1 to about 4.
  • the reaction may be conducted with elemental sulfur or a halide thereof, for example, sulfur dichloride or, more preferably, sulfur monochloride. If elemental sulfur is used, the sulfurization reaction may be effected by heating the alkyl phenol compound at from 50 to 250, preferably at least 100, °C. The use of elemental sulfur will typically yield a mixture of bridging groups -(S)x- as described above.
  • the sulfurization reaction may be effected by treating the alkyl phenol at from -10 to 120, preferably at least 60, °C.
  • the reaction may be conducted in the presence of a suitable diluent.
  • the diluent advantageously comprises a substantially inert organic diluent, for example mineral oil or an alkane.
  • the reaction is conducted for a period of time sufficient to effect substantial reaction. It is generally preferred to employ from 0.1 to 5 moles of the alkyl phenol material per equivalent of sulphurizing agent.
  • sulfurizing agent it may be desirable to use a basic catalyst, for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • a basic catalyst for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • sulfurized alkyl phenols useful in preparing overbased metal compounds generally comprise diluent and unreacted alkyl phenols and generally contain from 2 to 20, preferably 4 to 14, and most preferably 6 to 12, mass % sulfur based on the mass of the sulfurized alkyl phenol.
  • phenol as used herein includes phenols which have been modified by chemical reaction with, for example, an aldehyde, and Mannich base-condensed phenols.
  • Aldehydes with which phenols may be modified include, for example, formaldehyde, propionaldehyde and butyraldehyde.
  • the preferred aldehyde is formaldehyde.
  • Aldehyde-modified phenols suitable for use are described in, for example, US-A-5 259 967 .
  • Mannich base-condensed phenols are prepared by the reaction of a phenol, an aldehyde and an amine. Examples of suitable Mannich base-condensed phenols are described in GB-A-2 121 432 .
  • the phenols may include substituents other than those mentioned above provided that such substituents do not detract significantly from the surfactant properties of the phenols.
  • substituents are methoxy groups and halogen atoms.
  • Salicylic acids used in accordance with the invention may be non-sulfurized or sulfurized, and may be chemically modified and/or contain additional substituents, for example, as discussed above for phenols. Processes similar to those described above may also be used for sulfurizing a hydrocarbyl-substituted salicylic acid, and 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 overbased detergents in accordance with the invention may be derived are the substituents represented by R in the above discussion of phenols.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms.
  • Sulfonic acids used in accordance with the invention are typically obtained by sulfonation of hydrocarbyl-substituted, especially alkyl-substituted, aromatic hydrocarbons, for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • alkyl-substituted aromatic hydrocarbons for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives for example, chlorobenzene, chlorotoluene or chloronaphthalene.
  • Alkylation of aromatic hydrocarbons may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 100 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, and polyolefins, for example, polymers of ethylene, propylene, and/or butene.
  • alkylaryl sulphonic acids usually contain from 7 to 100 or more carbon atoms. They preferably contain from 16 to 80, or 12 to 40, carbon atoms per alkyl-substituted aromatic moiety, depending on the source from which they are obtained.
  • hydrocarbon solvents and/or diluent oils may also be included in the reaction mixture, as well as promoters and viscosity control agents.
  • Such sulfonic acids can be sulfurized. Whether sulfurized or non-sulfurized these sulfonic acids are believed to have surfactant properties comparable to those of sulfonic acids, rather than surfactant properties comparable to those of phenols.
  • Sulfonic acids suitable for use in accordance with the invention also include alkyl sulfonic acids, such as alkenyl sulfonic acids.
  • alkyl group suitably contains 9 to 100, advantageously 12 to 80, especially 16 to 60, carbon atoms.
  • Carboxylic acids which may be used in accordance with the invention include mono- and dicarboxylic acids.
  • Preferred monocarboxylic acids are those containing 1 to 30, especially 8 to 24, carbon atoms. (Where this specification indicates the number of carbon atoms in a carboxylic acid, the carbon atom(s) in the carboxylic group(s) is/are included in that number.)
  • Examples of monocarboxylic acids are iso-octanoic acid, stearic acid, oleic acid, palmitic acid and behenic acid. Iso-octanoic acid may, if desired, be used in the form of the mixture of C 8 acid isomers sold by Exxon Chemicals under the trade name "Cekanoic".
  • Suitable acids are those with tertiary substitution at the ⁇ -carbon atom and dicarboxylic acids with more than 2 carbon atoms separating the carboxylic groups. Further, dicarboxylic acids with more than 35, for example, 36 to 100, carbon atoms are also suitable. Unsaturated carboxylic acids can be sulphurized. Although salicylic acids contain a carboxylic group, for the purposes of the present invention they are considered to be a separate group of surfactants, and are not considered to be carboxylic acid surfactants. (Nor, although they contain a hydroxyl group, are they considered to be phenol surfactants.)
  • naphthenic acids especially naphthenic acids containing one or more alkyl groups
  • dialkylphosphonic acids dialkylthiophosphonic acids
  • dialkyldithiophosphoric acids dialkyldithiophosphoric acids
  • high molecular weight (preferably ethoxylated) alcohols preferably ethoxylated) alcohols
  • dithiocarbamic acids thiophosphines
  • dispersants of these types are well known to those skilled in the art.
  • detergents useful in the present invention are optionally sulfurized alkaline earth metal hydrocarbyl phenates that have been modified by carboxylic acids such as stearic acid, for examples as described in EP-A- 271 262 (LZ-Adibis); and phenolates as described in EP-A- 750 659 (Chevron).
  • overbased metal compounds preferably overbased calcium detergents, that contain at least two surfactant groups, such as phenol, sulfonic acid, carboxylic acid, salicylic acid and naphthenic acid, that may be obtained by manufacture of a hybrid material in which two or more different surfactant groups are incorporated during the overbasing process.
  • surfactant groups such as phenol, sulfonic acid, carboxylic acid, salicylic acid and naphthenic acid
  • hybrid materials are an overbased calcium salt of surfactants phenol and sulfonic acid; an overbased calcium salt of surfactants phenol and carboxylic acid; an overbased calcium salt of surfactants phenol, sulfonic acid and salicylic acid; and an overbased calcium salt of surfactants phenol and salicylic acid.
  • an “overbased calcium salt of surfactants” is meant an overbased detergent in which the metal cations of the oil-insoluble metal salt are essentially calcium cations. Small amounts of other cations may be present in the oil-insoluble metal salt, but typically at least 80, more typically at least 90, for example at least 95, mole %, of the cations in the oil-insoluble metal salt, are calcium ions. Cations other than calcium may be derived, for example, from the use in the manufacture of the overbased detergent of a surfactant salt in which the cation is a metal other than calcium.
  • the metal salt of the surfactant is also calcium.
  • the TBN of the overbased calcium detergent is at least 330, such as at least 350, more preferably at least 400, most preferably in the range of from 400 to 600, such as up to 500.
  • any suitable proportions by mass may be used, preferably the mass to mass proportion of any one overbased metal compound to any other metal overbased compound is in the range of from 5:95 to 95:5; such as from 90:10 to 10:90; more preferably from 20:80 to 80:20; especially from 70:30 to 30:70; advantageously from 60:40 to 40:60.
  • hybrid materials include, for example, those described in WO-A-97/46643 ; WO-A- 97/46644 ; WO-A- 97/46645 ; WO-A- 97/46646 ; and WO-A- 97/46647 .
  • the amount of overbased metal compound in the lubricant is at least 0.5, particularly in the range of from 0.5 to 20, such as from 3 to 12 or 2 to 7, mass % based on active ingredient per mass of lubricant.
  • the overbased metal compounds of the present invention may be borated, and typically the boron contributing compound, e.g the metal borate, is considered to form part of the overbasing.
  • the use of a borated dispersant and/or an oil-soluble or oil-dispersible boron compound may, or may not, be necessary provided the lubricant composition comprising the borated overbased metal compound has a viscosity index and TBN as defined herein.
  • non-borated dispersants are not excluded in the present invention in combination with a borated overbased metal compound.
  • such components are preferably "ashless” by which is meant that it is a non-metallic organic material that forms substantially no ash on combustion, in contrast to metal-containing and hence, ash forming compounds.
  • the auxiliary additive component (C), which is different from (B), comprises:
  • sulfurized alkylphenols such as those described above in connection with the preparation of overbased metal detergents for example present in the lubricant is an amount of at least 2, for example up to 8, 10, 15 or 20 mass %, and amine dithiophosphates, for example present in the lubricant in an amount of up to 10, such as in the range of 0.4 to 5, or 0.6 to 2, mass % .
  • the lubricants may include an antiwear agent as a co-additive and may also contain other co-additives, for example, antioxidants, antifoaming agents and/or rust inhibitors. Further details of particular co-additives are as follows.
  • Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service, evidence of such deterioration being, for example, the production of varnish-like deposits on metal surfaces and of sludge, and viscosity increase.
  • Suitable oxidation inhibitors include sulphurized alkyl phenols and alkali or alkaline earth metal salts thereof; diphenylamines; phenyl-naphthylamines; and phosphosulphurized or sulphurized hydrocarbons.
  • oxidation inhibitors or antioxidants which may be used in the lubricant comprise oil-soluble copper compounds.
  • the copper may be blended therein as any suitable oil-soluble copper compound.
  • oil-soluble is meant that the compound is oil-soluble under normal blending conditions in the base stock or an additive package.
  • the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid, for example, a C8 to C18 fatty acid, an unsaturated acid, or a branched carboxylic acid.
  • oil-soluble copper dithiocarbamates, sulphonates, phenates, and acetylacetonates are basic, neutral or acidic copper Cu I and/or Cu II salts derived from alkenyl succinic acids or anhydrides.
  • Additional detergents and metal rust inhibitors include the metal salts, which may be overbased and have a TBN less than 300, of sulphonic acids, alkyl phenols, sulphurized alkyl phenols, alkyl salicylic acids, thiophosphonic acids, naphthenic acids, and other oil-soluble mono- and dicarboxylic acids.
  • Representative examples of detergents/rust inhibitors, and their methods of preparation, are given in EP-A-208 560 .
  • the TBN of the metal salts may be less than 200.
  • Zinc dihydrocarbyl dithiophosphates are very widely used as antiwear agents.
  • ZDDPs are those of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 wherein R 1 and R 2 represent hydrocarbyl groups such as alkyl groups that contain from 1 to 18, preferably 2 to 12, carbon atoms.
  • Pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured. Such additives are well known.
  • Foam control may be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • Typical proportions for additives for an MDCL (a marine diesel cylinder lubricant), additional to additives (C) of this invention are as follows: Additive Mass Mass % a.i.* % a.i.* (Broad) (Preferred) Detergent(s) 1-40 2-27 (14-22 more preferred) Dispersant(s) 0-3 0-2 Anti-wear agent(s) 0-1,5 0-1.3 Anti-oxident 0-5 0-3 Pour point depressant 0-0.15 0-0.1 Mineral or synthetic base oil Balance Balance * Mass % active ingredient based on the final oil. Stabilisers and/or rust inhibitors may also be included.
  • additive package(s) When a plurality of additives is employed it may be desirable, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby several additives can be added simultaneously to the base stock to form the lubricant. Dissolution of the additive package(s) into the base stock 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 lubricant when the additive package(s) is/are combined with a predetermined amount of base stock.
  • components (B) and (C) in accordance with the present invention may be admixed with small amounts of base stock 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 and preferably from 5 to 75 and most preferably from 8 to 60, mass %, the remainder being base stock.
  • the final lubricant may typically contain about 5 to 40 mass % of the additive package(s), including diluent, the remainder being base stock.
  • a first sample of marine diesel cylinder lubricant was prepared by admixing with the basestock A 1 , the detergent B 1 and the stabiliser D 1 . This was a comparison sample and is designated as SAMPLE Z.
  • Second and third samples of a marine diesel cylinder lubricant were prepared by admixing with the basestock A 1 , the detergent B 1 and the stabiliser D 1 , in the same proportions as in SAMPLE Z, and also compound C 1 (3 mass % based on the lubricant mass) in the second sample and compound C 2 (0.8 mass % based on the lubricant mass) in the third sample.
  • the second and third samples are examples included in the invention and are designated as SAMPLES 1 and 2 respectively.
  • the admixing was carried out by blending the components and the basestock at 60°C for one hour.
  • HFRR High Frequency Reciprocating Rig
  • Sample Z the results are shown in Figure 1 , from which it is seen that the friction coefficient fell from about 0.16 at 75°C to about 0.1 at around 200°C, and fell, less steeply, to about 0.08 at around 280°C. Above 280°C, the coefficient arose steeply to about 0.25 or above and remained on or about 0.25 up to 350°C.
  • Sample 1 the results are shown in Figure 2 , from which it is seen that the friction coefficient remained on or about 0.15 from 75°C to 190°C and fell to about 0.1 at 200°C. It remained just above, or about, 0.1 from 200 to 325°C. The coefficient rose at 325 to 350°C, but not exceeding 0.15.
  • the neutralization of the acidic intermediate with the amine is in most instances exothermic and can be carried out simply by mixing the reactants at ordinary temperatures, preferably from 0°C to 200°C.
  • the chemical constitution of the neutralized product of the reaction depends to a large extent upon the temperature.
  • the product comprises predominantly a salt of the amine with the acid.
  • the product may contain amides, amidines, or mixtures thereof.
  • the reaction of the acidic intermediate with a tertiary amine results only in a salt.
  • the relative proportions of the acidic intermediate and the amines used in the reaction are preferably such that a substantial portion of the acidic intermediate is neutralized.
  • the lower limit as to the amount of amine used in the reaction is based primarily upon a considerable of the utility of the product formed. In most instances, enough amine should be used as to neutralize at least 50% of the acidity of the intermediate. For use as additives in hydrocarbon oils, substantially neutral products such as are obtained by neutralization of at least 90% of the acidity of the intermediate are desirable.
  • the amount of the amine used may vary within wide ranges depending upon the acidity desired in the product and also upon the acidity of the intermediate as determined by, for example, ASTM procedure designation D-664 or D-974.
  • a particularly preferred amine phosphate is when the acidic intermediate is derived from the reaction of P 2 O 5 with hydroxypropyl O,O-di(4-methyl-2-pentyl) phosphorodithioate. This acidic intermediate may then be neutralised or partially neutralised with a C 12 to C 14 tertiary aliphatic primary amine.
  • An example of such an amine may be commercially purchased under the trade name of Primene 81 R.
  • sulfurized alkylphenols such as those described above in connection with the preparation of overbased metal detergents for example present in the lubricant is an amount of at least 0.5, such as at least 1.5 or 2, for example up to 8, 10, 15 or 20 mass %, and amine dithiophosphates, for example present in the lubricant in an amount of at least 0.1, for example up to 10, such as in the range of 0.4 to 5, or 0.6 to 2, mass % .
  • the lubricants may include an antiwear agent as a co-additive and may also contain other co-additives, for example, antioxidants, antifoaming agents and/or rust inhibitors. Further details of particular co-additives are as follows.
  • Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service, evidence of such deterioration being, for example, the production of varnish-like deposits on metal surfaces and of sludge, and viscosity increase.
  • Suitable oxidation inhibitors include sulphurized alkyl phenols and alkali or alkaline earth metal salts thereof; diphenylamines; phenyl-naphthylamines; and phosphosulphurized or sulphurized hydrocarbons.
  • oxidation inhibitors or antioxidants which may be used in the lubricant comprise oil-soluble copper compounds.
  • the copper may be blended therein as any suitable oil-soluble copper compound.
  • oil-soluble is meant that the compound is oil-soluble under normal blending conditions in the base stock or an additive package.
  • the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid, for example, a C8 to C18 fatty acid, an unsaturated acid, or a branched carboxylic acid.
  • oil-soluble copper dithiocarbamates, sulphonates, phenates, and acetylacetonates are basic, neutral or acidic copper Cu I and/or Cu II salts derived from alkenyl succinic acids or anhydrides.
  • Additional detergents and metal rust inhibitors include the metal salts, which may be overbased and have a TBN less than 300, of sulphonic acids, alkyl phenols, sulphurized alkyl phenols, alkyl salicylic acids, thiophosphonic acids, naphthenic acids, and other oil-soluble mono- and dicarboxylic acids.
  • Representative examples of detergents/rust inhibitors, and their methods of preparation, are given in EP-A-208 560 .
  • the TBN of the metal salts may be less than 200.
  • Zinc dihydrocarbyl dithiophosphates are very widely used as antiwear agents.
  • ZDDPs are those of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 wherein R 1 and R 2 represent hydrocarbyl groups such as alkyl groups that contain from 1 to 18, preferably 2 to 12, carbon atoms.
  • Foam control may be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • Typical proportions for additives for an MDCL (a marine diesel cylinder lubricant), additional to additives (C) of this invention are as follows: Additive Mass Mass % a.i.* % a.i.* (Broad) (Preferred) Detergent(s) 1-40 2-27 (14-22 more preferred) Dispersant(s) 0-3 0-2 Anti-wear agent(s) 0-1.5 0-1.3 Anti-oxident 0-5 0-3 Pour point depressant 0-0.15 0-0.1 Mineral or synthetic base oil Balance Balance * Mass % active ingredient based on the final oil. Stabilisers and/or rust inhibitors may also be included.
  • additive package(s) When a plurality of additives is employed it may be desirable, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby several additives can be added simultaneously to the base stock to form the lubricant. Dissolution of the additive package(s) into the base stock 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 lubricant when the additive package(s) is/are combined with a predetermined amount of base stock.
  • components (B) and (C) in accordance with the present invention may be admixed with small amounts of base stock 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 and preferably from 5 to 75 and most preferably from 8 to 60, mass %, the remainder being base stock.
  • the final lubricant may typically contain about 5 to 40 mass % of the additive package(s), including diluent, the remainder being base stock.
  • FIG. 1 represents, as the results of an HFRR test to be described below, a trace in graphical form where the x-axis represents temperature in °C and the y-axis represents coefficient of friction.
  • a first sample of marine diesel cylinder lubricant was prepared by admixing with the basestock A 1 , the detergent B 1 and the stabiliser D 1 . This was a comparison sample and is designated as SAMPLE Z.
  • Second and third samples of a marine diesel cylinder lubricant were prepared by admixing with the basestock A 1 , the detergent B 1 and the stabiliser D 1 , in the same proportions as in SAMPLE Z, and also compound C 1 (3 mass % based on the lubricant mass) in the second sample and compound C 2 (0.8 mass % based on the lubricant mass) in the third sample.
  • the second and third samples are examples included in the invention and are designated as SAMPLES 1 and 2 respectively.
  • the admixing was carried out by blending the components and the basestock at 60°C for one hour.
  • HFRR High Frequency Reciprocating Rig
  • Sample Z the results are shown in Figure 1 , from which it is seen that the friction coefficient fell from about 0.16 at 75°C to about 0.1 at around 200°C, and fell, less steeply, to about 0.08 at around 280°C. Above 280°C, the coefficient arose steeply to about 0.25 or above and remained on or about 0.25 up to 350°C.
  • Sample 1 the results are shown in Figure 2 , from which it is seen that the friction coefficient remained on or about 0.15 from 75°C to 190°C and fell to about 0.1 at 200°C. It remained just above, or about, 0.1 from 200 to 325°C. The coefficient rose at 325 to 350°C, but not exceeding 0.15.

Claims (7)

  1. Verfahren zum Schmieren eines Zylinders eines Zweitakt-Kreuzkopfschiffsdieselmotors, bei dem die Wände des Zylinders mit einem Zylinderschmierstoff ausgestattet werden, der
    (A) Basismaterial mit Schmierviskosität in einer größeren Menge,
    (B) mindestens ein überbasisches Metalldetergens in einer geringeren Menge und
    (C) mindestens eine zusätzliche, vorzugsweise aschefreie oder nicht metallhaltige, Additivkomponente in einer geringeren Menge, die sich von (B) unterscheidet, die
    (C1) mindestens 1,5 Massen-% eines öllöslichen sulfurierten Alkylphenols und/oder
    (C2) mindestens 0,1 Massen-% eines öllöslichen Amindithiophosphats enthält,
    enthält oder durch Mischen davon hergestellt ist,
    wobei der Zylinder durch eine Leistungsabgabe von 4000 oder größer, wie 4200 oder größer, vorzugsweise 4500 oder größer, insbesondere im Bereich von 4500 bis 6000 kW gekennzeichnet ist.
  2. Verfahren nach Anspruch 1, bei dem der Zylinder ferner durch eine Bohrung von 850 oder größer, wie 900 oder größer, vorzugsweise im Bereich von 900 bis 1000 cm gekennzeichnet ist.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, bei dem das überbasische Metalldetergens ein Calciumsalicylat ist.
  4. Verfahren nach einem der Ansprüche 1 - 3, bei dem das sulfurierte Alkylphenol ein Alkylphenolsulfid ist.
  5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das sulfurierte Alkylphenol in dem Schmierstoff in einer Menge von mindestens 2, zum Beispiel bis zu 8, 10, 15 oder 20 Massen-% vorliegt.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Amindithiophosphat in dem Schmierstoff in einer Menge von bis zu 10, wie im Bereich von 0,4 bis 5, oder 0,6 bis 2 Massen-% vorliegt.
  7. Verfahren nach einem der vorhergehenden Ansprüche zum Erhöhen der Temperatur des Einsetzens von mechanischem Verschleiß vom Typ "Fressen" (Engl. : Scuffing) der Wände eines Zylinders eines Zweitakt-Kreuzkopfschiffsdieselmotors.
EP00202994A 1999-09-13 2000-08-18 Eine Methode zum Schmieren für Zweitakt-Schiffsdieselmotoren Expired - Lifetime EP1085076B1 (de)

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EP00202994A EP1085076B1 (de) 1999-09-13 2000-08-18 Eine Methode zum Schmieren für Zweitakt-Schiffsdieselmotoren

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EP99203006 1999-09-13
EP99203006 1999-09-13
EP00202994A EP1085076B1 (de) 1999-09-13 2000-08-18 Eine Methode zum Schmieren für Zweitakt-Schiffsdieselmotoren

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EP1085076B1 true EP1085076B1 (de) 2010-12-15

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7875577B2 (en) 2005-12-28 2011-01-25 Chevron Japan Ltd. Diesel engine lubricating oil composition for large-bore two-stroke cross-head diesel engines

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1262721A (en) 1985-07-11 1989-11-07 Jacob Emert Oil soluble dispersant additives useful in oleaginous compositions
GB8826961D0 (en) * 1988-11-18 1988-12-21 Castrol Ltd Lubricant compositions
GB9400417D0 (en) * 1994-01-11 1994-03-09 Bp Chemicals Additives Lubricating oil composition
SG55446A1 (en) * 1996-10-29 1998-12-21 Idemitsu Kosan Co Lube oil compositions for diesel engines
GB9800436D0 (en) * 1998-01-09 1998-03-04 Exxon Chemical Patents Inc Marine lubricant compositions

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