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WO1996026995A1 - Lubricating oil compositions - Google Patents

Lubricating oil compositions Download PDF

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Publication number
WO1996026995A1
WO1996026995A1 PCT/GB1996/000364 GB9600364W WO9626995A1 WO 1996026995 A1 WO1996026995 A1 WO 1996026995A1 GB 9600364 W GB9600364 W GB 9600364W WO 9626995 A1 WO9626995 A1 WO 9626995A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricating oil
hydrocarbyl
composition
substituted
weight
Prior art date
Application number
PCT/GB1996/000364
Other languages
French (fr)
Inventor
Stephen James Cook
Paul Kristian Robinson
Original Assignee
Bp Chemicals (Additives) Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bp Chemicals (Additives) Limited filed Critical Bp Chemicals (Additives) Limited
Publication of WO1996026995A1 publication Critical patent/WO1996026995A1/en

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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
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02—Natural products
    • C10M159/04—Petroleum fractions, e.g. tars, solvents
    • 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
    • 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
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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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104—Aromatic fractions
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
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    • 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
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/028—Overbased salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
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    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
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    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
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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
    • C10M2215/26—Amines
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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
    • 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
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/046—Overbased sulfonic 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
    • C10M2219/089—Overbased salts
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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
    • C10N2040/252—Diesel 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
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
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    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to lubricating oil compositions and in particular to lubricating oil compositions suitable for medium- or low-speed diesel engines, typically the four-stroke trunk-piston engine.
  • Lubricating oils for medium- or low-speed diesel engines are known and will typically contain a range of additives which will perform a variety of functions, for example they may comprise dispersants to minimise deposit formation in various parts of the engine, or detergent additives.
  • contamination of these lubricating oil compositions with unburnt residual fuel oil is a problem recognised in the industry. This leads to severe engine cleanliness problems in service which is sometimes referred to as "black paint”.
  • the problem is particularly widespread in 4-stroke trunk-piston engines where dirty cam boxes and crankcases are encountered.
  • 2- stroke cross-head engines can also suffer from the problem. These 2-stroke engines will usually use two separate lubricating oils, one for the crankcase and one for the cylinder, but it is in the crankcase where the heavy deposits potentially occur.
  • a lubricating oil composition suitable for use in low or medium speed diesel engines comprising a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a "black paint" reducing amount of a hydrocarbyl- substituted phenol.
  • the lubricating oil composition of the present invention will be suitable for use in either a low- or medium-speed engine especially a marine diesel engine.
  • a low- or medium-speed engine especially a marine diesel engine.
  • a marine diesel engine can be a 4-stroke trunk piston engine having an engine speed of 50-1,000 rpm, e.g. 100-500 rpm, and a brake horse-power (BHP) per cylinder of 10-3,000 preferably 250-2,000.
  • BHP brake horse-power
  • the engine can also be a 2-stroke cross-head engine having a speed of 40-1,000 rpm preferably 100-500 rpm, and a BHP per cylinder of 100-8,000.
  • a method of reducing deposits in a low- or medium-speed diesel engine comprising lubricating the moving parts of the engine with a lubricating oil composition suitable for use in such an engine which comprises a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a "black paint" reducing amount of a hydrocarbyl-substituted phenol.
  • the lubricating oil compositions of the present invention will have a TBN in the range 0.1 to lOOmgKOH g.
  • the TBN is preferably in the range 5-70, more preferably 8-50mgKOH/g; where it is to be used in a 2-stroke cross-head engine and particularly for the crankcase, the TBN of the composition is preferably in the range 0.1 to 15, more preferably 1 to 10 mgKOH/g.
  • the lubricating oil composition of the present invention will usually be a monograde lubricant, i.e. one which exhibits little or no viscosity index improvement properties, e.g. an SA30 oil.
  • the lubricating oil may be any oil suitable for the lubrication of a low- or medium-speed diesel engine, particularly a marine diesel 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, paraffin 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 oil may be suitable for lubricating a low- or medium-speed marine diesel engine without adjustment of its viscosity. If viscosity adjustment is required it may be achieved by the addition of, for example, bright stock.
  • the lubricating oil will generally comprise greater than 70% by weight, typically greater than 80% by weight of the composition.
  • the lubricating oil composition will be contaminated with a fuel oil which has a residual oil content.
  • a fuel oil will be suitable for use as a diesel fuel oil.
  • Fuel oils can in general be divided into two main categories - distillates and heavy fuels. Distillates consist of one or more distilled fractions. Heavy fuels are fuels which comprise at least a proportion of a residual oil, that is an oil which remains after the distilled fractions have been removed from an unrefined oil.
  • the composition of the residual oil will vary with the composition of the starting oil which is usually a crude oil and will also vary depending upon the distillation conditions. However, by its nature residual oil is of high molecular weight and high boiling point and the man skilled in the art will know what is meant by residual oil.
  • Heavy fuels can also comprise, in addition to residual oil, distillates. However, heavy fuels will generally comprise at least 90%, for example at least 95%, typically at least 99% by weight residual oil.
  • the present invention is concerned with lubricating oil compositions that are contaminated with a heavy fuel.
  • the amount of heavy fuel in the lubricating oil composition will vary. Typically the composition will comprise between 0.1 to 10, e.g. 0.3 to 5, especially 0.5 to 3%, by weight heavy fuel oil which as defined above is a fuel oil which has a residual oil content.
  • the hydrocarbyl-substituted phenol may be a mono-hydrocarbyl-substituted phenol or a poly-hydrocarbyl-substituted phenol or a mixture of both mono- and poly-substituted phenols.
  • the hydrocarbyl-substituent is preferably an alkyl group which may be branched or unbranched. Suitable alkyl groups contain from 4 to 50, preferably from 9 to 29, carbon atoms.
  • a particularly suitable alkyl phenol is the predominantly Ci2-.alkyl phenol obtained by alkylating phenol with propylene tetramer.
  • a particularly suitable poly-substituted phenol is dinonyl phenol.
  • Hydrocarbyl-substituted phenols are well-known commercial materials which are usually manufactured by alkylating phenol at elevated temperature in the presence of an acidic catalyst.
  • composition of the invention may contain other additives, chief amongst which is a dispersant.
  • a suitable dispersant is one derived from a hydrocarbyl-substituted succinic acid or anhydride by reaction with an amine, i.e. a hydrocarbyl-substituted succinimide, e.g. a polyisobutene (PIB) succinimide.
  • a hydrocarbyl-substituted succinimide e.g. a polyisobutene (PIB) succinimide.
  • PIB polyisobutene
  • Succinimide production is described in, for example, US-A-2,992,708; US- A-3,018,291; US-A-3,024,237; US-A-3, 100,673; US-A-3,219,666; US-A- 3,172,892 and US-A-3, 272,746.
  • Succinimide dispersants which are mono- or bis- succinimides may be employed.
  • the amount of dispersant present in the low- or medium-speed diesel engine lubricating oil composition of the present invention may suitably be in the range from 0.01 to 5.0, preferably from 0.1 to 2.5% by weight based on the weight of the composition.
  • compositions may additionally contain additives conventionally employed in low- or medium-speed diesel engine lubricating oil compositions.
  • additives include detergents, foam inhibitors, extreme pressure/antiwear agents, rust inhibitors, antioxidants, and the like.
  • Detergents generally employed in the compositions of the invention include hydrocarbyl-substituted alkaline earth metal phenates, salicylates, naphthenates, sulphonates or carboxylates, which may be normal or overbased materials.
  • the detergent in addition to providing detergency, is generally employed to adjust the total base number of the composition to a desired value, typically about 30mg KOH/g.
  • a preferred composition according to the present invention comprises from 0 to 5.0%, preferably from 0.10 to 3.0%, by weight of a hydrocarbyl-substituted succinimide dispersant; sufficient of a hydrocarbyl-substituted alkaline earth metal phenate, salicylate, naphthenate, sulphonate or carboxylate detergent to adjust the TBN to a value in the range from 8 to 50mgKOH/g for use in a 4-stroke trunk piston engine or to a value in the range from 1 to lOmgKOH/g for use in a 2-stroke cross-head marine engine; from 0.5 to 10%, preferably from 2.0 to 5.0% by weight of a hydrocarbyl-substituted phenol; from 0.1 to 10%, typically from 0.5 to 3% by weight heavy fuel oil (i.e. a fuel oil which has a residual oil content); and, comprising the remainder of the composition, a low- or medium-speed diesel engine lubricating oil.
  • the composition of the invention may be prepared by diluting a concentrate comprising a solution of the hydrocarbyl-substituted phenol and optionally the other additives referred to hereinbefore in a suitable carrier with low- or medium- speed diesel engine lubricating oil.
  • a suitable carrier with low- or medium- speed diesel engine lubricating oil.
  • the carrier there may be employed any solvent for the phenol which is compatible both with the lubricating oil and with the use of the composition.
  • the carrier may be any inert hydrocarbon solvent.
  • the hydrocarbyl-substituted phenol may suitably be present in the concentrate in an amount in the range from 0.1 to 20% by weight.
  • test method ten grams of the test oil which has previously been subjected to ageing at 100°C for 24hr is filtered through a filter medium. After solvent washing and drying the total sediment on the filter medium is weighed. The test is carried out in duplicate. Results
  • Ml Mass of filter medium after filtration in g
  • M2 Mass of filter medium before filtration in g
  • M3 Mass of sample filtered in g.
  • the Comparison Test was repeated except that in addition 0.66% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer was added.
  • the Comparison Test was repeated except that in addition 1.48% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer (as used in Example 1) was added.
  • the Comparison Test was repeated except that in addition 2.54% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer (as used in Example 1) was added.
  • the Comparison Test was repeated except that in addition 3.95% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer (as used in Example 1 ) was added.

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Abstract

A lubricating oil composition suitable for use in low- or medium-speed diesel engines, especially a four-stroke trunk-piston engine, comprises a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a 'black paint' reducing amount of a hydrocarbyl-substituted phenol, and desirably a dispersant, e.g. a hydrocarbyl-substituted succinimide. Also a method of reducing black paint in a low- or medium-speed diesel engine.

Description

LUBRICATING OIL COMPOSITIONS
The present invention relates to lubricating oil compositions and in particular to lubricating oil compositions suitable for medium- or low-speed diesel engines, typically the four-stroke trunk-piston engine.
Lubricating oils for medium- or low-speed diesel engines are known and will typically contain a range of additives which will perform a variety of functions, for example they may comprise dispersants to minimise deposit formation in various parts of the engine, or detergent additives. However contamination of these lubricating oil compositions with unburnt residual fuel oil is a problem recognised in the industry. This leads to severe engine cleanliness problems in service which is sometimes referred to as "black paint". The problem is particularly widespread in 4-stroke trunk-piston engines where dirty cam boxes and crankcases are encountered. However, the problem is not confined to 4-stroke engines. 2- stroke cross-head engines can also suffer from the problem. These 2-stroke engines will usually use two separate lubricating oils, one for the crankcase and one for the cylinder, but it is in the crankcase where the heavy deposits potentially occur.
It might be expected that the problem would be overcome simply by using more of the conventional dispersant additive in the lubricating oil but this measure has met with very limited success. We have now found that the aforementioned problem is solved by including in the lubricating oil compositions a hydrocarbyl- substituted phenol.
Thus according to the present invention there is provided a lubricating oil composition suitable for use in low or medium speed diesel engines comprising a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a "black paint" reducing amount of a hydrocarbyl- substituted phenol.
The lubricating oil composition of the present invention will be suitable for use in either a low- or medium-speed engine especially a marine diesel engine. Typically such an engine can be a 4-stroke trunk piston engine having an engine speed of 50-1,000 rpm, e.g. 100-500 rpm, and a brake horse-power (BHP) per cylinder of 10-3,000 preferably 250-2,000. The engine can also be a 2-stroke cross-head engine having a speed of 40-1,000 rpm preferably 100-500 rpm, and a BHP per cylinder of 100-8,000.
In a further aspect of the present invention there is provided a method of reducing deposits in a low- or medium-speed diesel engine comprising lubricating the moving parts of the engine with a lubricating oil composition suitable for use in such an engine which comprises a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a "black paint" reducing amount of a hydrocarbyl-substituted phenol. The lubricating oil compositions of the present invention will have a TBN in the range 0.1 to lOOmgKOH g. Where the composition is to be used in a 4- stroke trunk piston engine the TBN is preferably in the range 5-70, more preferably 8-50mgKOH/g; where it is to be used in a 2-stroke cross-head engine and particularly for the crankcase, the TBN of the composition is preferably in the range 0.1 to 15, more preferably 1 to 10 mgKOH/g.
The lubricating oil composition of the present invention will usually be a monograde lubricant, i.e. one which exhibits little or no viscosity index improvement properties, e.g. an SA30 oil.
As regards the lubricating oil, this may be any oil suitable for the lubrication of a low- or medium-speed diesel engine, particularly a marine diesel engine. The lubricating oil may suitably be an animal, a vegetable or a mineral oil. Suitably the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffin base, or mixed base oil. Alternatively, 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 oil may be suitable for lubricating a low- or medium-speed marine diesel engine without adjustment of its viscosity. If viscosity adjustment is required it may be achieved by the addition of, for example, bright stock. The lubricating oil will generally comprise greater than 70% by weight, typically greater than 80% by weight of the composition.
The lubricating oil composition will be contaminated with a fuel oil which has a residual oil content. Such a fuel oil will be suitable for use as a diesel fuel oil. Fuel oils can in general be divided into two main categories - distillates and heavy fuels. Distillates consist of one or more distilled fractions. Heavy fuels are fuels which comprise at least a proportion of a residual oil, that is an oil which remains after the distilled fractions have been removed from an unrefined oil. The composition of the residual oil will vary with the composition of the starting oil which is usually a crude oil and will also vary depending upon the distillation conditions. However, by its nature residual oil is of high molecular weight and high boiling point and the man skilled in the art will know what is meant by residual oil. Heavy fuels can also comprise, in addition to residual oil, distillates. However, heavy fuels will generally comprise at least 90%, for example at least 95%, typically at least 99% by weight residual oil. The present invention is concerned with lubricating oil compositions that are contaminated with a heavy fuel. The amount of heavy fuel in the lubricating oil composition will vary. Typically the composition will comprise between 0.1 to 10, e.g. 0.3 to 5, especially 0.5 to 3%, by weight heavy fuel oil which as defined above is a fuel oil which has a residual oil content.
The hydrocarbyl-substituted phenol may be a mono-hydrocarbyl-substituted phenol or a poly-hydrocarbyl-substituted phenol or a mixture of both mono- and poly-substituted phenols. The hydrocarbyl-substituent is preferably an alkyl group which may be branched or unbranched. Suitable alkyl groups contain from 4 to 50, preferably from 9 to 29, carbon atoms. A particularly suitable alkyl phenol is the predominantly Ci2-.alkyl phenol obtained by alkylating phenol with propylene tetramer. A particularly suitable poly-substituted phenol is dinonyl phenol.
Hydrocarbyl-substituted phenols are well-known commercial materials which are usually manufactured by alkylating phenol at elevated temperature in the presence of an acidic catalyst.
In addition to the lubricating oil and the hydrocarbyl-substituted phenol the composition of the invention may contain other additives, chief amongst which is a dispersant.
Although any type of dispersant may be employed in the composition, a suitable dispersant is one derived from a hydrocarbyl-substituted succinic acid or anhydride by reaction with an amine, i.e. a hydrocarbyl-substituted succinimide, e.g. a polyisobutene (PIB) succinimide. Such succinimides are well known in the art.
Succinimide production is described in, for example, US-A-2,992,708; US- A-3,018,291; US-A-3,024,237; US-A-3, 100,673; US-A-3,219,666; US-A- 3,172,892 and US-A-3, 272,746.
Succinimide dispersants which are mono- or bis- succinimides may be employed.
The amount of dispersant present in the low- or medium-speed diesel engine lubricating oil composition of the present invention may suitably be in the range from 0.01 to 5.0, preferably from 0.1 to 2.5% by weight based on the weight of the composition.
In addition to the foregoing the composition may additionally contain additives conventionally employed in low- or medium-speed diesel engine lubricating oil compositions. Examples of such additives include detergents, foam inhibitors, extreme pressure/antiwear agents, rust inhibitors, antioxidants, and the like. Detergents generally employed in the compositions of the invention include hydrocarbyl-substituted alkaline earth metal phenates, salicylates, naphthenates, sulphonates or carboxylates, which may be normal or overbased materials. The detergent, in addition to providing detergency, is generally employed to adjust the total base number of the composition to a desired value, typically about 30mg KOH/g.
A preferred composition according to the present invention comprises from 0 to 5.0%, preferably from 0.10 to 3.0%, by weight of a hydrocarbyl-substituted succinimide dispersant; sufficient of a hydrocarbyl-substituted alkaline earth metal phenate, salicylate, naphthenate, sulphonate or carboxylate detergent to adjust the TBN to a value in the range from 8 to 50mgKOH/g for use in a 4-stroke trunk piston engine or to a value in the range from 1 to lOmgKOH/g for use in a 2-stroke cross-head marine engine; from 0.5 to 10%, preferably from 2.0 to 5.0% by weight of a hydrocarbyl-substituted phenol; from 0.1 to 10%, typically from 0.5 to 3% by weight heavy fuel oil (i.e. a fuel oil which has a residual oil content); and, comprising the remainder of the composition, a low- or medium-speed diesel engine lubricating oil.
The composition of the invention may be prepared by diluting a concentrate comprising a solution of the hydrocarbyl-substituted phenol and optionally the other additives referred to hereinbefore in a suitable carrier with low- or medium- speed diesel engine lubricating oil. As the carrier there may be employed any solvent for the phenol which is compatible both with the lubricating oil and with the use of the composition. The carrier may be any inert hydrocarbon solvent. The hydrocarbyl-substituted phenol may suitably be present in the concentrate in an amount in the range from 0.1 to 20% by weight.
The use of a hydrocarbyl-substituted phenol as described hereinabove for reducing black paint in low- or medium- speed diesel engines is a further embodiment of the present invention. The invention will now be further illustrated by reference to the following
Examples. In the Examples the total sediment content of residual fuel contaminated compounded oils is determined.
In the test method, ten grams of the test oil which has previously been subjected to ageing at 100°C for 24hr is filtered through a filter medium. After solvent washing and drying the total sediment on the filter medium is weighed. The test is carried out in duplicate. Results
The mass percentage of Total Sediment to the nearest 0.01% m/m is calculated using:- S = M1 - M2 x l00
M3 where S = Total Sediment in % m/m
Ml = Mass of filter medium after filtration in g M2 = Mass of filter medium before filtration in g M3 = Mass of sample filtered in g.
In the following Comparison Test and Examples all percentages are percentages by weight. Comparison Test
A fully formulated 30TBN trunk piston engine oil lubricant at SAE40 containing a hydrocarbyl-substituted calcium phenate detergent (ex. Adibis) (X) and 20% residual fuel was tested in the Adibis Test Method for "black paint".
The result of the Test is given in the accompanying Table. Example 1
The Comparison Test was repeated except that in addition 0.66% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer was added.
The result of the Test is given in accompanying Table. Example 2
The Comparison Test was repeated except that in addition 1.48% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer (as used in Example 1) was added.
The result of the Test is given in the accompanying Table. Example 3
The Comparison Test was repeated except that in addition 2.54% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer (as used in Example 1) was added.
The result of the Test is given in the accompanying Table. Example 4
The Comparison Test was repeated except that in addition 3.95% by weight of the alkyl phenol product obtained by alkylating phenol with propylene tetramer (as used in Example 1 ) was added.
The result of the Test is given in the accompanying Table.
TABLE
Figure imgf000008_0001
It can be seen from the Table that addition of alkyl phenol leads to a marked reduction in sediment.

Claims

Claims:
1. A lubricating oil composition suitable for use in low- or medium-speed diesel engines comprising a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a "black paint" reducing amount of a hydrocarbyl-substituted phenol.
2. A lubricating oil composition as claimed in claim 1 for use in a 4-stroke piston engine wherein the TBN of the composition is in the range 5 to 70 mg KOH/g.
3. A lubricating oil composition as claimed in claim 1 for use in a 2-stroke cross-head engine wherein the TBN of the composition is in the range 0.1 to 15 mg KOH/g.
4. A lubricating oil composition as claimed in any one of the preceding claims wherein the composition comprises between 0.5 to 3% by weight of the fuel oil with a residual oil content.
5. A lubricating oil composition as claimed in any one of the preceding claims wherein the hydrocarbyl substituent of the hydrocarbyl-substituted phenol is an alkyl group containing from 4 to 50 carbon atoms.
6. A lubricating oil composition as claimed in any one of the preceding claims wherein the alkyl phenol is the predominantly Ci2_al phenol obtained by alkylating phenol with propylene tertramer.
7. A lubricating oil composition as claimed in any one of the preceding claims containing a dispersant which is a hydrocarbyl-substituted succinimide. 8 A lubricating oil composition as claimed in claim 1 which comprises from 0 to 5.0% by weight of a hydrocarbyl-substituted succinimide; sufficient of a hydrocarbyl-substituted alkaline earth metal phenate, salicylate, naphthenate, sulphonate or carboxylate detergent to adjust the TBN to a value in the range from
8 to 50 mg KOH/g; from 0.5 to 10% by weight of a hydrocarbyl-substituted phenol; from 0.1 to 10% by weight of the fuel oil with a residual oil content; and, comprising the remainder of the composition, a low- or medium-speed diesel engine lubricating oil.
9. A lubricating oil composition as claimed in claim 1 which comprises from 0 to 5.0% by weight of a hydrocarbyl-substituted succinimide dispersant; sufficient of a hydrocarbyl-substituted alkaline earth metal phenate, salicylate, naphthenate, sulphonate or carboxylate detergent to adjust the TBN to a value in the range from 1 to 10 mg KOH/g; from 0.5 to 10% by weight of a hydrocarbyl-substituted phenol; from 0.1 to 10% by weight of the fuel oil with a residual oil content; and, comprising the remainder of the composition, a low- or medium-speed diesel engine lubricating oil.
10. A method of reducing black paint in a low- or medium-speed diesel engine comprising lubricating the moving parts of the engine with a lubricating oil composition suitable for use in such an engine which comprises a fuel oil with a residual oil content characterised in that the lubricating oil composition further comprises a "black paint" reducing amount of a hydrocarbyl-substituted phenol.
11. The use of a hydrocarbyl-substituted phenol for reducing black paint in low- or medium- speed diesel engines.
PCT/GB1996/000364 1995-02-28 1996-02-15 Lubricating oil compositions WO1996026995A1 (en)

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JP2005133098A (en) * 2003-10-30 2005-05-26 Infineum Internatl Ltd Method for reducing deposit formation in centrifuge system in trunk piston diesel engine
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