WO1996026996A1 - Composition d'huiles lubrifiantes - Google Patents

Composition d'huiles lubrifiantes Download PDF

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Publication number
WO1996026996A1
WO1996026996A1 PCT/GB1996/000365 GB9600365W WO9626996A1 WO 1996026996 A1 WO1996026996 A1 WO 1996026996A1 GB 9600365 W GB9600365 W GB 9600365W WO 9626996 A1 WO9626996 A1 WO 9626996A1
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WIPO (PCT)
Prior art keywords
lubricating oil
composition
demulsifier
oil composition
oil
Prior art date
Application number
PCT/GB1996/000365
Other languages
English (en)
Inventor
Stephen James Cook
Paul Kristian Robinson
Original Assignee
Bp Chemicals (Additives) Limited
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Publication date
Application filed by Bp Chemicals (Additives) Limited filed Critical Bp Chemicals (Additives) Limited
Publication of WO1996026996A1 publication Critical patent/WO1996026996A1/fr

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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms 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
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    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel 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
    • 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
    • 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
    • F02B75/00—Other engines
    • F02B75/02—Engines characterised by their cycles, e.g. six-stroke
    • F02B2075/022—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle
    • F02B2075/027—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle four
    • 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 demulsifier for water-in-oil emulsions.
  • 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 demulsifier for water-in-oil emulsions.
  • 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 from 0J 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.
  • 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.
  • 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 0J 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 demulsifier there may be used one or more of the following compounds. - (i) alkyl phenoxypo!y(ethylenoxy)ethyl mono- and diesters of phosphoric acid, (ii) the reaction products of various organic amines, carboxylic acid amides, and quaternary ammonium salts with an alkylene oxide, eg ethylene oxide, (iii) alkylene oxide, eg ethylene oxide, condensation products of an N-alkyl alkylene diamine, (iv) alkylene oxide, eg ethylene oxide, condensation products of primary fatty amines, and
  • Preferred demulsifiers comprise polyoxyalkylene polyols and derivatives thereof, for example esters thereof obtained by reacting the polyols with various carboxylic acids, for example lauric acid, stearic acid, succinic acid and alkyl or alkenyl, for example polyisobutene-substituted succinic acids.
  • Preferred polyols are prepared as block copolymers.
  • a hydroxy-substituted compound, R-(OH) n (where n is 1 to 6, and R is the residue of a mono- or polyhydric alcohol, phenol, naphthol, etc) may be reacted with propylene oxide to form a hydrophobic base.
  • R-(OH) n examples include alkylene polyols, such as the alkylene glycols, alkylene triols, alkylene tetrols etc, such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and the like.
  • Aromatic hydroxy compounds such as alkylated mono- and polyhydric phenols and naphthols can also be used.
  • a useful class of demulsifier are glycols of the formula:-
  • a commercially available demulsifier which generally comprise a demulsifier package.
  • a commercially available demulsifier may comprise for example:
  • R mixed alkyl
  • m an integer
  • OA mixed alkylene oxides
  • component (2) may be either supplemented with, or replaced by, a fatty acid ester of a polyalkanolamine, eg polyethanolamine.
  • a fatty acid ester of a polyalkanolamine eg polyethanolamine.
  • a particularly suitable commercially available demulsifier is Tolad (RTM)
  • the demulsifier may be present in the composition in an amount from 0.001 to 0.5%, preferably from 0.01 to 0.3% by weight based on the weight of the composition.
  • the 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-3J00,673; US-A-3,219,666; US-A- 3J 72,892 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.
  • a preferred composition according to the present invention comprises from 0J to 5.0%, preferably from 0.10% to 3.0% of a hydrocarbyl-substituted succinimide dispersant, in which from 2 to 10%, preferably from 4 to 8%, of the dispersant is replaced by demulsifier and, comprising the remainder of the composition, a low- or medium-speed diesel engine lubricating oil.
  • 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.
  • the composition of the invention may be prepared by diluting a concentrate comprising a solution of the demulsifier 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 demulsifier which is compatible both with the lubricating oil and with the use of the composition.
  • the carrier may be any inert hydrocarbon solvent.
  • the demulsifier may suitably be present in the concentrate in an amount in the range from 0.1 to 20% by weight, typically from 0.1 to 10% by weight.
  • the use of a demulsifier for water-in-oil emulsions as described hereinabove for reducing black paint in low- or medium- speed diesel engines is a futher embodiment of the present invention.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Cette invention concerne une composition d'huile lubrifiante convenant à l'utilisation dans les moteurs Diesel de vitesse faible ou moyenne, et particulièrement adaptée à un moteur à quatre temps à piston fourreau, ladite composition comportant un mazout présentant une certaine teneur en résidu de distillation et se caractérisant en ce que la composition d'huile lubrifiante comporte également une quantité de désémulsionneur pour émulsion eau-dans-l'huile, par exemple un polyoxyalkylène polyol, permettant de réduire la 'peinture noire' et de préférence un additif dispersant, par exemple un succinimide à substitution hydrocarbyle. Cette invention concerne également un procédé permettant de réduire la peinture noire dans un moteur Diesel de vitesse faible ou moyenne.
PCT/GB1996/000365 1995-02-28 1996-02-15 Composition d'huiles lubrifiantes WO1996026996A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9503994.7 1995-02-28
GBGB9503994.7A GB9503994D0 (en) 1995-02-28 1995-02-28 Lubricating oil compositons

Publications (1)

Publication Number Publication Date
WO1996026996A1 true WO1996026996A1 (fr) 1996-09-06

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ID=10770386

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Country Status (2)

Country Link
GB (1) GB9503994D0 (fr)
WO (1) WO1996026996A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057163A1 (fr) * 2000-02-07 2001-08-09 Bp Oil International Limited Utilisations et procedes mettant en oeuvre des condensats
WO2008128656A2 (fr) 2007-04-24 2008-10-30 Infineum International Limited Détergent
EP2123740A1 (fr) 2008-05-20 2009-11-25 Infineum International Limited Lubrification de moteur marin
EP2123739A1 (fr) 2008-05-20 2009-11-25 Infineum International Limited Lubrification de moteur marin
DE102009034983A1 (de) 2008-09-11 2010-04-29 Infineum International Ltd., Abingdon Verfahren zum Vermindern von Asphaltenablagerung in einem Motor
DE102009034984A1 (de) 2008-09-11 2010-07-01 Infineum International Ltd., Abingdon Detergens
WO2010115594A1 (fr) 2009-04-07 2010-10-14 Infineum International Limited Lubrification de moteur marin
CN104087386A (zh) * 2014-07-14 2014-10-08 广西大学 一种乳化柴油发动机油组合物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1186659A (en) * 1967-09-20 1970-04-02 Lubrizol Corp Improved Lubricating Composition
US4129508A (en) * 1977-10-13 1978-12-12 The Lubrizol Corporation Demulsifier additive compositions for lubricants and fuels and concentrates containing the same
EP0098717A1 (fr) * 1982-06-24 1984-01-18 Nippon Mining Company Limited Huile lubrifiante pour moteurs diesel
JPS61166892A (ja) * 1984-12-14 1986-07-28 Nippon Oil Co Ltd 舶用デイ−ゼルエンジン用潤滑油組成物
EP0391649A2 (fr) * 1989-04-03 1990-10-10 Exxon Chemical Patents Inc. Compositions lubrifiantes sans cendres pour moteurs à combustion interne
WO1992013933A1 (fr) * 1991-01-31 1992-08-20 Exxon Chemical Patents Inc. Desemulsion des huiles
WO1995008608A1 (fr) * 1993-09-23 1995-03-30 Bp Chemicals (Additives) Limited Compositions d'huiles lubrifiantes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1186659A (en) * 1967-09-20 1970-04-02 Lubrizol Corp Improved Lubricating Composition
US4129508A (en) * 1977-10-13 1978-12-12 The Lubrizol Corporation Demulsifier additive compositions for lubricants and fuels and concentrates containing the same
EP0098717A1 (fr) * 1982-06-24 1984-01-18 Nippon Mining Company Limited Huile lubrifiante pour moteurs diesel
JPS61166892A (ja) * 1984-12-14 1986-07-28 Nippon Oil Co Ltd 舶用デイ−ゼルエンジン用潤滑油組成物
EP0391649A2 (fr) * 1989-04-03 1990-10-10 Exxon Chemical Patents Inc. Compositions lubrifiantes sans cendres pour moteurs à combustion interne
WO1992013933A1 (fr) * 1991-01-31 1992-08-20 Exxon Chemical Patents Inc. Desemulsion des huiles
WO1995008608A1 (fr) * 1993-09-23 1995-03-30 Bp Chemicals (Additives) Limited Compositions d'huiles lubrifiantes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8636, Derwent World Patents Index; AN 86-236361, XP002003749 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057163A1 (fr) * 2000-02-07 2001-08-09 Bp Oil International Limited Utilisations et procedes mettant en oeuvre des condensats
WO2008128656A2 (fr) 2007-04-24 2008-10-30 Infineum International Limited Détergent
EP2123740A1 (fr) 2008-05-20 2009-11-25 Infineum International Limited Lubrification de moteur marin
EP2123739A1 (fr) 2008-05-20 2009-11-25 Infineum International Limited Lubrification de moteur marin
DE102009034983A1 (de) 2008-09-11 2010-04-29 Infineum International Ltd., Abingdon Verfahren zum Vermindern von Asphaltenablagerung in einem Motor
DE102009034984A1 (de) 2008-09-11 2010-07-01 Infineum International Ltd., Abingdon Detergens
WO2010115594A1 (fr) 2009-04-07 2010-10-14 Infineum International Limited Lubrification de moteur marin
CN104087386A (zh) * 2014-07-14 2014-10-08 广西大学 一种乳化柴油发动机油组合物

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