EP1051467A1 - Marine lubricant for two-stroke engine - Google Patents
Marine lubricant for two-stroke engineInfo
- Publication number
- EP1051467A1 EP1051467A1 EP99901656A EP99901656A EP1051467A1 EP 1051467 A1 EP1051467 A1 EP 1051467A1 EP 99901656 A EP99901656 A EP 99901656A EP 99901656 A EP99901656 A EP 99901656A EP 1051467 A1 EP1051467 A1 EP 1051467A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant
- weight
- koh
- group
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- 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
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- 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
- the present invention relates to a marine lubricant for a two-stroke engine with improved neutralization properties with respect to sulfuric acid formed during the combustion of fuels, in particular fuels, said to be high in sulfur content, that is to say greater than 1% by weight. It relates more particularly to a lubricant having a neutralizing power of sulfuric acid improved compared to that of marine lubricants on the market.
- the cylinder oils on the one hand, ensuring the lubrication of the piston-cylinder assembly, and the system oils on the other hand, ensuring the lubrication of all the moving parts outside the piston-cylinder assembly.
- the Applicant has noticed that the BN is not representative of the neutralization phenomenon itself even, as it takes place at the level of the oil film ensuring lubrication in the piston-cylinder assembly.
- oils are non-polar hydrocarbons
- the acid products of the combustion of fuels of polar nature and therefore hardly soluble in hydrocarbons, diffuse in oils.
- This diffusion phenomenon varies according to various factors such as the oil flow, the engine rotation speed and the wettability of the metal surface. All these factors are important as well as the BN to predict corrosive wear by sulfuric acid.
- two factors can be controlled by the lubricant manufacturers, BN and the wettability on the metal wall, which both depend on the chemical composition of the additives in the lubricating oil.
- the present invention relates to a lubricant having a sufficient basicity and a rapidity of neutralization of the sulfuric acid formed sufficient to prevent the corrosive wear phenomena observed in the 2-stroke, slow, buttered engine cylinders.
- the subject of the present invention is therefore a lubricant for a 2-stroke, slow-stick, stock engine, supplied by a fuel with a sulfur content greater than or equal to 1%, consisting of a mixture of distillates used as lubricant bases containing x% by weight of succinimide dispersing additive, y% by weight of overbased detergent additive of sulfonate type, and z% by weight of overbased detergent additive of phenate type characterized in that x, y and z are chosen in the intervals 0.5 ⁇ x ⁇ 2.5, 3.5 ⁇ y ⁇ 10 and ll ⁇ z ⁇ 24.5 such that 15 ⁇ x + y + z ⁇ 36 and 1.5 ⁇ y / x ⁇ 13, that the BN of the lubricant, determined according to standard ASTM D-2896, is greater than or equal to 70 mg of KOH / g, and that the rate of neutralization by the sulfuric acid lubricant, defined by the maximum speed of pressure increase in a closed enclosure,
- the Applicant has found that in order to promote the increase in the speed of neutralization, the said lubricant must necessarily contain a sufficient quantity of a mixture of at least one overbased detergent of sulfonate type with at least one dispersant. succinimide type to avoid corrosion by sulfuric acid, and that this mixture was synergistic.
- the Applicant has made a particular selection of a mixture of additives to obtain a lubricant capable of rapidly neutralizing any acid invasion of the film formed inside the cylinder part of the engine where acid corrosion is generally observed.
- the mass ratio y / x, overbased detergent of sulfonate type / dispersant of succinimide type preferably varies from 1.5 to 5.
- the overbased detergents of the preferred sulfonate type are chosen from the group consisting of neutral and basic, alkaline and alkaline-earth metal salts of petroleum sulfonic acids and long chain BN alkylarylsulfonic acids determined by the standard. ASTM D-2896 varying from 300 to 500 mg KOH / g.
- these sulfonate compounds are alkaline earth metal alkylarylsulfonates, and preferably calcium mono and dialkylarylsulfonates, each alkyl group comprising from 12 to 18 carbon atoms, the aryl group being a benzyl, a tolyl or a xylenyl.
- overbased detergents of the sulfonate type are effective with regard to the neutralization of sulfuric acid in the film of lubricant when taken in combination with at least one dispersant of the succinimide type, this dispersant being chosen from the group consisting of derivatives succinimides from the group comprising polyalkenylsuccinimide borates in which the succinic acid or anhydride is derived from a polymer of a C 3 or C 4 olefin, preferably polyisobutylene with an average molecular weight of between 1000 and 3000, this acid or anhydride having reacted with a polyalkylpolyamine from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and their mixture, and in which for each polyalkenyl group corresponds to 1 to 2 succinimide groups.
- this dispersant being chosen from the group consisting of derivatives succinimides from the group comprising polyalkenylsuccinimide borates
- the lubricant contains an overbased detergent of the calcium phenate type, of BN determined by standard ASTM D-2896 varying from 50 to 400 mg of KOH / g, chosen from the group consisting of alkali and alkaline earth metal phenates of alkylphenols and alkylmercaptophenols, alkyl groups, linear or branched, comprising from 4 to 50 carbon atoms, preferably from 9 to 15 carbon atoms, taken alone or mixed.
- the alkyl group comprising from 9 to 15 carbon atoms of BN varying from 200 to 400 mg of KOH / g and from 0 to 5% by weight of a calcium alkylmercaptophenate of BN less than 150 mg of KOH / g, the alkyl group comprising from 9 to 15 carbon atoms.
- the said lubricant for marine engine will advantageously contain x% by weight of polyisobutylenesuccinimide, comprising a group polyisobutylene for 1.1 to 1.8 succinimide groups, y% by weight of BN calcium sulfonate of between 300 and 500 mg of KOH / g, z% by weight of a mixture of calcium alkylmercaptophenates and 64 to 85% by weight of a mixture of hydrocarbons consisting of lubricating mineral bases with a density at 15 ° C varying from 850 to 950 Kg / m, known to those skilled in the art.
- the lubricant according to the invention may also contain from 0 to 1% of other additives, in particular an anti-foam additive.
- the purpose of this example is to describe the method used to measure the speed of neutralization of a lubricant.
- This method uses the device represented in FIG. 1.
- This consists of a cylindrical glass container (1), heated by a thermostated oil bath (2), into which the sample of lubricating composition is introduced. test, by a motor (3) allowing the cylindrical container (1) to rotate around its axis of revolution, and by two magnetic bars, one outside (4) and the other (5) inside said container ( 1), so as to form a film 100 ⁇ m thick on the glass wall (6).
- the cylindrical glass container (1) is connected at one of its planar ends to a tube (7) provided with a septum allowing the introduction of acid with a syringe, and to the other end of an expansion vessel (8) fitted with a pressure sensor (9) enabling pressure variations to be monitored inside the cylindrical container / expansion vessel (l) / (8) assembly during the entire period of introduction of the acid and even during neutralization.
- a recorder (10) is connected to said sensor (9) on which the pressure variations in the cylindrical container / expansion vessel (l) / (8) assembly are followed.
- Figure 2 shows a record of the pressure change for the test described.
- the curve includes three phases, phase 1 of initiation of the reaction, phase 2 of neutralization whose slope allows us to calculate the speed of neutralization and phase 3 of stabilization of the pressure in the cylindrical container (1).
- the present example aims to show the influence of the chemical composition of the lubricant or of its BN on the neutralization rate as measured according to the method and with the device described in previous example I.
- the lubricant samples are prepared with a mineral base obtained by mixing at least one distillate 1 with a density at 15 ° C. of between 880 and
- Table I groups together the respective neutralization rates of the BN lubricant samples equal to either 40 mg of KOH / g, or to 80 mg of KOH / g, the sulfonate / dispersant mass ratio of which is varied for a constant content. as calcium phenates of BN 250 and BN 100 in the lubricant.
- Table II groups together the respective neutralization rates of the lubricant samples whose sulfonate / dispersant mass ratio remains constantly equal to 4.46, and for which the BN is varied from 40 at 100 mg KOH / g, that is to say by varying the dilution rate of the additives in the mixture of distillates.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Lubrication Of Internal Combustion Engines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9801127A FR2774387B1 (en) | 1998-02-02 | 1998-02-02 | MARINE LUBRICANT FOR TWO-STROKE ENGINE |
FR9801127 | 1998-02-02 | ||
PCT/FR1999/000181 WO1999038940A1 (en) | 1998-02-02 | 1999-01-29 | Marine lubricant for two-stroke engine |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1051467A1 true EP1051467A1 (en) | 2000-11-15 |
EP1051467B1 EP1051467B1 (en) | 2002-08-28 |
Family
ID=9522440
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99901656A Revoked EP1051467B1 (en) | 1998-02-02 | 1999-01-29 | Marine lubricant for two-stroke engine |
Country Status (12)
Country | Link |
---|---|
US (1) | US6528459B1 (en) |
EP (1) | EP1051467B1 (en) |
JP (1) | JP2002501974A (en) |
KR (1) | KR100655004B1 (en) |
AT (1) | ATE222943T1 (en) |
CA (1) | CA2320332A1 (en) |
DE (1) | DE69902631T2 (en) |
DK (1) | DK1051467T3 (en) |
ES (1) | ES2179614T3 (en) |
FR (1) | FR2774387B1 (en) |
PT (1) | PT1051467E (en) |
WO (1) | WO1999038940A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE491775T1 (en) * | 1999-09-13 | 2011-01-15 | Infineum Int Ltd | A METHOD OF LUBRICATION FOR TWO-STROKE MARINE DIESEL ENGINES |
JP4011815B2 (en) * | 2000-02-14 | 2007-11-21 | シェブロンジャパン株式会社 | Lubricating oil composition for two-cycle crosshead diesel internal combustion engine and additive composition for lubricating oil composition |
EP1471130A1 (en) * | 2003-04-23 | 2004-10-27 | Ethyl Petroleum Additives Ltd | Fuel composition containing molybdenum source and metal-containing detergent, and its use in two-stroke engines |
US20110143977A1 (en) * | 2004-05-14 | 2011-06-16 | Cook Stephen J | Lubricating Compositions Containing Sulphonates and Phenates |
WO2006041810A1 (en) * | 2004-10-06 | 2006-04-20 | The Lubrizol Corporation | Lubricating compositions containing sulphonates |
EP1903093B1 (en) | 2006-09-19 | 2017-12-20 | Infineum International Limited | A lubricating oil composition |
EP1914295B1 (en) * | 2006-10-11 | 2013-12-04 | Total Marketing Services | Marine lubricant for a low or high sulfur content fuel |
JP2010523733A (en) * | 2007-03-30 | 2010-07-15 | ビーピー ピー・エル・シー・ | Lubrication method |
FR2932813B1 (en) * | 2008-06-18 | 2010-09-03 | Total France | LUBRICANT CYLINDER FOR MARINE ENGINE TWO TIMES |
SG11201401057TA (en) | 2011-09-30 | 2014-11-27 | Jx Nippon Oil & Energy Corp | Cylinder lubricating oil composition for crosshead diesel engine |
EP2719751B1 (en) * | 2012-06-07 | 2021-03-31 | Infineum International Limited | Marine engine lubrication |
US20140360451A1 (en) * | 2013-06-06 | 2014-12-11 | James C. Dodd | Marine Engine Lubrication |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4420407A (en) * | 1981-10-22 | 1983-12-13 | Texaco Inc. | Method of lubricating upper cylinder of marine diesel engine |
US4375418A (en) * | 1981-10-28 | 1983-03-01 | Texaco Inc. | Lubricating oil composition |
GB8602627D0 (en) * | 1986-02-04 | 1986-03-12 | Exxon Chemical Patents Inc | Marine lubricating composition |
GB8804171D0 (en) * | 1988-02-23 | 1988-03-23 | Exxon Chemical Patents Inc | Dispersant for marine diesel cylinder lubricant |
US5320763A (en) * | 1993-03-12 | 1994-06-14 | Chevron Research And Technology Company | Low viscosity group II metal overbased sulfurized C10 to C16 alkylphenate compositions |
CA2184159A1 (en) * | 1994-12-28 | 1996-07-04 | William F. King | Overbased alkyl oxy benzene sulfonates as detergents |
US6140280A (en) * | 1996-10-29 | 2000-10-31 | Idemitsu Kosan Co., Ltd. | Succinimide compound and method for producing it, lubricating oil additive comprising the compound and lubricating oil composition comprising the compound for diesel engine |
SG55446A1 (en) * | 1996-10-29 | 1998-12-21 | Idemitsu Kosan Co | Lube oil compositions for diesel engines |
US6339051B1 (en) * | 1998-06-11 | 2002-01-15 | Mobil Oil Corporation | Diesel engine cylinder oils |
-
1998
- 1998-02-02 FR FR9801127A patent/FR2774387B1/en not_active Expired - Lifetime
-
1999
- 1999-01-29 WO PCT/FR1999/000181 patent/WO1999038940A1/en not_active Application Discontinuation
- 1999-01-29 PT PT99901656T patent/PT1051467E/en unknown
- 1999-01-29 JP JP2000529402A patent/JP2002501974A/en active Pending
- 1999-01-29 DE DE69902631T patent/DE69902631T2/en not_active Revoked
- 1999-01-29 ES ES99901656T patent/ES2179614T3/en not_active Expired - Lifetime
- 1999-01-29 AT AT99901656T patent/ATE222943T1/en not_active IP Right Cessation
- 1999-01-29 US US09/600,158 patent/US6528459B1/en not_active Expired - Lifetime
- 1999-01-29 EP EP99901656A patent/EP1051467B1/en not_active Revoked
- 1999-01-29 DK DK99901656T patent/DK1051467T3/en active
- 1999-01-29 CA CA002320332A patent/CA2320332A1/en not_active Abandoned
- 1999-01-29 KR KR1020007008403A patent/KR100655004B1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO9938940A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1051467B1 (en) | 2002-08-28 |
KR100655004B1 (en) | 2006-12-07 |
DK1051467T3 (en) | 2003-01-06 |
FR2774387B1 (en) | 2000-12-01 |
PT1051467E (en) | 2003-01-31 |
CA2320332A1 (en) | 1999-08-05 |
ATE222943T1 (en) | 2002-09-15 |
FR2774387A1 (en) | 1999-08-06 |
DE69902631D1 (en) | 2002-10-02 |
US6528459B1 (en) | 2003-03-04 |
KR20010040538A (en) | 2001-05-15 |
WO1999038940A1 (en) | 1999-08-05 |
DE69902631T2 (en) | 2003-04-10 |
JP2002501974A (en) | 2002-01-22 |
ES2179614T3 (en) | 2003-01-16 |
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