EP1914295B1 - Lubrifiant marin pour fioul à basse et haute teneur en soufre - Google Patents

Lubrifiant marin pour fioul à basse et haute teneur en soufre Download PDF

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Publication number
EP1914295B1
EP1914295B1 EP06291590.5A EP06291590A EP1914295B1 EP 1914295 B1 EP1914295 B1 EP 1914295B1 EP 06291590 A EP06291590 A EP 06291590A EP 1914295 B1 EP1914295 B1 EP 1914295B1
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EP
European Patent Office
Prior art keywords
lubricant
cylinder
additives
chosen
detergents
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EP06291590.5A
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German (de)
English (en)
French (fr)
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EP1914295A1 (fr
Inventor
Valérie Doyen
Jean-Marie Bourmaud
Denis Lancon
Florence Bredon
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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Priority to PT62915905T priority Critical patent/PT1914295E/pt
Application filed by Total Marketing Services SA filed Critical Total Marketing Services SA
Priority to PL06291590T priority patent/PL1914295T3/pl
Priority to ES06291590.5T priority patent/ES2447428T3/es
Priority to EP06291590.5A priority patent/EP1914295B1/fr
Priority to DK06291590.5T priority patent/DK1914295T5/en
Priority to PCT/FR2007/001629 priority patent/WO2008043901A2/fr
Priority to JP2009531867A priority patent/JP5624319B2/ja
Priority to KR1020097009415A priority patent/KR101425832B1/ko
Priority to BRPI0715232A priority patent/BRPI0715232B1/pt
Priority to RU2009113418/04A priority patent/RU2460763C2/ru
Priority to SG2011073814A priority patent/SG175607A1/en
Priority to CN200780038021.0A priority patent/CN101522868B/zh
Priority to US12/445,255 priority patent/US8980805B2/en
Priority to ARP070104462A priority patent/AR063183A1/es
Publication of EP1914295A1 publication Critical patent/EP1914295A1/fr
Priority to HK08111567.2A priority patent/HK1119735B/xx
Application granted granted Critical
Publication of EP1914295B1 publication Critical patent/EP1914295B1/fr
Priority to CY20141100153T priority patent/CY1114909T1/el
Priority to JP2014129836A priority patent/JP2014169459A/ja
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/06—Sulfur
    • 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
    • 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
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • 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
    • 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]
    • 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
    • C10M2215/24—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
    • 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—Overbased sulfonic acid 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/52—Base number [TBN]
    • 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
    • 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 two-cycle marine engine cylinder lubricant for use with both high sulfur and low sulfur fuel oils. It relates more particularly to a lubricant having sufficient neutralization capacity vis-à-vis the sulfuric acid formed during the combustion of high-sulfur fuel oil, while limiting the formation of deposits during the use of fuel oils. low sulfur content.
  • the marine oils used in slow-moving 2-stroke engines are of two types.
  • the cylinder oils on the one hand, ensuring the lubrication of the cylinder piston assembly, and the system oils on the other hand, ensuring the lubrication of all moving parts out of the cylinder piston assembly.
  • the combustion residues containing acid gases are in contact with the lubricating oil.
  • Acid gases are formed from the combustion of fuel oils; they are in particular sulfur oxides (SO 2 , SO 3 ), which are then hydrolysed when in contact with the moisture present in the combustion gases and / or in the oil. This hydrolysis generates sulfurous acid (HSO 3 ) or sulfuric acid (H 2 SO 4 ).
  • these acids must be neutralized, which is usually done by reaction with the basic sites included in the lubricant.
  • the capacity of neutralization of an oil is measured by its BN or Base Number in English, characterizing its basicity. It is measured according to ASTM D-2896 and is expressed in equivalent weight of potash per gram of oil or mg of KOH / g.
  • the BN is a standard criterion for adjusting the basicity of cylinder oils to the sulfur content of the fuel oil used, in order to neutralize all the sulfur contained in the fuel, and likely to be converted into sulfuric acid by combustion and hydrolysis.
  • MARPOL Annex 6 (Regulations for the Prevention of air pollution from ships) of IMO (International Maritime Organization) entered into force in May 2005. It provides for a maximum sulfur content of 4.5% m / m of fuel oils. as well as the creation of controlled release zones in sulfur oxides, called SECAs (SOx Emission Control Areas). Vessels entering these areas shall use fuel with a maximum sulfur content of 1.5% m / m or other alternative treatment to limit SOx emissions to meet the specified values.
  • SECAs SOx Emission Control Areas
  • the notation% m / m denotes the weight percentage of a compound relative to the total weight of fuel oil or lubricating composition in which it is included.
  • the switching between these two categories of fuel oil may require adaptation of the operating conditions of the engine, in particular the use of appropriate cylinder lubricants.
  • marine lubricants with a BN of about 70 are used.
  • marine lubricants with a BN of about 40 are used.
  • each of these lubricants has limitations of use resulting from the following observations: the use of a BN 70 cylinder lubricant in the presence of a low sulfur fuel oil (1.5% w / w and less) and at fixed lubrication rate, creates a large excess of basic sites (strong BN) and a risk of destabilization of unused overbased detergent micelles, which contain insoluble metal salts. This destabilization results in the formation of insoluble metal salt deposits (eg calcium carbonate), mainly on the piston crown, and eventually can lead to a risk of excessive wear of polishing shirt.
  • insoluble metal salt deposits eg calcium carbonate
  • the optimization of the cylinder lubrication of a slow 2-stroke engine then requires the selection of the lubricant with the BN adapted to the fuel oil and to the operating conditions of the engine. This optimization reduces the operating flexibility of the engine and requires a high degree of technical skill of the crew in defining the conditions under which the changeover from one type of lubricant to the other must be achieved.
  • the document US3178368 discloses a process for producing sulfurized and overbased alkaline earth metal phenates. These phenates are used in lubricating compositions as additives having acid neutralizing properties.
  • EP1630223 discloses the use of a hydrocarbon-substituted polyphenol structure compound, which compound is used as an anti-wear additive in a marine diesel engine composition.
  • the document EP0008193 discloses a lubricating composition for marine engines comprising a lubricating base oil, a hydrocarbyl amine and dispersants for the hydrocarbyl amine salts which may be formed during use.
  • the object of the present invention is to provide a lubricating oil that can ensure good lubrication of the marine engine cylinder and can withstand the stresses of high sulfur fuel oils and the stresses of low sulfur fuel oils.
  • the present invention provides a cylinder lubricant having a BN determined according to ASTM D-2896 greater than or equal to 40 milligrams of potash per gram of lubricant, comprising a marine engine lubricating base stock and at least one overbased detergent. based on alkali or alkaline earth metals, characterized in that it additionally contains an amount of from 0.1% to 2% by weight, relative to the total weight of the lubricant, of one or more compounds (A) chosen from primary, secondary or tertiary mono-alcohols whose alkyl chain is saturated or comprises at most two ethylenic double bond unsaturations, said chain is linear or branched and comprises at least 12 carbon atoms.
  • A compounds chosen from primary, secondary or tertiary mono-alcohols whose alkyl chain is saturated or comprises at most two ethylenic double bond unsaturations, said chain is linear or branched and comprises at least 12 carbon atoms.
  • the Applicant has found that the introduction of certain types of surfactant compounds in a conventional cylinder lubricant formulation having a determined BN, leads to greatly increase the efficiency of said conventional lubricant vis-à-vis the neutralization of the lubricant.
  • the improvement in performance is particularly related to the rate or kinetics of neutralization of the sulfuric acid formed which is substantially increased.
  • This performance differential is characterized by a neutralization efficiency index measured using the enthalpy test described in the examples below.
  • the Applicant has found that the BN does not appear to be the sole criterion for the adaptability of the lubricant to the sulfur content of the fuel used. Although giving an indication of the potential for neutralization, the BN is not necessarily representative of the availability and accessibility of the basic sites constituting the BN vis-à-vis the acid molecules to be neutralized.
  • these surface-active compounds do not in themselves bring additional basicity to the lubricant in which they are dissolved.
  • their hydrophilic / lipophilic balance leads, when they are introduced into a lubricant with a given BN, to make the basic sites contained in the overbased detergents of the lubricant more accessible, and thus to make the reaction of the lubricant more efficient. neutralization of the sulfuric acid formed during the combustion of the fuel oil.
  • the present invention provides a cylinder lubricant having a specific BN in the range of 40 to 70 milligrams of potash per gram of lubricant, preferably 50 to 60, or even more preferably 55 milligrams of potash per gram of lubricant. as described in the claims.
  • the compounds A are chosen from heavy monoalcohols which have a linear main alkyl chain having 12 to 24 carbon atoms, this linear chain being optionally substituted by one or more alkyl groups having 1 to 23 carbon atoms.
  • the compounds A are chosen from myristic, palmitic, cetyl, stearic, eicosenoic and behenic alcohol. More preferably compound A is iso-tridecanol.
  • the cylinder lubricant comprises one or more functional additives chosen from dispersing additives, anti-wear agents, anti-foam additives, anti-oxidant and / or anti-rust additives.
  • the cylinder lubricant comprises at least one overbased detergent selected from the group consisting of carboxylates, sulfonates, salicylates, naphthenates, phenates, and mixed overbased detergents associating at least two of these types of detergents, especially lubricant.
  • cylinder comprises at least 10% of one or more overbased detergent compounds.
  • the overbased detergents are compounds based on metals selected from the group consisting of calcium, magnesium, sodium or barium, preferably calcium or magnesium.
  • the overbased detergents are compounds based on metals selected from the group consisting of calcium, magnesium, sodium or barium, preferably calcium or magnesium.
  • the detergents are overbased with metal insoluble salts selected from the group of alkali metal and alkaline earth metal carbonates, hydroxides, oxalates, acetates, glutamates.
  • the overbased detergents are alkali or alkaline earth metal carbonates or at least one of the detergents is overbased with calcium carbonate.
  • the cylinder lubricant comprises at least 0.1% of a dispersant additive selected from the family of succinimide PIBs.
  • the invention relates to the use of a lubricant as described above as a single cylinder lubricant that can be used with any type of fuel oil whose sulfur content is less than 4.5%, preferably of which the Sulfur content is 0.5 to 4% w / w.
  • the single cylinder lubricant is usable both with fuel oil with a sulfur content of less than 1.5% w / w and with fuel oils with a sulfur content of more than 3% w / w.
  • the invention relates to the use of a lubricant as described above for preventing corrosion and / or reducing the formation of deposits of insoluble metal salts in two-stroke marine engines during the combustion of fuel.
  • a lubricant as described above for preventing corrosion and / or reducing the formation of deposits of insoluble metal salts in two-stroke marine engines during the combustion of fuel.
  • the invention relates to the use of one or more compounds chosen from primary, secondary or tertiary monoalcohols whose alkyl chain is saturated or unsaturated, linear or branched and comprises at least 12 carbon atoms. , as surfactants in a cylinder lubricant having a BN, as measured by ASTM D-2896, greater than or equal to 40 milligrams of potash per gram of lubricant, to improve the efficiency of said cylinder lubricant with respect to the speed of neutralization of the sulfuric acid formed during the combustion of any type of fuel whose sulfur content is less than 4.5% m / m in a two-stroke marine engine.
  • the surfactant is present in an amount of from 0.01% to 10% by weight, preferably from 0.1% to 2% by weight relative to the total weight lubricant.
  • the invention relates to a method of manufacturing a lubricant as described above in which compound A is added as a separate component of the cylinder lubricant having a BN determined according to the standard ASTM D-2896 greater than or equal to 40 milligrams of potassium hydroxide per gram of lubricant and optionally comprising one or more functional additives.
  • the lubricant is prepared by diluting a marine lubricant additive concentrate in which compound A is incorporated.
  • the heavy monoalcohols have a linear main alkyl chain having 12 to 24 carbon atoms, this linear chain being optionally substituted by one or more alkyl groups having 1 to 23 carbon atoms.
  • the heavy monohydric alcohols used in the invention are nonionic surfactants whose hydrophilic polar head is represented by an OH hydroxyl group and whose lipophilic part is represented by a carbon chain which contains enough carbon atoms to confer a lipophilic character. sufficient to the molecule.
  • the heavy monohydric alcohols are used alone or in a mixture and are selected from primary, secondary or tertiary monoalcohols whose alkyl chain is saturated or unsaturated, linear or branched and comprises at least 12 carbon atoms.
  • the alkyl chain preferably comprises at most 60 carbon atoms.
  • the alkyl chain comprises from 12 to 50 carbon atoms. It is saturated or generally comprises at most two unsaturations of ethylenic double bond type.
  • the heavy monoalcohols have a linear main alkyl chain having 12 to 24 carbon atoms, this linear chain being optionally substituted by one or more alkyl groups having 1 to 23 carbon atoms.
  • the monoalcohols used in the invention generally come from the corresponding fatty acids according to known transformation methods.
  • fatty acids of vegetable origin are used.
  • linear monoalcohols examples include myristic, palmitic, cetyl, stearic, eicosenoic or behenic alcohols derived from the corresponding fatty acids.
  • branched monoalcohols there may be mentioned, for example, isotridecanol.
  • linear alkyl chain monoalcohols comprising an even number of carbon atoms of between 12 and 24 carbon atoms.
  • the present application describes that the amounts of surfactants used range from 0.1 to 2% by weight relative to the total weight of the lubricant.
  • the viscosity or the level of gelling of the final lubricant may vary according to the nature of the one or more heavy monoalcohol chosen, an amount in the range of 0.1% to 2% by weight of one or more monoalcohols relative to total weight of the lubricant. It will thus be possible to retain the final marine lubricant according to the invention, a viscosimetric grade conforming to the specifications of use.
  • the BN of the lubricants according to the present invention is provided by the overbased detergents based on alkaline or alkaline earth metals.
  • the value of this BN measured according to ASTM D-2896 can vary from 5 to 100 mg KOH / g in marine lubricants.
  • a lubricant of BN value fixed will be chosen according to the conditions of use of said lubricants and in particular according to the sulfur content of the fuel oil used and in combination with the cylinder lubricants.
  • the lubricants according to the present invention are suitable for use as a cylinder lubricant, irrespective of the sulfur content of the fuel oil used as fuel in the engine.
  • the cylinder lubricants for two-stroke marine engines according to the invention have a BN greater than or equal to 40, preferably ranging from 40 to 70, or from 50 to 60, or even equal to 55.
  • the lubricant formulation has a BN level, measured according to ASTM D-2896, intermediate between the levels required for the sulfur content limits of currently used fuel oils, that is, that is to say a BN of 50 to 60, preferably equal to 55.
  • BN level measured according to ASTM D-2896
  • This is coupled with a formulation including heavy monoalcohol type surfactants, allowing increased accessibility of the basic sites provided by overbased detergents, so as to neutralize the as efficiently as conventional formulations of higher BN.
  • a lubricating formulation according to the invention having a BN of 55 will have at least the same sulfuric acid neutralization efficiency as a traditional BN formulation of 70.
  • Conventional BN 55 oils thus reformulated according to the invention can properly prevent corrosion problems when using fuel oils with high sulfur content (of the order of 3% m / m).
  • An oil according to the present invention also allows a reduction in the formation of insoluble metallic salt deposits providing overbasing (eg CaCO 3 ) when using low sulfur fuel oils (1.5% w / w and less) this reduction is directly related to the lowering of the BN made possible in the present formulation configuration.
  • overbasing eg CaCO 3
  • the lubricants according to the present invention retain sufficient detergency when formulated both for use with low and high sulfur fuel oils, since their BN (and hence the amount of detergents present) can be set at an intermediate level between that required for both categories of fuel oil.
  • overbased detergents used in the lubricating compositions according to the present invention are well known to those skilled in the art.
  • the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head.
  • the associated cation is typically a metal cation of an alkali or alkaline earth metal.
  • the detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates.
  • the alkaline and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
  • metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents.
  • the excess metal providing the overbased detergent character is in the form of oil insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
  • the metals of these insoluble salts may be the same as those of the oil-soluble detergents or may be different. It is preferentially chosen from calcium, magnesium, sodium or barium.
  • the overbased detergents are thus in the form of micelles composed of insoluble metal salts maintained in suspension in the lubricating composition by the detergents in the form of oil-soluble metal salts.
  • These micelles may contain one or more types of insoluble metal salts, stabilized by one or more detergent types.
  • Overbased detergents with a single type of detergent soluble metal salt will generally be named after the nature of the hydrophobic chain of the latter detergent.
  • the overbased detergents will be said to be of mixed type if the micelles comprise several types of detergents, different from each other by the nature of their hydrophobic chain.
  • the oil-soluble metal salts will preferably be phenates, sulphonates salicylates, and mixed detergents phenate-sulphonate and / or salicylates calcium, magnesium, sodium or barium.
  • the insoluble metal salt providing the overbased character is calcium carbonate.
  • the overbased detergents used in the lubricating compositions according to the present invention will preferably be phenates, sulphonates, salicylates and mixed detergents phenates-sulphonates-salicylates, overbased with calcium carbonate.
  • At least 10% of one or more overbased detergent compounds is used, providing basicity to the lubricant in an amount sufficient to neutralize the acids formed upon combustion.
  • the amount of overbased detergents is typically determined to reach the targeted BN.
  • the base oils used for the formulation of lubricants according to the present invention can be oils of mineral, synthetic or vegetable origin as well as their mixtures.
  • the mineral or synthetic oils generally used in the application belong to one of the classes defined in the API classification as summarized below: Saturated content Sulfur content Viscosity index Group 1 Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group 2 Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group 3 Hydroisomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group 4 PAO Group 5 Other bases not included in groups 1 to 4
  • the Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes and then purification of these distillates by methods such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
  • the oils of Groups 2 and 3 are obtained by more severe purification methods, for example a combination among hydrotreatment, hydrocracking, hydrogenation and catalytic dewaxing.
  • Group 4 and 5 synthetic bases include polyalphaolefins, polybutenes, polyisobutenes, alkylbenzenes.
  • base oils can be used alone or as a mixture.
  • a mineral oil can be combined with a synthetic oil.
  • Cylinder oils for 2-stroke marine diesel engines have a SAE-40 SAE-40 viscometric grade, typically SAE-50 equivalent to a kinematic viscosity at 100 ° C of between 16.3 and 21.9 mm 2 / s.
  • This viscosity can be obtained by mixing additives and base oils, for example containing Group 1 mineral bases such as Neutral Solvent bases (for example 500NS or 600 NS) and the Brightstock. Any other combination of mineral, synthetic or vegetable bases having, in admixture with the additives, a viscosity compatible with the grade SAE-50 may be used.
  • a conventional cylinder lubricant formulation for slow 2-cycle marine diesel engines is SAE 40 to SAE60, preferably SAE50 (SA37 J300) and includes at least 50% by weight of original lubricating base oil.
  • mineral and / or synthetic, suitable for use in a marine engine for example of API Group 1, that is to say obtained by distillation of selected crudes and purification of these distillates by processes such as solvent extraction , solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
  • Their Viscosity Index (VI) is between 80 and 120; their sulfur content is greater than 0.03% and their saturated content is less than 90%.
  • the lubricant formulation according to the present invention may also contain functional additives adapted to their use, for example dispersant additives, anti-wear, anti-foam additives, anti-oxidant and / or anti-rust additives. These are known to those skilled in the art. These additives are generally present at a content by weight of 0.1 to 5%.
  • Dispersants are well known additives used in the formulation of lubricating composition, especially for application in the marine field. Their primary role is to maintain in suspension the particles present initially or appearing in the lubricant composition during its use in the engine. They prevent their agglomeration by playing on steric hindrance. They can also have a synergistic effect on the neutralization.
  • the dispersants used as lubricant additives typically contain a polar group, associated with a relatively long hydrocarbon chain, generally containing from 50 to 400 carbon atoms.
  • the polar group typically contains at least one nitrogen, oxygen or phosphorus element.
  • the compounds derived from succinic acid are dispersants particularly used as lubrication additives.
  • succinimides obtained by condensation of succinic anhydrides and amines
  • succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols.
  • These compounds can then be treated with various compounds including sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or zinc-blocked succinimides.
  • Mannich bases obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants.
  • At least 0.1% of a dispersing additive is used. It is possible to use a dispersant in the family of succinimide PIBs, for example borated or blocked with zinc.
  • lubricant compositions according to the present invention may also optionally contain other additives,
  • anti-wear additives which may for example be chosen from the family of zinc dithiophosphates, antioxidant / anti-rust additives, for example organo-metallic or thiadiazole detergents, and anti-foam additives to counteract the effect of detergents, which may for example be polar polymers such as polymethylsiloxanes, polyacrylates.
  • compositions of the lubricants described refer to the compounds taken separately before mixing, it being understood that said compounds may or may not retain the same chemical form before and after mixing.
  • the surfactant compounds contained in the lubricants according to the present invention may in particular be incorporated in a lubricant as a separate additive, for example to increase the neutralization efficiency of a conventional lubricant formulation already known.
  • the surfactants according to the invention are in this case preferably included in a conventional cylinder lubricant formulation for slow 2-stroke marine diesel engines of grade SAE 40 to SAE60, preferably SAE50 (according to SAE classification J300).
  • Additive concentrates for marine lubricants are additive concentrates for marine lubricants.
  • the surfactant compounds contained in the lubricants of the present invention may also be incorporated into a marine lubricant additive concentrate.
  • the marine cylinder lubricant additive concentrates generally consist of a mixture of the constituents described above, detergents, dispersants, other functional additives, pre-dilution base oil, in proportions which make it possible to obtain, after dilution in an oil base of the cylinder lubricants having a BN determined according to ASTM D-2896 greater than or equal to 40 milligrams of potash per gram of lubricant.
  • This mixture generally contains, relative to the total weight of concentrate, a detergent content greater than 80%, preferably greater than 90%, a dispersant additive content of 2 to 15%, preferably 5 to 10%, a content of other functional additives from 0 to 5%, preferably from 0.1 to 1%.
  • the additive concentrate for marine lubricant comprises one or more surfactants in a proportion which makes it possible to obtain an amount of surfactant in the lubricant cylinder according to the invention of 0.1 to 2%.
  • the marine lubricant additive concentrate contains, relative to the total weight of concentrate, from 0.5 to 15% by weight of one or more compounds (A) chosen from primary, secondary monoalcohols. or tertiary whose alkyl chain is saturated or comprises at most two ethylenic double bond unsaturation, said chain is linear or branched and comprises at least 12 carbon atoms.
  • A compounds chosen from primary, secondary monoalcohols. or tertiary whose alkyl chain is saturated or comprises at most two ethylenic double bond unsaturation, said chain is linear or branched and comprises at least 12 carbon atoms.
  • This measurement is characterized by a neutralization efficiency index measured according to the enthalpic test method described precisely in the examples and in which the progress of the exothermic neutralization reaction is followed by the rise in the temperature observed when the lubricant containing the basic sites is put in the presence of sulfuric acid.
  • Example 1 This example aims at describing the enthalpic test for measuring the neutralization efficiency of lubricants with respect to sulfuric acid
  • the acid-base neutralization reactions are generally exothermic and it is therefore possible to measure the heat release obtained by reaction of sulfuric acid with the lubricants to be tested. This evolution is followed by the evolution of the temperature over time in an adiabatic reactor of the DEWAR type.
  • the duration S is equal to the difference t f - t i between the time at the end of reaction temperature and the time at the reaction start temperature.
  • the time t i at the reaction start temperature corresponds to the first rise in temperature after stirring is started.
  • the time t f at the final reaction temperature is that from which the temperature signal remains stable for a duration greater than or equal to half the reaction time.
  • the lubricant is all the more effective as it leads to short periods of neutralization and therefore to a high index.
  • the reactor and agitator geometries as well as the operating conditions were chosen so as to be in a chemical regime, where the effect of the diffusional stresses in the oil phase is negligible.
  • the fluid height must be equal to the inside diameter of the reactor, and the stirring propeller must be positioned at about 1/3 of the height of the fluid.
  • the apparatus consists of a cylindrical type adiabatic reactor of 250 ml, the internal diameter of which is 48 mm and the inner height of 150 mm, of a stirring rod provided with a propeller with inclined blades, 22 mm in diameter; the diameter of the blades is between 0.3 and 0.5 times the diameter of the DEWAR, that is to say from 9.6 to 24 mm.
  • the position of the propeller is set at a distance of 15 mm from the bottom of the reactor.
  • the stirring system is driven by a variable speed motor of 10 to 5000 rpm and a temperature acquisition system as a function of time.
  • This system is suitable for measuring reaction times of the order of 5 to 20 seconds and the temperature rise measurement of a few tens of degrees from a temperature of about 20 ° C to 35 ° C preferably about 30 ° C.
  • the position of the temperature acquisition system in the DEWAR is fixed.
  • the stirring system will be adjusted so that the reaction occurs in a chemical regime: in the configuration of the present experiment, the speed of rotation is set at 2000 rpm, and the position of the system is fixed.
  • the chemical regime of the reaction is also dependent on the oil height introduced into the DEWAR, which must be equal to the diameter of the latter, and which corresponds in the context of this experiment to the mass of 70 g of the lubricant tested.
  • the acquisition system is started and the stirring system is set to go into chemical mode.
  • This oil is obtained from a mineral base obtained by mixing a distillate of density at 15 ° C of between 880 and 900 Kg / m 3 with a distillation residue having a density of between 895 and 915 Kg / m. 3 (Brightstock) in a distillate / residue ratio of 3.
  • BN 70 mg KOH / g.
  • the lubricant thus obtained has a viscosity at 100 ° C of between 19 and 20.5 mm 2 / s.
  • the neutralization reaction time of this oil (hereinafter referred to as Href) is 10.3 seconds and its neutralization efficiency index is set to 100.
  • Two other lubricant samples of BN 55 and 40 are prepared from the same additive concentrate diluted respectively by 1.25 and 1.7 according to the desired BN and a lubricating base whose mixture of the distillate and the residue is adapted to obtain in the end a viscosity at 100 ° C of between 19 and 20.5 mm 2 / s.
  • H55 and H40 are also free of surfactant additive additives according to the present invention.
  • Table 1 shows the values of the neutralization indices obtained for the BN 40 and 55 samples prepared by dilution of the additives included in the BN 70 reference oil. ⁇ u> Table 1 ⁇ / u> BN Neutralization efficiency index href 70 100 H 55 55 88 H 40 40 77
  • Example 2 This example describes the influence of the additives according to the invention for a constant BN formulation 55.
  • the reference is the cylinder oil for two-stroke marine engine BN 70, not additive according to the present invention, and referenced Href in the previous example.
  • the samples additive BN 55 to be tested are prepared from the non-additive lubricant referenced H 55 in the previous example.
  • Table 2 below groups the values of the efficiency indices of the different samples thus prepared.
  • the lubricants with additives according to the present invention have, at BN 55, a neutralization efficiency index higher than that of the same oil of BN 55 not thus additive.
  • BN 55 oils additivated according to the present invention have a higher neutralization efficiency index than that of a non-additivated BN 70 oil taken as a reference.
  • index values calculated for BN 55 oils according to the present invention are overall from 9 to 27% higher than the reference, even though the introduction of the additives according to the present invention has no influence on the value. of their BN.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
EP06291590.5A 2006-10-11 2006-10-11 Lubrifiant marin pour fioul à basse et haute teneur en soufre Active EP1914295B1 (fr)

Priority Applications (17)

Application Number Priority Date Filing Date Title
PL06291590T PL1914295T3 (pl) 2006-10-11 2006-10-11 Środek smarujący okrętowy do oleju napędowego z niską lub wysoką zawartością siarki
ES06291590.5T ES2447428T3 (es) 2006-10-11 2006-10-11 Lubricante marino para fuel con bajo y alto contenido de azufre
EP06291590.5A EP1914295B1 (fr) 2006-10-11 2006-10-11 Lubrifiant marin pour fioul à basse et haute teneur en soufre
DK06291590.5T DK1914295T5 (en) 2006-10-11 2006-10-11 Lubricant for ship engines that use fuel oil with low or high sulfur content
PT62915905T PT1914295E (pt) 2006-10-11 2006-10-11 Lubrificante marítimo para óleo combustível com alto ou baixo teor de enxofre
RU2009113418/04A RU2460763C2 (ru) 2006-10-11 2007-10-05 Смазочное масло, используемое в судовых двигателях, работающих на дизельном топливе, имеющем высокое и низкое содержание серы
KR1020097009415A KR101425832B1 (ko) 2006-10-11 2007-10-05 다양한 황 함량을 갖는 연료유를 위한 선박용 윤활제
BRPI0715232A BRPI0715232B1 (pt) 2006-10-11 2007-10-05 lubrificante marítimo para óleo combustível com alto e baixo teor de enxofre
PCT/FR2007/001629 WO2008043901A2 (fr) 2006-10-11 2007-10-05 Lubrifiant marin pour fioul a basse ou haute teneur en soufre
SG2011073814A SG175607A1 (en) 2006-10-11 2007-10-05 Marine lubricant for fuel oil having high and low sulphur contents
CN200780038021.0A CN101522868B (zh) 2006-10-11 2007-10-05 适用于高硫及低硫燃料油的船用润滑油
US12/445,255 US8980805B2 (en) 2006-10-11 2007-10-05 Marine lubricant for fuel oil having high and low sulphur contents
JP2009531867A JP5624319B2 (ja) 2006-10-11 2007-10-05 高硫黄分及び低硫黄分の燃料油に適した船舶用潤滑剤
ARP070104462A AR063183A1 (es) 2006-10-11 2007-10-09 Lubricante marino para fuel con bajo y alto contenido de azufre
HK08111567.2A HK1119735B (en) 2008-10-20 Marine lubricant for a low or high sulfur content fuel
CY20141100153T CY1114909T1 (el) 2006-10-11 2014-02-26 Λιπαντικο ναυτιλιας για μαζουτ με χαμηλη ή me υψηλη περιεκτικοτητα σε θειο
JP2014129836A JP2014169459A (ja) 2006-10-11 2014-06-25 高硫黄分及び低硫黄分の燃料油に適した船舶用潤滑剤

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06291590.5A EP1914295B1 (fr) 2006-10-11 2006-10-11 Lubrifiant marin pour fioul à basse et haute teneur en soufre

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EP1914295A1 EP1914295A1 (fr) 2008-04-23
EP1914295B1 true EP1914295B1 (fr) 2013-12-04

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US (1) US8980805B2 (enExample)
EP (1) EP1914295B1 (enExample)
JP (2) JP5624319B2 (enExample)
KR (1) KR101425832B1 (enExample)
CN (1) CN101522868B (enExample)
AR (1) AR063183A1 (enExample)
BR (1) BRPI0715232B1 (enExample)
CY (1) CY1114909T1 (enExample)
DK (1) DK1914295T5 (enExample)
ES (1) ES2447428T3 (enExample)
PL (1) PL1914295T3 (enExample)
PT (1) PT1914295E (enExample)
RU (1) RU2460763C2 (enExample)
SG (1) SG175607A1 (enExample)
WO (1) WO2008043901A2 (enExample)

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US8619956B2 (en) * 2007-02-05 2013-12-31 Avaya Inc. Private-branch exchange that provides call bridging to an off-premises terminal in the presence of a third-party application
FR2928934B1 (fr) * 2008-03-20 2011-08-05 Total France Lubrifiant marin
FR2932813B1 (fr) * 2008-06-18 2010-09-03 Total France Lubrifiant cylindre pour moteur marin deux temps
US20120202728A1 (en) 2009-10-09 2012-08-09 Jose Luis Garcia Ojeda Lubricating composition
FR2974111B1 (fr) 2011-04-14 2013-05-10 Total Raffinage Marketing Lubrifiant cylindre pour moteur marin deux temps
FR2980799B1 (fr) 2011-09-29 2013-10-04 Total Raffinage Marketing Composition lubrifiante pour moteur marin
FR3000103B1 (fr) 2012-12-21 2015-04-03 Total Raffinage Marketing Composition lubrifiante a base d'ether de polyglycerol
FR3005474B1 (fr) 2013-05-07 2016-09-09 Total Raffinage Marketing Lubrifiant pour moteur marin
FR3017875B1 (fr) 2014-02-24 2016-03-11 Total Marketing Services Composition d'additifs et carburant de performance comprenant une telle composition
FR3017876B1 (fr) 2014-02-24 2016-03-11 Total Marketing Services Composition d'additifs et carburant de performance comprenant une telle composition
FR3066200A1 (fr) * 2017-05-15 2018-11-16 Total Marketing Services Compositions lubrifiantes pour ameliorer la proprete d'un moteur de vehicule 4-temps
CN109722284B (zh) * 2017-10-27 2020-11-06 中国石油化工股份有限公司 一种重油预处理的方法
CN109722303B (zh) * 2017-10-27 2020-11-10 中国石油化工股份有限公司 一种高硫重油生产低硫船用燃料油调和组分的方法
CN110646564A (zh) * 2018-06-26 2020-01-03 中国石油天然气股份有限公司 一种评价清净剂的碱值保持性的方法
US11987766B2 (en) * 2020-08-31 2024-05-21 Eneos Corporation Lubricating oil composition for internal combustion engine
US11732207B2 (en) * 2020-08-31 2023-08-22 Eneos Corporation Lubricating oil composition for internal combustion engine

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JP2010506023A (ja) 2010-02-25
ES2447428T3 (es) 2014-03-12
KR20090086544A (ko) 2009-08-13
SG175607A1 (en) 2011-11-28
AR063183A1 (es) 2008-12-30
RU2460763C2 (ru) 2012-09-10
CN101522868A (zh) 2009-09-02
BRPI0715232B1 (pt) 2017-03-07
US20100167969A1 (en) 2010-07-01
WO2008043901A3 (fr) 2008-06-19
CN101522868B (zh) 2014-01-15
JP2014169459A (ja) 2014-09-18
EP1914295A1 (fr) 2008-04-23
WO2008043901A2 (fr) 2008-04-17
PL1914295T3 (pl) 2014-05-30
HK1119735A1 (en) 2009-03-13
RU2009113418A (ru) 2010-11-20
KR101425832B1 (ko) 2014-07-31
DK1914295T3 (da) 2014-02-10
BRPI0715232A2 (pt) 2015-07-21
US8980805B2 (en) 2015-03-17
DK1914295T5 (en) 2014-03-17
PT1914295E (pt) 2014-03-05
JP5624319B2 (ja) 2014-11-12
CY1114909T1 (el) 2016-12-14

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