EP2697344B1 - Lubrifiant cylindre pour moteur marin deux temps - Google Patents

Lubrifiant cylindre pour moteur marin deux temps Download PDF

Info

Publication number
EP2697344B1
EP2697344B1 EP12714700.7A EP12714700A EP2697344B1 EP 2697344 B1 EP2697344 B1 EP 2697344B1 EP 12714700 A EP12714700 A EP 12714700A EP 2697344 B1 EP2697344 B1 EP 2697344B1
Authority
EP
European Patent Office
Prior art keywords
lubricant
cylinder
milligrams
detergents
per gram
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.)
Not-in-force
Application number
EP12714700.7A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2697344A1 (fr
Inventor
Denis Lancon
Valérie Doyen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
Original Assignee
Total Marketing Services SA
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 Total Marketing Services SA filed Critical Total Marketing Services SA
Priority to PL12714700T priority Critical patent/PL2697344T3/pl
Publication of EP2697344A1 publication Critical patent/EP2697344A1/fr
Application granted granted Critical
Publication of EP2697344B1 publication Critical patent/EP2697344B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M7/00—Lubrication means specially adapted for machine or engine running-in
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2207/027—Neutral 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
    • C10M2207/02—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
    • C10M2207/10—Carboxylix acids; Neutral 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • 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
    • C10M2215/02—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
    • 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
    • C10M2215/02—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
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

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 milligram equivalent of potash per gram of oil (also referred to as "mg of KOH / g" or "BN point").
  • the BN is a standard criterion for adjusting the basicity of cylinder oils to the sulfur content of the fuel used, in order to neutralize all the sulfur contained in the fuel, and likely to be converted into sulfuric acid by combustion and hydrolysis.
  • BN ranging from 5 to 100 mg KOH / g.
  • the detergents mainly of the anionic type, are, for example, metal salicylate, phenate, sulphonate or carboxylate soaps which form micelles in which the insoluble metal salt particles are kept in suspension.
  • the usual overbased detergents intrinsically have a BN conventionally between 150 and 700 mg KOH per gram of detergent. Their mass percentage is fixed in the lubricant as a function of the level of BN that one wishes to achieve.
  • a part of the BN can also be provided by non-overbased or "neutral” detergents with a NO 2 typically of less than 150.
  • neutral detergents with a NO 2 typically of less than 150.
  • the insoluble metal salts of the overbased detergents for example calcium carbonate, thus contribute significantly to the BN of the usual lubricants. It can be considered that at least 50%, typically 75%, of the BN of the cylinder lubricants is thus provided by these insoluble salts.
  • the detergent part itself, or metal soaps, found in both neutral and overbased detergents typically provides the bulk of the BN complement.
  • MARPOL Annex 6 (Regulations for the Prevention of Air Pollution from Ships) of IMO (International Maritime Organization) entered into force in May 2005. It sets a maximum sulfur content of 4.5% w / w heavy fuel oils and the creation of Sulfur Emission Control Areas (Sulfur Emission Control Areas). Vessels entering these areas must use fuel with a maximum sulfur content of 1.5% m / m or other alternative treatment to limit SOx emissions to meet the values. specified.
  • 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 (this value will in the future be reduced).
  • 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 fixed lubrication rate, creates a large excess of basic sites (strong BN) and a risk of destabilization of micelles of unused overbased detergents, which contain insoluble metal salts. This destabilization results in the formation of insoluble metal salt deposits and having a high hardness (for example calcium carbonate), mainly on the piston ring, and eventually can lead to a risk of excessive wear polishing shirt.
  • a BN 70 cylinder lubricant in the presence of a low sulfur fuel oil (1.5% w / w and less)
  • fixed lubrication rate creates a large excess of basic sites (strong BN) and a risk of destabilization of micelles of unused overbased detergents, which contain insoluble metal salts.
  • This destabilization results in the formation of insoluble metal
  • 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 demand WO 2009/153453 discloses two-cycle marine engine cylinder lubricants for use with both high and low sulfur fuels.
  • the said lubricating compositions have a BN greater than or equal to 15, and comprise one or more lubricating base oils for a marine engine, at least one overbased detergent, optionally in combination with a neutral detergent, one or more oil-soluble fatty amines. .
  • Fatty amines bring at least 10 points of BN, and detergents overbased at most 20 points of BN, to the lubricant.
  • These lubricating compositions can have a BN of the order of 50 and are as effective from the point of view of acid neutralization kinetics as much higher (typically 70) BN cylinder lubricants, specifically designed for high solids content fuels. sulfur; their reduced rate of overbased detergents also allows them to be adapted to low sulfur content.
  • the demand FR 2094182 discloses a lubricating composition
  • a lubricating composition comprising from 0.01 to 5% of an acid neutralization accelerator which may be an ethoxylated fatty diamine, and sufficient alkaline earth metal carbonate to impart a BN of 0.5 to 100 mg KOH / g to the composition.
  • an acid neutralization accelerator which may be an ethoxylated fatty diamine
  • alkaline earth metal carbonate to impart a BN of 0.5 to 100 mg KOH / g to the composition.
  • These carbonates can be dispersed in the lubricant by phenates or sulfonates.
  • compositions have a thermal resistance (measured in particular by their ability to form deposits in the ECBT test) mediocre.
  • the present invention relates to a lubricant composition that can be used as cylinder lubricants for two-stroke marine engines, which can be used with both high and low sulfur fuels, and which makes it possible to overcome the disadvantages mentioned above.
  • Lubricating compositions according to the invention comprise alkoxylated fatty amines in limited amounts, combined with neutral detergents and overbased detergents in specific proportions.
  • compositions according to the invention have very good antiwear properties, and a heat resistance superior to the compositions of the prior art. They are more resistant to aging and retain these properties throughout their residence time in the cylinder of the marine engine.
  • the BN of the alkoxylated fatty amines determined according to ASTM D-2896 is between 120 and 500, preferably between 150 and 400, preferably between 200 and 300 milligrams of potash per gram.
  • the weight percentage of alkoxylated fatty amines relative to the total weight of lubricant is chosen so that the BN supplied by these compounds represents a contribution of between 3 and 7 milligrams of potassium hydroxide. per gram of lubricant, preferably between 3.5 and 5 milligrams of potash per gram of total BN lubricant of said cylinder lubricant, determined according to ASTM D-2896.
  • the cylinder lubricants according to the invention have a BN, determined according to ASTM D-2896, greater than or equal to 20, preferably greater than 30, advantageously greater than 40 milligrams of potash per gram of lubricant.
  • the cylinder lubricants according to the invention have a BN, determined according to ASTM D-2896, less than 55 milligrams of potash per gram of lubricant.
  • the cylinder lubricants according to the invention have a BN, determined according to ASTM D-2896, of between 40 and 50 milligrams of potash per gram of lubricant, preferably between 42 and 45 milligrams of potash per gram of lubricant.
  • the cylinder lubricants according to the invention have a BN, determined according to the ASTM D-2896 standard, between 50 and 55 milligrams of potash per gram of lubricant, preferably between 51 and 53 milligrams of potash per gram of lubricant.
  • the BN supplied by the metal salts of carbonates represents a contribution of between 10% and 60%, preferably between 20% and 55%, preferably between 30% and 50%, of the total BN. said cylinder lubricant.
  • the oil-soluble alkoxylated fatty amine or amines are obtained from palm, olive, peanut, conventional or oleic rapeseed oil, Classic or oleic sunflower, soya, cotton, from beef tallow, or palmitic, stearic, oleic, linoleic acid.
  • the oil-soluble alkoxylated fatty amine or amines are obtained from fatty acids comprising between 16 and 18 carbon atoms.
  • the overbased detergents (b) and the neutral detergents (c) are chosen from carboxylates, sulphonates, salicylates, naphthenates, phenates, and mixed detergents combining at least two of these types of detergents.
  • At least one overbased detergent (b) is a sulphonate.
  • At least one neutral detergent (c) is a phenate or a sulphonate, preferably a phenate.
  • the cylinder lubricants according to the invention have a kinematic viscosity measured according to ASTM D445 at 100 ° C between 12.5 and 26.1 cSt, preferably between 16.3 and 21.9 cSt.
  • the present invention also relates to the use of a lubricant as described above as a single cylinder lubricant usable both with fuel oils with a sulfur content of less than 1.5% m / m and with fuel oil content in sulfur greater than 3.5% m / m in two-stroke marine engines.
  • the present invention also relates to the use of a lubricant as described above as a single cylinder lubricant usable with both fuel oils with a sulfur content of less than 1% w / w and with sulfur-containing fuel oils. greater than 3% m / m in two-stroke marine engines.
  • the present invention also relates to the use of a lubricant as described above as a cylinder lubricant usable with all fuel with a sulfur content of between 0.1% w / w and 3.5% w / w in two-stroke marine engines.
  • the present invention also 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 the cylinders of two-stroke marine engines during the combustion of any type of fuel oil with a sulfur content of less than 4.5% m / m.
  • Alkoxylated fatty amines and other accelerators of neutralization speed Alkoxylated fatty amines and other accelerators of neutralization speed:
  • the fatty amines used in the lubricants according to the present invention are alkoxylated fatty amines, preferably monoamines, or diamines containing one or more aliphatic chains.
  • the intrinsic BN of the alkoxylated fatty amines used in the present invention is typically comprised between 100 and 600 milligrams of potash per gram, preferably between 120 and 500 milligrams of potash per gram, preferably between 150 and 400 milligrams of potash per gram, preferably between 200 and 300 milligrams of potash per gram.
  • This polar head is constituted by the nitrogen atom and by the oxygen atom (s) provided by the alkoxylation, and the lipophilic part by the fatty aliphatic chain (s).
  • this polar head it is preferable, in order to obtain a surfactant character, for this polar head to consist of amine functions which are not very distant from one another (typically separated by 2 to 3 carbon atoms), and preferably in a restricted number (typically one or two functions).
  • alkoxylated with a limited number of alkylene oxide functions typically between 1 and 15, preferably between 2 and 10, preferentially between 3 and 7, preferentially between 3 and 4, and preferably with alkylene oxides comprising from 2 to 4 carbon atoms.
  • the alkoxylated fatty amines are obtained by known alkoxylation processes, for example described in the application FR 2 094 182 , by bringing together the fatty amines and the alkylene oxides, at temperatures for example between 100 and 200 ° C, in the presence of a basic catalyst which may be NaOH, KOH, NaOCH 3 .
  • the starting fatty amines are mainly obtained from carboxylic acids. These acids are dehydrated in the presence of ammonia to give nitriles, which then undergo catalytic hydrogenation to lead to primary, secondary or tertiary amines.
  • the starting fatty acids for obtaining fatty amines are, for example, caprylic, pelargonic, capric, undecylenic, lauric, tridecylenic, myristic, pentadecyl, palmitic, margaric, stearic, nonadecylic, arachic, heneicosanoic, behenic, tricosanoic, lignoceric, pentacosanoic acids.
  • the preferred fatty acids are derived from the hydrolysis of triglycerides present in vegetable and animal oils, such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soy oil and cotton oil.
  • vegetable and animal oils such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soy oil and cotton oil.
  • the natural oils may have been genetically modified to enrich their content of certain fatty acids, for example rapeseed oil or oleic sunflower oil.
  • the fatty amines used to prepare the alkoxylated fatty amines of the lubricants according to the invention are preferably obtained from natural, vegetable or animal resources. Treatments for producing fatty amines from natural oils can result in mixtures of primary, secondary and tertiary monoamines and polyamines.
  • q is an integer greater than 1, preferably between 1 and 12, or between 1 and 5, or between 1 and 2
  • r is an integer between 2 and 3
  • R and R 1 are fatty chains from or fatty acids present in the starting oil.
  • the same mono or fatty polyamine may contain several fatty chains from different fatty acids.
  • These products can also be used in purified form, mainly containing a single type of amines, for example predominantly monoamines or predominantly diamines.
  • R 1 may represent a plurality of fatty acids derived from a natural resource, for example tallow fat, or soybean oil, or coconut oil, or sunflower oil (oleic).
  • R 1 may represent a plurality of fatty acids from a natural resource, for example tallow fat , or soybean oil, or coconut oil, or sunflower oil (oleic).
  • amines obtained from oleic acid in particular primary monoamines of formula R 1 NH 2 or diamines of formula R 1 - [NH (CH 2 ) 3 ] -NH 2 where R 1 is the fatty chain of oleic acid.
  • the alkoxylated amines of the lubricants according to the present invention must be highly soluble in the oil matrix in order to be able to effectively increase the acid neutralization kinetics.
  • alkoxylated fatty amines The solubility of alkoxylated fatty amines is primarily due to their fatty chain. These amines are also all the more soluble that they comprise a limited number of alkylene oxide functions. The Applicant has also found that the alkoxylated amines where the nitrogen atoms are ternary (where no longer NH bond exist) are easier to solubilize, preferentially monoamines with ternary nitrogen.
  • alkoxylated amines are therefore all the more effective if they are well dispersed - solubilized in the oil matrix.
  • the fatty amines of the lubricants according to the present invention are not in emulsion or microemulsion form, but well dispersed in the oil matrix.
  • the fatty amines according to the present invention are therefore preferably those which comprise at least one aliphatic chain consisting of at least 12 carbon atoms, preferably at least 14 carbon atoms, preferably at least 16 carbon atoms, preferably at least 18 carbon atoms. carbon.
  • These compounds can be used in combination with the alkoxylated amines at contents of between 0.1 and 10% by weight, preferably between 0.1 and 2%, preferably between 0.3 and 1.5%, preferentially between 0.4 and 1.5% by weight. and 1%, preferably between 0.5 and 1%.
  • fatty monoalcohols whose alkyl chain is saturated or unsaturated, linear or branched, and comprise at least 12 carbon atoms, preferably between 12 and 24 carbon atoms, preferably from 16 to 18 atoms. of carbon.
  • these fatty monoalcohols are primary monoalcohols with a linear saturated alkyl chain, preferably containing from 16 to 18 carbon atoms.
  • esters of saturated fatty acids containing at least 14 carbon atoms and alcohols containing at most 6 carbon atoms preferably chosen from mono and diesters, preferably from monoesters of monoalcohol, and diesters. whose ester functions are at most four carbon atoms from the oxygen side of the ester function.
  • the BN of the lubricants according to the present invention is provided by neutral detergents, overbased detergents based on alkali or alkaline earth metals, and with one or more alkoxylated fatty amines.
  • the value of this BN, measured according to ASTM D-2896 can vary for a lubricant of 0.5 to 100 mg KOH / g, or beyond.
  • the BN of a marine engine cylinder lubricant 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 in combination with said 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 two-cycle marine engine cylinder lubricants according to the invention have a BN greater than or equal to 15 milligrams of potash per gram of lubricant, preferably greater than 20, preferably greater than 30, advantageously greater than 40.
  • the cylinder lubricants according to the invention have a BN of less than 55, typically between 40 and 55, preferably between 40 and 50, preferably between 42 and 45, typically of the order of 43 or 44 milligrams of potash per gram of lubricant.
  • BN typically of prior art cylinder lubricant formulations specifically used and only with low sulfur fuel oils where (almost) all BN is provided by overbased detergents.
  • the lubricants according to the invention have a BN between 50 and 55, typically between 51 and 53 milligram of potash per gram of lubricant.
  • the proportion of BN supplied by the alkoxylated fatty amines in the lubricants according to the invention is between 2 and 8, preferably between 3 and 7, preferably between 3.5 and 5 milligrams of potassium per gram of lubricant (or "BN points"). ").
  • the intrinsic BN of the alkoxylated amines of the lubricants according to the invention is between 100 and 600, preferably between 120 and 500, preferably between 150 and 400, preferably between 200 and 300.
  • the alkoxylated fatty amines provide between 0.33% (supply of 2 points of BN with an amine of BN 600) and 8% (supply of 8 points of BN with an amine of BN 100 ) of the total BN, preferably between 0.4% (contribution of 2 points of BN by an amine of BN 500) and 6.7% (contribution of 8 points of BN by an amine of BN 120) of the total BN, preferably between 0.5% (contribution of 2 points of BN by an amine of BN 400) and 5.3% (contribution of 8 points of BN by an amine of BN 150) of the total BN, preferentially between 0.7% (contribution of 2 BN points with an amine of BN 300) and 4% (contribution of 8 BN points with an amine of BN 200) of the total BN.
  • the detergents used in the lubricant 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.
  • neutral detergents typically have a BN, measured according to ASTM D2896, less than 150 mg KOH / g, or less than 100, or even less than 80 mg KOH / g.
  • neutral detergents can contribute in part to the BN lubricants according to the present invention.
  • neutral detergents of carboxylates, sulphonates, salicylates, phenates, alkali metal and alkaline earth metal naphthenates, for example calcium, sodium, magnesium or barium will be used.
  • BN is high, greater than 150 mg KOH / g, typically between 200 and 700 mg KOH / g, generally between 250 and 450 mg KOH / g.
  • 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. They are preferably selected 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 and sulphonates, salicylates, and mixed phenate-sulphonate and / or salicylate detergents, preferentially phenates and / or sulphonates. , calcium, magnesium, sodium or barium, preferably calcium phenates and / or sulfonates.
  • the insoluble metal salts providing the overbased character are alkali and alkaline earth metal carbonates, preferentially 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, preferentially sulphonates and phenates overbased with calcium carbonate.
  • part of the BN is provided by the insoluble metal salts of the overbased detergents, in particular the metal carbonates.
  • the BN supplied by the carbonate metal salts (or BN carbonate or BN CaCO3 ) is measured on the overbased detergent alone and / or on the final lubricant according to the method described in Example 1.
  • the BN brought The carbonate metal salts represent from 50 to 95% of the total BN of the overbased detergent alone.
  • neutral detergents also include some content (much less important than overbased detergents) in insoluble metal salts (calcium carbonate), and can themselves contribute to the BN carbonate.
  • the mass percentage of overbased (and neutral) detergents relative to the total weight of lubricant is chosen so that the BN supplied by the carbonate metal salts represents a contribution of at most 65%. preferably at most 60% of the total BN (according to ASTM D-2896) of said cylinder lubricant.
  • insoluble metal salts however, have a favorable anti-wear effect provided that they are kept dispersed in the lubricant in the form of stable micelles (which is not the case when they are in excess of the amount of sulfuric acid to neutralize in service).
  • the BN carbonate provided by the insoluble metal salts represent preferably between 10% and 60%, preferably between 20% and 55%, preferably between 30% and 50% of the total BN (ASTM D-2896) of said lubricant.
  • BN ASTM D-2896
  • ASTM D-2896 BN of the order of 40 to 50
  • the BN contribution provided by the Insoluble metal salts of overbased detergents are in the range of 20 to 25 milligrams of potash per gram of lubricant, typically 22 to 24 milligrams of potash per gram of lubricant or "BN point”.
  • the detergents themselves which are metal soaps of the essentially phenate, or sulfonate, or salicylate type, also contribute to the BN of the lubricants according to the present invention.
  • 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 in the table below.
  • Saturated content Sulfur content Viscosity index (VI) Group I Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group II Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group III Hydroisomerized Oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group IV PAO (polyalphaolefins) Group V
  • the Group I mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes and then purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation.
  • the oils of Groups II and III are obtained by more severe purification methods, for example a combination among hydrotreatment, hydrocracking, hydrogenation and catalytic dewaxing.
  • Group IV and V synthetic bases include polyalphaolefins (PAOs), polybutenes, polyisobutenes, alkylbenzenes.
  • PAOs polyalphaolefins
  • polybutenes polybutenes
  • polyisobutenes alkylbenzenes.
  • base oils can be used alone or as a mixture.
  • a mineral oil can be combined with a synthetic oil.
  • Cylinders 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 16.3 to 21.9 mm 2 / s.
  • Grade 40 oils have a kinematic viscosity at 100 ° C of between 12.5 and 16.3 cSt.
  • Grade 50 oils have a kinematic viscosity at 100 ° C of 16.3 to 21.9 cSt.
  • Grade 60 oils have a kinematic viscosity at 100 ° C of 21.9 to 26.1 cSt.
  • cylinder oils for 2-stroke marine diesel engines having a kinematic viscosity at 100 ° C. of between 18 and 21.5, preferably between 19 and 21.5 mm 2 / s (cSt). .
  • This viscosity can be obtained by mixing additives and base oils, for example containing Group I mineral bases such as Neutral Solvent (for example 500NS or 600 NS) and Brightstock bases. Any other combination of bases mineral, synthetic or vegetable origin having, in admixture with the additives, a viscosity compatible with the grade SAE-50 may be used.
  • Group I mineral bases such as Neutral Solvent (for example 500NS or 600 NS) and Brightstock bases.
  • a conventional cylinder lubricant formulation for slow 2-cycle marine diesel engines is SAE-40 to SAE-60, preferably SAE-50 (SA37 J300) and includes at least 50% by weight a lubricating base of mineral and / or synthetic origin, suitable for use in a marine engine, for example, API Group I, 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.
  • API Group I suitable for use in a marine engine, for example, API Group I, 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%.
  • a conventional cylinder lubricant formulation for slow 2-stroke marine diesel engines contains from 18 to 25% by weight, based on the total weight of lubricant, of a BSS type 1 base oil base oil (residue). distillation, kinematic viscosity at 100 ° C close to 30 mm 2 / s, typically between 28 and 32 mm 2 / s, and density at 15 ° C between 895 and 915 kg / m 3 ), and 50 to 60% by weight, based on the total weight of lubricant, of a Group I 600 NS base oil (distillate, density at 15 ° C between 880 and 900 kg / m 3 , viscosity kinematic at 100 ° C close to 12 mm2 / s).
  • 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% by weight of a dispersing additive is used, typically between 0.5 and 2%, typically between 1 and 1.5% by weight of dispersant.
  • a dispersant chosen from the family of PIB succinimides, optionally borated or blocked with zinc.
  • the lubricant formulation according to the present invention may also contain any functional additives adapted to their use, for example anti-foam additives to counteract the effect of detergents, which may for example be polar polymers such as polymethylsiloxanes, polyacrylates, antioxidant additives and / or or anti rust, for example organo metal detergents or thiadiazoles. These are known to those skilled in the art. These additives are generally present at a content by weight of 0.1 to 5%.
  • 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 lubricants according to the present invention obtained by mixing the compounds taken separately are not in the form of emulsion or microemulsion.
  • the alkoxylated fatty amines contained in the lubricants according to the present invention may in particular be incorporated in a lubricant as separate additives. However, they can also be incorporated into a marine lubricant additive concentrate.
  • Conventional 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 a base oil for cylinder lubricants having a BN determined according to ASTM D-2896 greater than or equal to 15, preferably greater than 20, preferably greater than 30, advantageously greater than 40 milligrams of potash per gram of lubricant.
  • This mixture generally contains, relative to the total weight of the concentrate, a detergent content greater than 70%, preferably greater than 80%, preferably greater than 90%, a dispersant additive content of 2 to 15%, preferably at 10%, a content of other functional additives from 0 to 5%, preferably from 0.1 to 1%.
  • the BN of said concentrates measured according to ASTM D 2896, is generally between 250 and 300 milligrams of potash per gram of concentrate, typically of the order of 275 milligrams of potash per gram of concentrate.
  • An additive concentrate for the preparation of cylinder lubricant having a BN determined according to ASTM D-2896 greater than or equal to 15, preferably greater than 20, preferably greater than 30, advantageously greater than 40 milligrams of potash per gram lubricant, is a concentrate having a BN between 180 and 250, and comprising one or more alkoxylated fatty amines of BN between 100 and 600 mg of potash / g of amine according to ASTM D-2896, the mass percentage of said fatty amines alkoxylated in the concentrate being chosen so as to provide said concentrate a BN contribution determined according to ASTM D-2896 between 10 and 40, preferably between 12 and 30, preferably between 15 and 25, typically of the order 20 milligrams of potash per gram of concentrate.
  • alkoxylated fatty amines of the concentrates according to the invention are those described above and in the examples below.
  • the concentrates may also contain base oil in a small amount (typically between 0 and 5% by weight), but sufficient to facilitate the use of said additive concentrates.
  • the concentrates are diluted 4 to 5 times in a base oil or in a base oil mixture in order to obtain the cylinder lubricants according to the invention.
  • a method for preparing the cylinder lubricants according to the invention comprises the step of mixing such a concentrate in one or more base oils, preferably of group 1, so that said concentrate represents between 20 and 30% by weight , typically of the order of 25% by weight, in the cylinder lubricant.
  • 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 temperature observed when said lubricant containing the basic sites is put in the presence of sulfuric acid.
  • Example 1 This example is intended to describe the method for measuring the contribution of the insoluble metal salts present in the BN-based overbased detergents of the lubricant compositions containing said overbased detergents:
  • BN carbonate hereinafter referred to as BN CaCO3
  • BN CaCO3 is measured on the finished oil or the overbased detergents alone, according to the following procedure. It is his principle to attack the overbasing, carbonate (of calcium), of the sample by sulfuric acid. This carbonate is transformed into carbon dioxide according to the reaction;
  • the reaction vessel may be pyrex, glass, polycarbonate, ... or any other material that promotes heat exchange with the surrounding environment, so that the internal temperature of the vessel equilibrates rapidly with that of the ambient environment.
  • a small amount of 600 NS type fluid base oil is introduced into the reaction vessel containing a small magnet bar. About 2 ml of concentrated sulfuric acid is placed in the reaction vessel, being careful not to stir the medium at this stage.
  • the cap and pressure gauge assembly is screwed onto the reaction vessel.
  • the threads can be greased. We tighten to have a perfect seal.
  • the whole is cleaned with a solvent of the heptane type.
  • the result obtained is the BN CaCO3 expressed in mgKOH / g.
  • the BN supplied by the metallic soaps of detergents also designated by "organic BN" is obtained by difference between the total BN according to ASTM D2896 and the BN CaCO3 thus measured.
  • Example 2 This example aims to describe the enthalpic test for measuring the neutralization efficiency of lubricants vis-à-vis 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 release is followed by the evolution of the temperature over time in an adiabatic reactor of the DEWAR type
  • BN of the lubricants to be tested is preferably in excess of the BN required to neutralize the amount of added acid.
  • BN 70 lubricants the following examples thus add an amount of acid corresponding to the neutralization of 55 BN points.
  • 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 the half-duration of reaction.
  • 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 adiabatic reactor of 300 ml, the inner diameter of which is 52 mm and the internal height 185 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 15.6 to 26 mm.
  • the position of the propeller is set at a distance of about 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 adapted to the measurement of reaction times of the order of 5 to 20 seconds and to the temperature rise measurement of a few tens of degrees to 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 proceeds 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 this experiment to a mass of about 86. g of the lubricant tested.
  • the amount of acid corresponding to the neutralization of 55 BN points is introduced into the reactor.
  • stirring is started to follow the reaction in chemical regime .
  • the acquisition system is permanent.
  • 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.
  • a concentrate in which there is a BN overbased calcium sulfonate equal to 400 mg KOH / g, a dispersant, a BN-based calcium phenate equal to 250 mg KOH / g.
  • This oil is formulated specifically to have sufficient neutralization capacity to be used with high sulfur fuels, namely S contents above 3% or even 3.5%.
  • the reference lubricant contains 25.50% by weight of this concentrate. Its BN of 70 is exclusively provided by the overbased detergents (phenates and overbased sulfonates) contained in said concentrate.
  • This reference lubricant has a viscosity at 100 ° C of between 18 and 21.5 mm 2 / s.
  • the neutralization reaction time of this oil (hereinafter referred to as Href) is 10.59 seconds and its neutralization efficiency index is set to 100.
  • the total BN according to ASTM D-2896, the BN Carbonate, was measured according to the method described in Example 1, the neutralization efficiency index, according to the method described in the example 2.
  • This test uses a Falex brand tribometer with pawn and blocks.
  • the lubricant to be tested is placed in a heated container to the desired temperature.
  • the blocks are placed in the gap of the jaws and the pin fixed on the mandrel.
  • the pion-blocks assembly is immersed in the oil bath.
  • a fixed load (3760 N in our case) is applied on the set pion-blocks through the jaws and a pneumatic cylinder.
  • the pin is rotated at a fixed speed.
  • a distance sensor located on the cylinder permanently measures the gap of the jaws and therefore the wear of the pin and blocks. This wear is recorded and the final wear result reported as a test result.
  • thermal resistance of these compositions was also measured by means of the continuous ECBT test, where the mass of deposits (in mg) generated under given conditions is measured. The lower this mass, the better the thermal resistance.
  • This test simulates both the thermal stability and the detergency of marine lubricants.
  • the test uses aluminum beakers that simulate the shape of pistons. These beakers are placed in a glass container, maintained at a controlled temperature of the order of 60 ° C.
  • the lubricant is placed in these containers, themselves equipped with a wire brush, partially immersed in the lubricant. This brush is rotated at a speed of 1000 rpm, which creates a projection of lubricant on the bottom surface of the beaker.
  • the beaker is maintained at a temperature of 310 ° C by a heating electric resistance, regulated by a thermocouple.
  • compositions B, F, G and H are compositions according to the invention, whose BN is of the order of 43 to 44.
  • compositions according to the invention may for example be used as cylinder oil for marine engine 2 times, with fuels whose content is of the order of 4.5% m / m.
  • the reduction of the overbased detergent content (and therefore insoluble metal salts) thus made possible also allows their use as a cylinder oil for marine engine 2 times, with fuels whose content is low, of the order of 1.5% m / m and less.
  • compositions A and C which do not contain an alkoxylated amine, it is found that the wear properties of the compositions according to the invention are greatly improved.
  • compositions D and E where the contribution of BN by the amines is high (of the order of 10 to 15 points of BN), a deterioration of the thermal resistance is observed with respect to the compositions according to the invention.
  • compositions I, J and K where the percentage of BN provided by the carbonates is high (of the order of 70% and above), there is also a degradation of the thermal resistance compared to the compositions according to the invention. invention.
  • compositions according to the invention have the advantage of a neutralization efficiency enabling them to be used both with high and low sulfur fuels, while having improved anti-wear and thermal resistance properties.
  • Table 1 Lubricating compositions and properties ⁇ / b> AT B C D E F G H I J K Neutral detergents 1.90 1.90 1.90 1.90 7.70 3.85 5.80 0.00 2.80 0.00 Detergents overbased 13.65 13.65 13.65 13.65 9.20 11,10 11.40 10 8.60 12.70 Ethoxylated amine *** - 3.00 6.20 9.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Diamine grasse **** - 3.15 dispersed 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 Defoamers 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Fatty alcohol C1618 0.50 Group I bases 80.21 80.06 77.01 74.21 78.86 80.
  • composition L the lubricant compositions L to O according to the invention have a good neutralization efficiency, good anti-wear properties and thermal resistance regardless of the base oil used (composition L), the neutral detergent used (composition M) the overbased detergent used (composition N) or the ethoxylated amine used (composition O).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)
EP12714700.7A 2011-04-14 2012-04-13 Lubrifiant cylindre pour moteur marin deux temps Not-in-force EP2697344B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL12714700T PL2697344T3 (pl) 2011-04-14 2012-04-13 Smar do cylindrów dla silników okrętowych dwusuwowych

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1153276A FR2974111B1 (fr) 2011-04-14 2011-04-14 Lubrifiant cylindre pour moteur marin deux temps
PCT/EP2012/056812 WO2012140215A1 (fr) 2011-04-14 2012-04-13 Lubrifiant cylindre pour moteur marin deux temps

Publications (2)

Publication Number Publication Date
EP2697344A1 EP2697344A1 (fr) 2014-02-19
EP2697344B1 true EP2697344B1 (fr) 2019-01-09

Family

ID=45974343

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12714700.7A Not-in-force EP2697344B1 (fr) 2011-04-14 2012-04-13 Lubrifiant cylindre pour moteur marin deux temps

Country Status (16)

Country Link
US (1) US9605568B2 (enExample)
EP (1) EP2697344B1 (enExample)
JP (1) JP5914633B2 (enExample)
KR (1) KR101958808B1 (enExample)
CN (1) CN103649285B (enExample)
AR (1) AR086009A1 (enExample)
DK (1) DK2697344T3 (enExample)
ES (1) ES2718833T3 (enExample)
FR (1) FR2974111B1 (enExample)
LT (1) LT2697344T (enExample)
PL (1) PL2697344T3 (enExample)
PT (1) PT2697344T (enExample)
RU (1) RU2598848C2 (enExample)
SG (1) SG194140A1 (enExample)
TR (1) TR201904927T4 (enExample)
WO (1) WO2012140215A1 (enExample)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0615152Y2 (ja) 1988-03-14 1994-04-20 日産自動車株式会社 車両用動力伝達装置
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
FR3002947B1 (fr) * 2013-03-06 2016-03-25 Total Raffinage Marketing Composition lubrifiante pour moteur marin
FR3005474B1 (fr) 2013-05-07 2016-09-09 Total Raffinage Marketing Lubrifiant pour moteur marin
FR3017876B1 (fr) 2014-02-24 2016-03-11 Total Marketing Services Composition d'additifs et carburant de performance comprenant une telle composition
FR3017875B1 (fr) 2014-02-24 2016-03-11 Total Marketing Services Composition d'additifs et carburant de performance comprenant une telle composition
FR3027607B1 (fr) * 2014-10-27 2018-01-05 Total Marketing Services Lubrifiant pour moteur marin
CA2987635C (en) 2015-06-12 2023-09-12 The Lubrizol Corporation Michael adduct amino esters as total base number boosters for marine diesel engine lubricating compositions
FR3039835B1 (fr) * 2015-08-03 2019-07-05 Total Marketing Services Utilisation d'une amine grasse pour prevenir et/ou reduire les pertes metalliques des pieces dans un moteur
FR3043691A1 (fr) * 2015-11-12 2017-05-19 Total Marketing Services Compositions lubrifiantes pour prevenir ou diminuer la combustion anormale dans un moteur de vehicule automobile
PL3424056T3 (pl) * 2016-02-29 2024-08-05 Lord Corporation Dodatek do cieczy magnetoreologicznych
EP3211062B1 (en) * 2016-02-29 2022-07-27 TotalEnergies OneTech Lubricant for a two-stroke marine engine
CN109790480A (zh) 2016-09-12 2019-05-21 路博润公司 船用柴油发动机润滑组合物的总碱值增进剂
FR3065964B1 (fr) * 2017-05-04 2020-03-13 Total Marketing Services Utilisation d'une amine grasse pour reduire et/ou controler la combustion anormale du gaz dans un moteur marin
FR3071252B1 (fr) * 2017-09-19 2020-04-03 Total Marketing Services Utilisation d'ester dans une composition lubrifiante pour ameliorer la proprete moteur
EP3768808A4 (en) 2018-03-20 2021-12-22 Basf Se LUBRICANT COMPOSITION
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010016856A1 (en) * 2007-12-12 2010-02-11 The Lubrizol Corporation Marine diesel cylinder lubricants for improved fuel efficiency

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711406A (en) 1970-06-11 1973-01-16 Chevron Res Lubricating oil containing an hydroxylated amine and an overbased sulfonate or phenate
CA1118750A (en) * 1978-08-01 1982-02-23 Ernst L. Neustadter Lubricating composition
RU1829401C (ru) * 1991-06-28 1996-02-20 Всероссийский научно-исследовательский институт по переработке нефти Смазочная композиция
AU4048793A (en) * 1992-04-15 1993-11-18 Exxon Chemical Patents Inc. Lubricant composition containing mixed friction modifiers
US6333298B1 (en) * 1999-07-16 2001-12-25 Infineum International Limited Molybdenum-free low volatility lubricating oil composition
SG87171A1 (en) * 1999-09-21 2002-03-19 Infineum Int Ltd Lubricating oil compositions
EP1229101A1 (en) * 2001-02-06 2002-08-07 Infineum International Limited Marine diesel engine lubricant
EP1401991A2 (en) * 2001-06-29 2004-03-31 The Lubrizol Corporation Lubricant based on a water in oil emulsion with a suspended solid base
FR2879621B1 (fr) 2004-12-16 2007-04-06 Total France Sa Huile pour moteur marin 4-temps
ES2447428T3 (es) * 2006-10-11 2014-03-12 Total Marketing Services Lubricante marino para fuel con bajo y alto contenido de azufre
EP2045314B1 (en) * 2007-10-04 2017-11-08 Infineum International Limited An overbased metal sulphonate detergent
FR2924439B1 (fr) 2007-12-03 2010-10-22 Total France Composition lubrifiante pour moteur quatre temps a bas taux de cendres
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
FR2943678B1 (fr) 2009-03-25 2011-06-03 Total Raffinage Marketing Polymeres (meth)acryliques de bas poids moleculaire, exempts de composes soufres,metalliques et halogenes et de taux de monomeres residuels faible,leur procede de preparation et leurs utilisations
FR2945754A1 (fr) 2009-05-20 2010-11-26 Total Raffinage Marketing Nouveaux additifs pour huiles transmission
FR2968011B1 (fr) 2010-11-26 2014-02-21 Total Raffinage Marketing Composition lubrifiante pour moteur

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010016856A1 (en) * 2007-12-12 2010-02-11 The Lubrizol Corporation Marine diesel cylinder lubricants for improved fuel efficiency

Also Published As

Publication number Publication date
FR2974111A1 (fr) 2012-10-19
PT2697344T (pt) 2019-04-30
US9605568B2 (en) 2017-03-28
SG194140A1 (en) 2013-11-29
TR201904927T4 (tr) 2019-05-21
CN103649285B (zh) 2016-08-17
CN103649285A (zh) 2014-03-19
PL2697344T3 (pl) 2019-07-31
RU2598848C2 (ru) 2016-09-27
KR20140044799A (ko) 2014-04-15
LT2697344T (lt) 2019-05-10
US20140041610A1 (en) 2014-02-13
EP2697344A1 (fr) 2014-02-19
KR101958808B1 (ko) 2019-03-15
ES2718833T3 (es) 2019-07-04
JP2014510824A (ja) 2014-05-01
RU2013145284A (ru) 2015-05-20
AR086009A1 (es) 2013-11-13
DK2697344T3 (en) 2019-04-23
JP5914633B2 (ja) 2016-05-11
FR2974111B1 (fr) 2013-05-10
WO2012140215A1 (fr) 2012-10-18

Similar Documents

Publication Publication Date Title
EP2697344B1 (fr) Lubrifiant cylindre pour moteur marin deux temps
EP2304006B1 (fr) Lubrifiant cylindre pour moteur marin deux temps
EP2994521B1 (fr) Lubrifiant pour moteur marin
EP2271731B1 (fr) Lubrifiant marin
WO2008043901A2 (fr) Lubrifiant marin pour fioul a basse ou haute teneur en soufre
FR2980799A1 (fr) Composition lubrifiante pour moteur marin
EP3212745B1 (fr) Lubrifiant pour moteur marin
WO2018065606A1 (fr) Composition lubrifiante pour moteur marin ou moteur stationnaire
EP2964736A1 (fr) Composition lubrifiante pour moteur marin

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20131113

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20161027

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TOTAL MARKETING SERVICES

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602012055675

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10M0163000000

Ipc: C10M0159200000

RIC1 Information provided on ipc code assigned before grant

Ipc: C10M 159/20 20060101AFI20180705BHEP

Ipc: C10M 163/00 20060101ALI20180705BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180828

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1087279

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012055675

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: VALIPAT S.A. C/O BOVARD SA NEUCHATEL, CH

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20190415

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 2697344

Country of ref document: PT

Date of ref document: 20190430

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20190404

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: EE

Ref legal event code: FG4A

Ref document number: E017140

Country of ref document: EE

Effective date: 20190403

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2718833

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20190704

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1087279

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190409

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20190401115

Country of ref document: GR

Effective date: 20190620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190509

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012055675

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

26N No opposition filed

Effective date: 20191010

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20200325

Year of fee payment: 9

Ref country code: SE

Payment date: 20200320

Year of fee payment: 9

Ref country code: IE

Payment date: 20200318

Year of fee payment: 9

Ref country code: LT

Payment date: 20200317

Year of fee payment: 9

Ref country code: PL

Payment date: 20200318

Year of fee payment: 9

Ref country code: PT

Payment date: 20200319

Year of fee payment: 9

Ref country code: GR

Payment date: 20200318

Year of fee payment: 9

Ref country code: BG

Payment date: 20200327

Year of fee payment: 9

Ref country code: EE

Payment date: 20200317

Year of fee payment: 9

Ref country code: MC

Payment date: 20200320

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20200323

Year of fee payment: 9

Ref country code: BE

Payment date: 20200319

Year of fee payment: 9

Ref country code: LU

Payment date: 20200319

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20200325

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20200410

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20120413

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

REG Reference to a national code

Ref country code: LT

Ref legal event code: MM4D

Effective date: 20210413

REG Reference to a national code

Ref country code: EE

Ref legal event code: MM4A

Ref document number: E017140

Country of ref document: EE

Effective date: 20210430

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210413

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210414

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211013

Ref country code: RO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210413

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

Ref country code: BG

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211031

Ref country code: LT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210413

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210413

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190109

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20220420

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20220420

Year of fee payment: 11

Ref country code: GB

Payment date: 20220425

Year of fee payment: 11

Ref country code: FR

Payment date: 20220421

Year of fee payment: 11

Ref country code: ES

Payment date: 20220629

Year of fee payment: 11

Ref country code: DE

Payment date: 20220420

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210413

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602012055675

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20230501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230413

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230413

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230501

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230413

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230430

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230413

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20240531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210413