CA2484391C - Marine diesel cylinder lubricants comprising complex detergents - Google Patents
Marine diesel cylinder lubricants comprising complex detergents Download PDFInfo
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- CA2484391C CA2484391C CA2484391A CA2484391A CA2484391C CA 2484391 C CA2484391 C CA 2484391C CA 2484391 A CA2484391 A CA 2484391A CA 2484391 A CA2484391 A CA 2484391A CA 2484391 C CA2484391 C CA 2484391C
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- marine diesel
- lubricant composition
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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
- 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
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
Abstract
A marine diesel cylinder lubricant composition having a total base number of at least 30. The composition includes at least 40 wt% of an oil of lubricating viscosity, at least one detergent prepared from at least two surfactants, preferably phenate and sulphonate surfactants, at least one boron-containing dispersant providing at least 100 ppm of boron, and at least one zinc- containing antiwear additive, preferably a zinc dihydrocarbyl dithiophosphate, providing at least 230 ppm, preferably at least 250 ppm, of zinc. The marine diesel cylinder lubricant composition exhibits reduced wear even when used with high sulphur fuels.
Description
MARINE DIESEL CYLINDER LUBRICANTS COMPRISING
COMPLEX DETERGENTS
This invention concerns a lubricant composition, in particular, a marine diesel cylinder lubricant (MDCL) composition. Marine diesel cylinder lubricant compositions are total loss lubricants and their purpose is to provide a strong oil film between the cylinder liner and the piston rings and to neutralise acids formed by combustion of sulphur compounds in the fuel.
Fuels used for diesel engines generally have a high sulphur content (such as, for example, at least 3.5% sulphur), which results in exhaust gases from diesel engines containing large amounts of sulphur oxides (SOX).. The sulphur oxides react with moisture also present in the exhaust gases to form sulphuric acid which corrodes the engine. Marine diesel cylinder lubricant compositions therefore include overbased metallic detergents to neutralise the sulphuric acid.
Commercial marine diesel cylinder lubricant compositions generally have a,total base number (`TBN') of at least 70 (as determined using ASTM D2896).
Environmental concerns have prompted many areas, such as coastal areas, to require the use of low sulphur fuels, i.e. fuels including less than 1.00% by weight of sulphur, which allows the use of marine diesel cylinder lubricant compositions having lower total base numbers such as, for example, 40. This therefore creates the need for ships to carry tanks for two different lubricants.
US 4,842,755 discloses a marine diesel cylinder lubricant having a base number of at least 60. The composition includes a borated ashless dispersant, one or more overbased metal compounds and a zinc dialkyl dithiophosphate providing 0.02 to 0.023 wt% (200-230 ppm) of zinc (see claim 1). The specific examples show that increasing the amount of zinc above 230 ppm results in a loss in performance benefits in ring and liner wear.
COMPLEX DETERGENTS
This invention concerns a lubricant composition, in particular, a marine diesel cylinder lubricant (MDCL) composition. Marine diesel cylinder lubricant compositions are total loss lubricants and their purpose is to provide a strong oil film between the cylinder liner and the piston rings and to neutralise acids formed by combustion of sulphur compounds in the fuel.
Fuels used for diesel engines generally have a high sulphur content (such as, for example, at least 3.5% sulphur), which results in exhaust gases from diesel engines containing large amounts of sulphur oxides (SOX).. The sulphur oxides react with moisture also present in the exhaust gases to form sulphuric acid which corrodes the engine. Marine diesel cylinder lubricant compositions therefore include overbased metallic detergents to neutralise the sulphuric acid.
Commercial marine diesel cylinder lubricant compositions generally have a,total base number (`TBN') of at least 70 (as determined using ASTM D2896).
Environmental concerns have prompted many areas, such as coastal areas, to require the use of low sulphur fuels, i.e. fuels including less than 1.00% by weight of sulphur, which allows the use of marine diesel cylinder lubricant compositions having lower total base numbers such as, for example, 40. This therefore creates the need for ships to carry tanks for two different lubricants.
US 4,842,755 discloses a marine diesel cylinder lubricant having a base number of at least 60. The composition includes a borated ashless dispersant, one or more overbased metal compounds and a zinc dialkyl dithiophosphate providing 0.02 to 0.023 wt% (200-230 ppm) of zinc (see claim 1). The specific examples show that increasing the amount of zinc above 230 ppm results in a loss in performance benefits in ring and liner wear.
An aim of the present invention is to provide a marine diesel cylinder lubricant composition having a total base number of at least 30, preferably at least 35, more preferably at least 40, and more preferably at least 60, (ASTM D 2896-01), that is suitable for use with both high and low sulphur fuels.
A further aim of the present invention is to provide a marine diesel cylinder lubricant composition having a total base number of at least 30, preferably 35 or more (ASTM D 2896-01), that is suitable for use with both high and low sulphur fuels, whilst still providing the required level of protection against corrosive wear when used with a high sulphur fuel.
In accordance with the present invention there is provided a marine diesel cylinder lubricant composition having a total base number, as determined according to ASTM D2896, of at least 30, preferably at least 35 or more, and comprising:
- at least 40 wt%, based on the total amount of the marine diesel cylinder lubricant composition, of an oil of lubricating viscosity, - at least one detergent prepared from at least two surfactants, preferably phenate and sulphonate surfactants, - at least one boron-containing dispersant providing at least 100 ppm of boron, and - at least one zinc-containing antiwear additive, preferably a zinc dihydrocarbyl dithiophosphate, providing more than 230 ppm, preferably at least 250 ppm, of zinc.
The inventors have surprisingly found, considering the teachings of US
4,842,755, that in a marine diesel cylinder lubricant composition including a detergent prepared from at least two surfactants, the use of more than 230 ppm zinc provides increased protection against wear.
The inventors have also found that the marine diesel cylinder lubricant composition defined above provides a good level of wear protection even at a low total base number, such as, for example, 40, when used with a high sulphur fuel.
In accordance with the present invention there is also provided a method of operating a marine diesel engine, the method including the step of using the marine diesel cylinder lubricant composition defined above to lubricate the engine.
In accordance with the present invention there is also provided use of the marine diesel cylinder lubricant composition defined above to reduce wear in a marine diesel engine.
Oil of Lubricating Viscosity The oil of lubricating viscosity (sometimes referred to as lubricating oil) may be any oil suitable for the lubrication of a marine engine. The lubricating oil may suitably be an animal, a vegetable or a mineral oil. Suitably the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil. Alternatively, the lubricating oil may be a synthetic lubricating oil.
Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed. The lubricating oil may generally comprise greater than 60, typically greater than 70, mass % of the composition, and typically have a kinematic viscosity at 100 C
of from 2 to 40, for example for 3 to 15, mm2s'' and a viscosity index of from 80 to 100, for example from 90 to 95.
Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures. Hydrocracked oils typically have a kinematic viscosity at 100 C of from 2 to 40, for example from 3 to 15, mm2s" and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
The oil may include `brightstock' which refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100 C of from 28 to 36 mm2s 1 and are typically used in a proportion of less than 40, preferably less than 30, more preferably less than 20, mass %, based on the mass of the composition.
The marine diesel cylinder lubricant composition preferably includes at least wt% of oil of lubricating viscosity, more preferably at least 60 wt% of oil of lubricating viscosity, even more preferably at least 70 wt% of oil of lubricating viscosity, based on the total amount of the marine diesel cylinder lubricant ' composition.
Deteraent including at least two Surfactants A detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
The detergent comprises a polar head with a long hydrophobic tail. Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
The detergent includes at least two surfactants, preferably at least phenate and sulphonate surfactants. The detergent may be referred to as a complex/hybrid detergent. The complex detergent preferably includes at least 5 mass% of phenate, more preferably at least 10 mass% of phenate, based on the total 5 amount of the detergent. The complex detergent preferably includes at least mass% of sulphonate, more preferably at least 8 mass% of sulphonate, based on the total amount of the detergent. The detergent preferably also includes a salicylate surfactant. The detergent preferably includes at least 5 mass% of salicylate, more preferably at least 10 mass% of salicylate, based on the total amount of the detergent. The amount of surfactant in the complex detergent can be determined using techniques such as chromatography, spectroscopy and/or titration, well known to persons skilled in the art. The detergent may also include other surfactants such as, for example, a thiophosphate, a naphthenate, or an oil-soluble carboxylate. The surfactant groups are incorporated during the overbasing process. The metal may be an alkali metal or an alkaline earth metal such as sodium, potassium, lithium, calcium and magnesium. Calcium is preferred.
Examples of complex detergents are described in WO 97/46643, WO 97/46644, WO 97/46645, WO 97/46646 and WO 97/46647.
Preferably, the detergent has a TBN in the range of 250 to 500, more preferably 280 to 480, even more preferably 300 to 450.
The marine diesel cylinder lubricant composition preferably includes at least wt%, preferably at least 5 wt%, more preferably at least 8 wt%, of detergent including at least two surfactants, based on the total amount of the marine diesel cylinder lubricant composition.
The marine diesel cylinder lubricant may also include further detergents such as a calcium phenate detergent, a calcium sulphonate detergent or a calcium salicylate detergent. The further detergent may have a low TBN of less than 50, a medium TBN ranging from 50 to 150 or a high TBN of more than 150. The marine diesel cylinder lubricant composition preferably includes at least 4 wt%, preferably at least 6 wt%, of a further detergent, based on the total amount of the marine diesel cylinder lubricant composition.
Disaersant The marine diesel cylinder lubricant composition includes at least one dispersant providing at least 100 ppm of boron. A dispersant is an additive for a lubricating composition whose primary function in cylinder lubricants is to accelerate neutralization of acids by the detergent system.
A noteworthy class of dispersants are "ashless", meaning a non-metallic organic material that forms substantially no ash on combustion, in contrast to metal-containing, hence ash-forming, materials. Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g., an 0, P or N atom. The hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms. Thus, ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
Examples of ashless dispersants are borated succinimides, e.g. borated polyisobutene succinic anhydride; and polyamine condensation products that are borated.
The marine diesel cylinder lubricant composition preferably includes at least ppm, more preferably at least 200 ppm, of boron, based on the total amount of the marine diesel cylinder lubricant composition.
A further aim of the present invention is to provide a marine diesel cylinder lubricant composition having a total base number of at least 30, preferably 35 or more (ASTM D 2896-01), that is suitable for use with both high and low sulphur fuels, whilst still providing the required level of protection against corrosive wear when used with a high sulphur fuel.
In accordance with the present invention there is provided a marine diesel cylinder lubricant composition having a total base number, as determined according to ASTM D2896, of at least 30, preferably at least 35 or more, and comprising:
- at least 40 wt%, based on the total amount of the marine diesel cylinder lubricant composition, of an oil of lubricating viscosity, - at least one detergent prepared from at least two surfactants, preferably phenate and sulphonate surfactants, - at least one boron-containing dispersant providing at least 100 ppm of boron, and - at least one zinc-containing antiwear additive, preferably a zinc dihydrocarbyl dithiophosphate, providing more than 230 ppm, preferably at least 250 ppm, of zinc.
The inventors have surprisingly found, considering the teachings of US
4,842,755, that in a marine diesel cylinder lubricant composition including a detergent prepared from at least two surfactants, the use of more than 230 ppm zinc provides increased protection against wear.
The inventors have also found that the marine diesel cylinder lubricant composition defined above provides a good level of wear protection even at a low total base number, such as, for example, 40, when used with a high sulphur fuel.
In accordance with the present invention there is also provided a method of operating a marine diesel engine, the method including the step of using the marine diesel cylinder lubricant composition defined above to lubricate the engine.
In accordance with the present invention there is also provided use of the marine diesel cylinder lubricant composition defined above to reduce wear in a marine diesel engine.
Oil of Lubricating Viscosity The oil of lubricating viscosity (sometimes referred to as lubricating oil) may be any oil suitable for the lubrication of a marine engine. The lubricating oil may suitably be an animal, a vegetable or a mineral oil. Suitably the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil. Alternatively, the lubricating oil may be a synthetic lubricating oil.
Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed. The lubricating oil may generally comprise greater than 60, typically greater than 70, mass % of the composition, and typically have a kinematic viscosity at 100 C
of from 2 to 40, for example for 3 to 15, mm2s'' and a viscosity index of from 80 to 100, for example from 90 to 95.
Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures. Hydrocracked oils typically have a kinematic viscosity at 100 C of from 2 to 40, for example from 3 to 15, mm2s" and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
The oil may include `brightstock' which refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100 C of from 28 to 36 mm2s 1 and are typically used in a proportion of less than 40, preferably less than 30, more preferably less than 20, mass %, based on the mass of the composition.
The marine diesel cylinder lubricant composition preferably includes at least wt% of oil of lubricating viscosity, more preferably at least 60 wt% of oil of lubricating viscosity, even more preferably at least 70 wt% of oil of lubricating viscosity, based on the total amount of the marine diesel cylinder lubricant ' composition.
Deteraent including at least two Surfactants A detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
The detergent comprises a polar head with a long hydrophobic tail. Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
The detergent includes at least two surfactants, preferably at least phenate and sulphonate surfactants. The detergent may be referred to as a complex/hybrid detergent. The complex detergent preferably includes at least 5 mass% of phenate, more preferably at least 10 mass% of phenate, based on the total 5 amount of the detergent. The complex detergent preferably includes at least mass% of sulphonate, more preferably at least 8 mass% of sulphonate, based on the total amount of the detergent. The detergent preferably also includes a salicylate surfactant. The detergent preferably includes at least 5 mass% of salicylate, more preferably at least 10 mass% of salicylate, based on the total amount of the detergent. The amount of surfactant in the complex detergent can be determined using techniques such as chromatography, spectroscopy and/or titration, well known to persons skilled in the art. The detergent may also include other surfactants such as, for example, a thiophosphate, a naphthenate, or an oil-soluble carboxylate. The surfactant groups are incorporated during the overbasing process. The metal may be an alkali metal or an alkaline earth metal such as sodium, potassium, lithium, calcium and magnesium. Calcium is preferred.
Examples of complex detergents are described in WO 97/46643, WO 97/46644, WO 97/46645, WO 97/46646 and WO 97/46647.
Preferably, the detergent has a TBN in the range of 250 to 500, more preferably 280 to 480, even more preferably 300 to 450.
The marine diesel cylinder lubricant composition preferably includes at least wt%, preferably at least 5 wt%, more preferably at least 8 wt%, of detergent including at least two surfactants, based on the total amount of the marine diesel cylinder lubricant composition.
The marine diesel cylinder lubricant may also include further detergents such as a calcium phenate detergent, a calcium sulphonate detergent or a calcium salicylate detergent. The further detergent may have a low TBN of less than 50, a medium TBN ranging from 50 to 150 or a high TBN of more than 150. The marine diesel cylinder lubricant composition preferably includes at least 4 wt%, preferably at least 6 wt%, of a further detergent, based on the total amount of the marine diesel cylinder lubricant composition.
Disaersant The marine diesel cylinder lubricant composition includes at least one dispersant providing at least 100 ppm of boron. A dispersant is an additive for a lubricating composition whose primary function in cylinder lubricants is to accelerate neutralization of acids by the detergent system.
A noteworthy class of dispersants are "ashless", meaning a non-metallic organic material that forms substantially no ash on combustion, in contrast to metal-containing, hence ash-forming, materials. Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g., an 0, P or N atom. The hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms. Thus, ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
Examples of ashless dispersants are borated succinimides, e.g. borated polyisobutene succinic anhydride; and polyamine condensation products that are borated.
The marine diesel cylinder lubricant composition preferably includes at least ppm, more preferably at least 200 ppm, of boron, based on the total amount of the marine diesel cylinder lubricant composition.
Antiwear Additive The antiwear additive provides at least 230 ppm, preferably at least 250 ppm, of zinc, based on the total amount of the marine diesel cylinder lubricant composition. The antiwear additive preferably provides at least 275 ppm, more preferably at least 300 ppm, even more preferably at least 325 ppm, even more preferably at least 350 ppm, even more preferably at least 375ppm and most preferably at least 385 ppm, of zinc.
The antiwear additive may be prepared in accordance with known techniques by firstly forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary. To make the zinc salt, any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed.
Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
The preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
[(RO) (R'O) P(S)S]2 Zn where R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, 1-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil-solubility, the total number of carbon atoms (i.e. in R and R) in the dithiophoshoric acid will generally be 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
Anti-oxidants The marine diesel cylinder lubricant composition may include at least one anti-oxidant. The anti-oxidant may be aminic or phenolic. As examples of amines there may be mentioned secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms. As examples of anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
Preferably, the anti-oxidant, if present, is provided in the composition in an amount of up to 3 mass %, based on the total amount of the marine diesel cylinder lubricant.
Other additives such as pour point depressants, anti-foamants, and/or demulsifiers may be provided, if necessary.
The terms `oil-soluble' or `oil-dispersable' as used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
The antiwear additive may be prepared in accordance with known techniques by firstly forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary. To make the zinc salt, any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed.
Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
The preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
[(RO) (R'O) P(S)S]2 Zn where R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, 1-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil-solubility, the total number of carbon atoms (i.e. in R and R) in the dithiophoshoric acid will generally be 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
Anti-oxidants The marine diesel cylinder lubricant composition may include at least one anti-oxidant. The anti-oxidant may be aminic or phenolic. As examples of amines there may be mentioned secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms. As examples of anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
Preferably, the anti-oxidant, if present, is provided in the composition in an amount of up to 3 mass %, based on the total amount of the marine diesel cylinder lubricant.
Other additives such as pour point depressants, anti-foamants, and/or demulsifiers may be provided, if necessary.
The terms `oil-soluble' or `oil-dispersable' as used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
The lubricant compositions of this invention comprise defined individual (i.e.
separate) components that may or may not remain the same chemically before and after mixing.
The present invention is illustrated by, but in no way limited to, the following examples.
Examples Marine diesel.cylinder lubricant compositions were prepared having TBNs of either 40 or 70: The lubricant compositions comprised: an overbased complex calcium detergent including phenate and sulphonate surfactants; a calcium phenate having a base number of 250; a borated dispersant; and an anti-wear agent.
TM
The lubricant compositions were subjected. to the Bolnes Test using a Bolnes crosshead engine (a single cylinder 2-stroke engine, the Bolnes 3DNL), calibrated and stabilized, operating on a fuel including about 3.5% sulphur.
The Bolnes engine speed was 500 rpm with a lubricant feed rate of 1.00 gtkwh. Each lubricant composition was tested for 96 hours. The test conditions were designed to create corrosive wear of the cylinder liner over this time. Wear was measured in microns in specific calibrated places on the cylinder liner. The average recorded wear is reported below. The lower the recorded result, the less wear of the cylinder liner.
Comparative Example 2 Example 3 Example 4 Example 5 Example 1 Detergent 15.24 12.10 10.80 including at least two surfactants Detergent 14.30 7.15 including at least two surfactants 250 TBN 3.34 8.00 10.00 8.02 6.00 Calcium Phenate Detergent Borated 3.05 3.00 Dispersant Borated 3.00 2.67 2.00 Dispersant Antiwear 0.28 1.00 0.50 0.67 0.50 Agent Antioxidant 0.50 Base oils 78.09 75.90 75.20 74.34 84.35 Base Number 70 70 70 70 40 (ASTM D
2896-01) Boron (ppm) 107 105 390 347 260 Zinc (ppm) 216 770 385 516 385 Bolnes Test Liner Wear, 19 10 11 12 12 average The above table clearly shows that less wear is produced with marine diesel 5 cylinder lubricants including 385 ppm or more of zinc when the detergent is prepared from at least two surfactants. It is particularly surprising that example 5, which has a TBN of 40, produces less wear with the high sulphur fuel than comparative example 1 which has a TBN of 70.
separate) components that may or may not remain the same chemically before and after mixing.
The present invention is illustrated by, but in no way limited to, the following examples.
Examples Marine diesel.cylinder lubricant compositions were prepared having TBNs of either 40 or 70: The lubricant compositions comprised: an overbased complex calcium detergent including phenate and sulphonate surfactants; a calcium phenate having a base number of 250; a borated dispersant; and an anti-wear agent.
TM
The lubricant compositions were subjected. to the Bolnes Test using a Bolnes crosshead engine (a single cylinder 2-stroke engine, the Bolnes 3DNL), calibrated and stabilized, operating on a fuel including about 3.5% sulphur.
The Bolnes engine speed was 500 rpm with a lubricant feed rate of 1.00 gtkwh. Each lubricant composition was tested for 96 hours. The test conditions were designed to create corrosive wear of the cylinder liner over this time. Wear was measured in microns in specific calibrated places on the cylinder liner. The average recorded wear is reported below. The lower the recorded result, the less wear of the cylinder liner.
Comparative Example 2 Example 3 Example 4 Example 5 Example 1 Detergent 15.24 12.10 10.80 including at least two surfactants Detergent 14.30 7.15 including at least two surfactants 250 TBN 3.34 8.00 10.00 8.02 6.00 Calcium Phenate Detergent Borated 3.05 3.00 Dispersant Borated 3.00 2.67 2.00 Dispersant Antiwear 0.28 1.00 0.50 0.67 0.50 Agent Antioxidant 0.50 Base oils 78.09 75.90 75.20 74.34 84.35 Base Number 70 70 70 70 40 (ASTM D
2896-01) Boron (ppm) 107 105 390 347 260 Zinc (ppm) 216 770 385 516 385 Bolnes Test Liner Wear, 19 10 11 12 12 average The above table clearly shows that less wear is produced with marine diesel 5 cylinder lubricants including 385 ppm or more of zinc when the detergent is prepared from at least two surfactants. It is particularly surprising that example 5, which has a TBN of 40, produces less wear with the high sulphur fuel than comparative example 1 which has a TBN of 70.
Claims (28)
1. A marine diesel cylinder lubricant composition having a total base number, as determined according to ASTM D2896, of at least 30 and comprising:
- at least 40 wt% of an oil of lubricating viscosity, - at least one detergent prepared from at least two surfactants, - at least one boron-containing dispersant providing at least 100 ppm of boron, and - at least one zinc-containing antiwear additive, providing more than 230 ppm of zinc.
- at least 40 wt% of an oil of lubricating viscosity, - at least one detergent prepared from at least two surfactants, - at least one boron-containing dispersant providing at least 100 ppm of boron, and - at least one zinc-containing antiwear additive, providing more than 230 ppm of zinc.
2. The marine diesel cylinder lubricant composition of claim 1, wherein the at least two surfactants are a phenate surfactant and a sulphonate surfactant.
3. The marine diesel cylinder lubricant composition of claim 1 or 2, wherein the at least one zinc-containing antiwear additive is a zinc dihydrocarbyl dithiophosphate.
4. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 3, wherein the at least one zinc-containing antiwear additive provides at least 250 ppm of zinc.
5. The marine diesel cylinder lubricant composition as claimed in claim 2, wherein the detergent includes at least 5 mass% of phenate and at least 5 mass%
of sulphonate, based on the total amount of the detergent.
of sulphonate, based on the total amount of the detergent.
6. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 5, wherein the detergent further includes a salicylate surfactant.
7. The marine diesel cylinder lubricant composition as claimed in claim 6, wherein the salicylate surfactant includes at least 5 mass % of salicylate, based on the total amount of the detergent.
8. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 7, wherein the lubricant has a base number of at least 35.
9. The marine diesel cylinder lubricant composition as claimed in claim 8, wherein the lubricant has a base number of at least 40.
10. The marine diesel cylinder lubricant composition as claimed in claim 8, wherein the lubricant has a base number of at least 60.
11. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 10, wherein the dispersant provides at least 150 ppm of boron, based on the total amount of the marine diesel cylinder lubricant composition.
12. The marine diesel cylinder lubricant composition as claimed in claim 11, wherein the dispersant provides at least 200 ppm of boron, based on the total amount of the marine diesel cylinder lubricant composition.
13. The marine diesel cylinder lubricant composition as claimed in any one of claims I to 12, wherein the antiwear additive provides at least 275 ppm of zinc.
14. The marine diesel cylinder lubricant composition as claimed in claim 13, wherein the antiwear additive provides at least 300 ppm of zinc.
15. The marine diesel cylinder lubricant composition as claimed in claim 13, wherein the antiwear additive provides at least 325 ppm of zinc.
16. The marine diesel cylinder lubricant composition as claimed in claim 13, wherein the antiwear additive provides at least 350 ppm of zinc.
17. The marine diesel cylinder lubricant composition as claimed in claim 13, wherein the antiwear additive provides at least 375 ppm of zinc.
18. The marine diesel cylinder lubricant composition as claimed in claim 13, wherein the antiwear additive provides at least 385 ppm of zinc.
19. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 18, wherein the antiwear additive is an oil-soluble salt of a dihydrocarbyl dithiophosphoric acid represented by the following formula:
[(RO) (R1O) P(S)S]2 Zn where R and R1 are the same or different hydrocarbyl radicals containing from to 18 carbon atoms.
[(RO) (R1O) P(S)S]2 Zn where R and R1 are the same or different hydrocarbyl radicals containing from to 18 carbon atoms.
20. The marine diesel cylinder lubricant composition as claimed in claim 19, wherein R and R1 are the same or different hydrocarbyl radicals containing from 2 to 12 carbon atoms.
21. The marine diesel cylinder lubricant composition as claimed in claim 19 or 20, wherein R and R1 are the same or different hydrocarbyl radicals comprising alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
22. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 21, further including an aminic or phenolic antioxidant.
23. A method of operating a marine diesel engine, the method including the step of using the marine diesel cylinder lubricant composition claimed in any one of claims 1 to 22 to lubricate the engine.
24. The method as claimed in claim 23, wherein the marine diesel engine uses a fuel having a sulphur content of at least 3.0%.
25. The method as claimed in claim 23, wherein the marine diesel engine uses a fuel having a sulphur content of at least 3.5%.
26. Use of the marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 22 to reduce wear in a marine diesel engine.
27. The use claimed in claim 26, wherein the marine diesel cylinder lubricant composition is used with the fuel having a sulphur level of at least 3.0%.
28. The use claimed in claim 26, wherein the marine diesel cylinder lubricant composition is used with the fuel having a sulphur level of at least 3.5%.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03256376.9 | 2003-10-09 | ||
EP03256376.9A EP1522572B1 (en) | 2003-10-09 | 2003-10-09 | Lubricant composition |
Publications (2)
Publication Number | Publication Date |
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CA2484391A1 CA2484391A1 (en) | 2005-04-09 |
CA2484391C true CA2484391C (en) | 2011-12-06 |
Family
ID=34307001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA2484391A Active CA2484391C (en) | 2003-10-09 | 2004-10-08 | Marine diesel cylinder lubricants comprising complex detergents |
Country Status (8)
Country | Link |
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US (1) | US20050153847A1 (en) |
EP (1) | EP1522572B1 (en) |
JP (2) | JP2005113151A (en) |
CN (2) | CN103351908A (en) |
AU (1) | AU2004218713B2 (en) |
CA (1) | CA2484391C (en) |
ES (1) | ES2604192T3 (en) |
SG (1) | SG111306A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5158780B2 (en) * | 2004-10-06 | 2013-03-06 | ザ ルブリゾル コーポレイション | Lubricating composition containing sulfonate |
EP1728849B1 (en) * | 2005-05-27 | 2019-12-18 | Infineum International Limited | A method of lubricating the cylinder liner and the crankcase of a cross-head marine diesel engine |
JP5158971B2 (en) | 2005-10-14 | 2013-03-06 | ザ ルブリゾル コーポレイション | Method for lubricating marine diesel engines |
KR20070055386A (en) * | 2005-11-25 | 2007-05-30 | 인피늄 인터내셔날 리미티드 | A method of operating a marine or stationary diesel engine |
JP5020622B2 (en) * | 2005-12-28 | 2012-09-05 | シェブロンジャパン株式会社 | Lubricating oil composition for diesel internal combustion engine |
EP1903093B1 (en) | 2006-09-19 | 2017-12-20 | Infineum International Limited | A lubricating oil composition |
US20080153723A1 (en) | 2006-12-20 | 2008-06-26 | Chevron Oronite Company Llc | Diesel cylinder lubricant oil composition |
FR2932813B1 (en) * | 2008-06-18 | 2010-09-03 | Total France | LUBRICANT CYLINDER FOR MARINE ENGINE TWO TIMES |
EP2507347A1 (en) * | 2009-11-30 | 2012-10-10 | The Lubrizol Corporation | Methods of controlling sulfur trioxide levels in internal combustion engines |
JP5483329B2 (en) * | 2009-12-24 | 2014-05-07 | Jx日鉱日石エネルギー株式会社 | Cylinder lubricating oil composition for crosshead type diesel engine |
EP3066180B1 (en) | 2013-11-06 | 2021-01-13 | Chevron Oronite Technology B.V. | Marine diesel cylinder lubricant oil compositions |
SG11201603378WA (en) | 2013-11-06 | 2016-05-30 | Chevron Oronite Technology Bv | Marine diesel cylinder lubricant oil compositions |
CN104531269B (en) * | 2014-12-05 | 2017-06-13 | 中国石油天然气股份有限公司 | A kind of plunger type engine lubricant oil composite peculiar to vessel |
EP3325584B1 (en) | 2015-07-22 | 2024-04-03 | Chevron Oronite Technology B.V. | Marine diesel cylinder lubricant oil compositions |
CN111500349A (en) * | 2020-05-27 | 2020-08-07 | 中国石油化工股份有限公司 | Marine diesel engine oil composition, preparation method and application thereof |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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GB8602627D0 (en) | 1986-02-04 | 1986-03-12 | Exxon Chemical Patents Inc | Marine lubricating composition |
GB8804171D0 (en) * | 1988-02-23 | 1988-03-23 | Exxon Chemical Patents Inc | Dispersant for marine diesel cylinder lubricant |
GB9611424D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
GB9709006D0 (en) * | 1997-05-02 | 1997-06-25 | Exxon Chemical Patents Inc | Lubricating oil compositions |
CN1105165C (en) * | 1997-11-28 | 2003-04-09 | 英菲诺姆美国公司 | Lubricating oil compositions |
US6277794B1 (en) * | 1998-12-28 | 2001-08-21 | Infineum Usa L.P. | Lubricant compositions |
JP2000192069A (en) * | 1998-12-28 | 2000-07-11 | Oronite Japan Ltd | Lubricating oil composition and additive composition for diesel internal combustion engine |
GB9900035D0 (en) * | 1999-01-04 | 1999-02-24 | Infineum Uk Ltd | Overbased metal detergents |
ATE491775T1 (en) * | 1999-09-13 | 2011-01-15 | Infineum Int Ltd | A METHOD OF LUBRICATION FOR TWO-STROKE MARINE DIESEL ENGINES |
JP4011815B2 (en) * | 2000-02-14 | 2007-11-21 | シェブロンジャパン株式会社 | Lubricating oil composition for two-cycle crosshead diesel internal combustion engine and additive composition for lubricating oil composition |
US6551965B2 (en) * | 2000-02-14 | 2003-04-22 | Chevron Oronite Company Llc | Marine diesel engine lubricating oil composition having improved high temperature performance |
DE60117913D1 (en) * | 2000-09-22 | 2006-05-11 | Infineum Int Ltd | Trunk piston engine lubrication |
EP1233052A1 (en) * | 2001-02-16 | 2002-08-21 | Infineum International Limited | Overbased detergent additives |
EP1298189A1 (en) * | 2001-09-28 | 2003-04-02 | Infineum International Limited | Lubricating oil compositions for marine diesel engines |
-
2003
- 2003-10-09 EP EP03256376.9A patent/EP1522572B1/en not_active Expired - Lifetime
- 2003-10-09 ES ES03256376.9T patent/ES2604192T3/en not_active Expired - Lifetime
-
2004
- 2004-09-22 US US10/947,093 patent/US20050153847A1/en not_active Abandoned
- 2004-10-08 JP JP2004296246A patent/JP2005113151A/en active Pending
- 2004-10-08 CA CA2484391A patent/CA2484391C/en active Active
- 2004-10-08 SG SG200406894A patent/SG111306A1/en unknown
- 2004-10-09 CN CN2013102855442A patent/CN103351908A/en active Pending
- 2004-10-09 CN CNA2004101038286A patent/CN1637126A/en active Pending
- 2004-10-11 AU AU2004218713A patent/AU2004218713B2/en not_active Ceased
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2012
- 2012-05-09 JP JP2012107307A patent/JP5436615B2/en active Active
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JP5436615B2 (en) | 2014-03-05 |
CN103351908A (en) | 2013-10-16 |
AU2004218713A1 (en) | 2005-04-28 |
AU2004218713B2 (en) | 2009-06-11 |
ES2604192T3 (en) | 2017-03-03 |
JP2012144747A (en) | 2012-08-02 |
EP1522572B1 (en) | 2016-11-16 |
CA2484391A1 (en) | 2005-04-09 |
JP2005113151A (en) | 2005-04-28 |
EP1522572A1 (en) | 2005-04-13 |
SG111306A1 (en) | 2005-05-30 |
CN1637126A (en) | 2005-07-13 |
US20050153847A1 (en) | 2005-07-14 |
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