EP2113021A1 - Lubricant base oils and lubricant compositions and methods for making them - Google Patents

Lubricant base oils and lubricant compositions and methods for making them

Info

Publication number
EP2113021A1
EP2113021A1 EP08709441A EP08709441A EP2113021A1 EP 2113021 A1 EP2113021 A1 EP 2113021A1 EP 08709441 A EP08709441 A EP 08709441A EP 08709441 A EP08709441 A EP 08709441A EP 2113021 A1 EP2113021 A1 EP 2113021A1
Authority
EP
European Patent Office
Prior art keywords
weight
base stock
base
liquid lubricant
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08709441A
Other languages
German (de)
French (fr)
Other versions
EP2113021B1 (en
Inventor
Stephen Bruce Ames
John Philip Davies
John Philip Liddy
Kok-Chye Lim
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.)
BP PLC
Original Assignee
BP PLC
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 BP PLC filed Critical BP PLC
Priority to EP08709441.3A priority Critical patent/EP2113021B1/en
Publication of EP2113021A1 publication Critical patent/EP2113021A1/en
Application granted granted Critical
Publication of EP2113021B1 publication Critical patent/EP2113021B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C10M101/025—Petroleum fractions waxes
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 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
    • 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
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • 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
    • C10M2203/104—Aromatic fractions
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/065—Saturated Compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/14—Metal deactivation
    • 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
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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
    • C10N2030/40—Low content or no content compositions
    • 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
    • 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

Definitions

  • This invention relates to compositions and methods and in particular to lubricant base oils and lubricant compositions and to methods for making them.
  • Lubricant compositions generally comprise a base oil and one or more additives.
  • base stocks which are used for base oils are defined as belonging to one of five Groups as set out in Table I below.
  • Group I base stocks are generally preferred to Group II base stocks for the manufacture of lubricant compositions for marine 2-stroke and 4-stroke engines, particularly for engines operating on heavy fuel oil.
  • Group II base stocks are becoming increasingly more readily available because older manufacturing capacity for Group I basestock is being closed and new manufacturing capacity tends to manufacture Group II base stock.
  • Group II base stocks may have some performance disadvantages compared to Group I base stocks when used in some lubricant compositions, for example in marine lubricants. These disadvantages may include poorer dispersancy, poorer seal swell performance, poorer solubility of additives, lower compatibility with fuel oil in marine engine applications (which can lead to deposit formation, for example in cool parts of the engine) and/or in some aspects, poorer oxidative stability.
  • Hydroprocessed base stocks may have advantages and disadvantages (Deckman, D.E. et al., Hart's Lubricants World, July 1997, pages 46 - 50) when used in industrial lubricant applications (Deckman D. E. et al., Hart's Lubricants World, Sept 1997, pages 20-26) and in commercial, personal vehicle and marine engine oils (Deckman D. E. et al., Hart's Lubricants World, Sept 1997, pages 27 - 28).
  • Base stocks which are made by hydroprocessing including Group II and Group III base stocks, have lower aromatics content and lower sulphur content than Group I base stocks.
  • Base stocks which are polyalphaolefins may also have a high degree of saturation.
  • Base stocks derived from Fischer-Tropsch synthesised, waxy, paraffmic hydrocarbon materials also have a low aromatics content and so may also exhibit at least some of the poorer performance of Group II and Group III base stocks compared to Group I base stocks.
  • WO 00/14187 and WO 2005/066314 relate to lubricant compositions comprising Fischer Tropsch derived base stock.
  • a liquid lubricant base oil composition comprising (i) a base stock comprising at least 95 % by weight saturated hydrocarbons and (ii) 0.2 to 30 % by weight, preferably 0.2 to 18 % or 1 to 30 % by weight, more preferably 1.0 to 18 % by weight, of an aromatic extract, in which the aromatic extract has a dimethyl sulphoxide extractable poly cyclic aromatics content of less than 3 weight %.
  • a method of making a liquid lubricant base oil composition as hereindefined comprises blending a base stock comprising at least 95 % by weight saturated hydrocarbons with sufficient aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % to make a liquid lubricant base oil composition as hereindefined.
  • a liquid lubricant composition comprising a lubricant base oil composition as hereindefined and one or more additives, preferably selected from the group consisting of detergents, dispersants, anti-wear additives, anti-oxidants, anti-foams, corrosion inhibitors, pour point depressants, friction modifiers, tackifiers and viscosity index improvers.
  • the present invention solves the problem defined above by the use of 0.2 to 30 % by weight of an aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % in a liquid lubricant base oil composition which base oil comprises a base stock comprising at least 95 % by weight saturated hydrocarbons.
  • This provides a lubricant base oil which overcomes or at least mitigates, at least some of the deficiencies which may be associated with such base stocks.
  • the lubricant base oil composition of the present invention comprises 0.2 to 30 % by weight of an aromatic extract.
  • the lubricant base oil composition of the present invention comprises 0.2 to 18 % or 1.0 to 30 % by weight of the aromatic extract. More preferably, the lubricant base oil composition of the present invention comprises 1.0 to 18 % by weight aromatic extract.
  • the base stock comprising at least 95 % by weight saturated hydrocarbons comprises a hydroprocessed base stock and/or a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material.
  • the present invention provides a lubricant base oil which overcomes or at least mitigates, at least one of the deficiencies which may be associated with such base stocks, for example those deficiencies selected from the group consisting of poor dispersancy (for example, of soot and/or deposits), poor seal swell performance, poor solubility of additives and low compatibility with fuel oil in marine engine applications (which can lead to deposit formation, for example in cool parts of the engine), and also in some aspects, poor oxidative stability.
  • a further aspect of the present invention there is provided the use of 0.2 to 30 % by weight of an aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % in a liquid lubricant base oil composition which base oil comprises a base stock comprising at least 95 % by weight saturated hydrocarbons, to mitigate at least one of the deficiencies of the base stock selected from the group consisting of poor dispersancy, poor seal swell performance, poor solubility of additives and low compatibility with fuel oil in marine engine applications.
  • the present invention provides a method which uses a defined amount of aromatic extract, to make a base oil using a hydroprocessed base stock which may comprise for example, a Group II base stock and/or a Group III base stock, and/or using a base stock which may comprise a polyalphaolefin and/or using a base stock derived from Fischer-Tropsch synthesised, waxy, paraffmic hydrocarbon material.
  • a hydroprocessed base stock which may comprise for example, a Group II base stock and/or a Group III base stock, and/or using a base stock which may comprise a polyalphaolefin and/or using a base stock derived from Fischer-Tropsch synthesised, waxy, paraffmic hydrocarbon material.
  • This base oil can be used in applications where a Group I base stock has conventionally been used, such as for example, in marine engine applications, for example in 2-stroke marine diesel engine cylinder oils, 2-stroke marine diesel engine system oils and 4-stroke marine diesel engine crankcase lubricant compositions
  • the aromatic extract is preferably made by the treatment of at least one refinery process stream in a solvent extraction process.
  • Suitable solvent extraction process include contacting the at least one refinery process stream with a solvent such as furfural, n- methylpyrrolidone, sulphur dioxide, Duo-SolTM or phenol to selectively extract from the refinery stream, aromatic and heterocyclic materials and to form a solution of these materials in the solvent.
  • the solvent is then recovered from the solution for recycle to the extraction process; the resultant product being the aromatic extract.
  • the aromatic extract may be a residual aromatic extract, which may be made by treatment in an extraction process, of solvent deasphalted vacuum residue (also known as DAO) made using Duo-SolTM, propane, butane or mixtures thereof as the solvent for the deasphalting.
  • the aromatic extract may be a distillate aromatic extract (DAE) which is an aromatic extract made by treatment in an extraction process, of a distillate stream from a vacuum distillation process.
  • the distillate aromatic extract is a treated distillate aromatic extract which is a distillate aromatic extract which has been subjected to at least one further treatment.
  • the at least one further treatment is selected from the group consisting of hydrotreatment, hydrogenation, hydrodesulphurisation, clay treatment, acid treatment and further solvent extraction.
  • the aromatic extract may have an aromatics content of 60 to 85 weight %, which may be measured by ASTM D 2007.
  • the aromatic extract may have properties such as those described in Concawe Product Dossier 92/101 "Aromatic Extracts”.
  • the distillate aromatic extract may have a boiling point in the range 250 - 680 °C, which may be measured according to ASTM D 2887.
  • the distillate aromatic extract may have a kinematic viscosity at 40 °C in the range 5 - 18000 mm 2 /s, which may be measured according to ASTM D 445.
  • the distillate aromatic extract may have a kinematic viscosity at 100 0 C in the range 3 - 60 mm 2 /s, which may be measured according to ASTM D 445.
  • the distillate aromatic extract may have an average molecular mass in the range 300 - 580, which may be measured according to ASTM D 2887.
  • the distillate aromatic extract may have a carbon number range in the range C 15 - C 54 , which may be measured according to ASTM D 2887.
  • the distillate aromatic extract may have an aromatic content in the range 65 - 85 weight %, which may be measured according to ASTM D 2007.
  • the residual aromatic extract may have a boiling point of greater than 380 °C, which may be measured according to ASTM D 2887.
  • the residual aromatic extract may have a kinematic viscosity at 40 0 C of greater than 4000 mm 2 /s, which may be measured according to ASTM D 445.
  • the residual aromatic extract may have a kinematic viscosity at 100 °C in the range 60 - 330 mm 2 /s, which may be measured according to ASTM D 445.
  • the residual aromatic extract may have an average molecular mass of greater than 400, which may be measured according to ASTM D 2887.
  • the residual aromatic extract may have a carbon number range of greater than C 25 , which may be measured according to ASTM D 2887.
  • the residual aromatic extract may have an aromatic content in the range 60 - 85 weight %, which may be measured according to ASTM D 2007.
  • Aromatic extracts may comprise polycyclic aromatic compounds (PACs) some of which are carcinogens.
  • the amount of material (weight %) which can be extracted into dimethyl sulphoxide (DMSO) is used as an indication of the amount of unacceptable material (including polycyclic aromatic compounds) in the aromatic extracts.
  • IP 346 Institute of Petroleum Test Method 3466 is a method used for determining weight % DMSO extract.
  • Aromatic extracts with greater that 3 weight % dimethyl sulphoxide extractable polycyclic aromatics content are classed as carcinogenic and give rise to requirements in several jurisdictions that the material be labelled with certain symbols and risk phrases to identify health, safety and environmental hazards.
  • the aromatic extract has less than 3 weight % dimethyl sulphoxide extractable polycyclic aromatics content (low PCA extract). More preferably, the aromatic extract is a residual aromatic extract or a treated distillate aromatic extract, with less than 3 weight % dimethyl sulphoxide extractable polycyclic aromatics content. Preferably, the aromatic extract does not contain any significant amount of wax, because if present, wax may deposit in use.
  • the base stock of the present invention comprising at least 95 % by weight saturated hydrocarbons may comprise both a hydroprocessed base stock and a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material.
  • base stock of the present invention comprising at least 95 % by weight saturated hydrocarbons may comprise a hydroprocessed base stock or a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material.
  • the hydroprocessed base stock is preferably a Group II and/or Group III base stock, such as defined according to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", November 2004 version 15th edition Appendix E.
  • the base stock comprising at least 95 % by weight saturated hydrocarbons preferably comprises a Group II and/or Group III base stock, such as defined according to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", November 2004 version 15th edition Appendix E, comprising at least 95% by weight saturated hydrocarbons.
  • the Group II base stock or Group III base stock is a hydroprocessed base stock which may be made by hydroprocessing, preferably of vacuum distillate or deasphalted vacuum residue, or by hydroisomerising the bottoms stream from a clean fuels hydrocracker.
  • hydroprocessing preferably of vacuum distillate or deasphalted vacuum residue, or by hydroisomerising the bottoms stream from a clean fuels hydrocracker.
  • the manufacture of base stock by hydroprocessing is known in the art and is described for example in "Lubricant base oil and wax processing" A. Sequeira, pages 119 - 152, pub. Marcel Dekker Inc. New York, 1994.
  • the base stock comprising at least 95 % by weight saturated hydrocarbons may comprise one or more polyalphaolefin.
  • the base stock derived from a Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material may be made by any suitable known process for the manufacture of base stock from Fischer Tropsch process. Processes for the manufacture of a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material which may be used, are described for example in US4943672, EP-A-0668342 and EP-A- 0776959, the contents of which are hereby incorporated by reference.
  • the base stock may be made by the steps of (i) producing Syngas, (ii) Fischer-Tropsch synthesis of hydrocarbons from the Syngas, (iii) hydrocracking of the hydrocarbons to produce naphtha and diesel/kerosene fuel process streams together with a waxy paraffinic residue and (iv) hydroisomerising the waxy residue to produce the base stock.
  • the liquid lubricant base oil composition according to the present invention may be made by blending a base stock comprising at least 95 % by weight saturated hydrocarbons with sufficient an aromatic extract to make the lubricant base oil composition.
  • the blending may be performed in a batch blending process or in a continuous blending process.
  • Batch blending may be performed by introducing the base stock and aromatic extract into a blend kettle whilst stirring and/or agitating the blending components.
  • Continuous blending may be performed using an in-line mixer to blend the base stock and aromatic extract. Heating may be necessary during the blending to facilitate handling of the aromatics extracts.
  • the liquid lubricant base oil composition of the present invention has a viscosity in the range 7 to 40 cSt at 100° C.
  • liquid lubricant base oil composition of the present invention is particularly useful for the manufacture of 2-stroke marine diesel engine cylinder oils, 2-stroke marine diesel engine system oils or 4-stroke marine diesel engine crankcase lubricant compositions.
  • the liquid lubricant composition according to the present invention comprises a liquid lubricant base oil composition as hereindefined and one or more additives, preferably selected from the group consisting of detergents, dispersants, anti-wear additives, anti-oxidants, anti-foams, corrosion inhibitors, pour point depressants, friction modifiers, tackifiers and viscosity index improvers.
  • additives preferably selected from the group consisting of detergents, dispersants, anti-wear additives, anti-oxidants, anti-foams, corrosion inhibitors, pour point depressants, friction modifiers, tackifiers and viscosity index improvers.
  • concentrations of additives in the lubricant composition according to the present invention depend upon the use for which the lubricant composition is intended.
  • One or more anti-oxidants may be present in the lubricant composition at a total concentration by weight of 0 to 1 %, usually at a concentration by weight of not greater than 0.5 %.
  • One or more anti-wear additives may be present in the lubricant composition at a total concentration by weight of 0 to 2 %, usually at a concentration by weight of not greater than 1 %.
  • One or more high over-based detergents may be present in the lubricant composition at a total concentration by weight of 0 to 40 %.
  • One or more low base detergents may be present in the lubricant composition at a total concentration by weight of 0 to 10 %.
  • One or more neutral detergents may be present in the lubricant composition at a total concentration by weight of 0 to 2 %:
  • One or more dispersants may be present in the lubricant composition at a total concentration by weight of 0 to 10%.
  • One or more anti-foams may be present in the lubricant composition at a total concentration by weight of 0 to 0.1 %.
  • One or more corrosion inhibitors may be present in the lubricant composition at a total concentration by weight of 0 to 1 %.
  • One or more pour point depressants may be present in the lubricant composition at a total concentration by weight of 0 to 1 %.
  • One or more friction modifiers may be present in the lubricant composition at a total concentration by weight of 0 to 5%.
  • One or more tackifiers may be present in the lubricant composition at a total concentration by weight of 0 to 15 %.
  • One or more viscosity index improvers may be present in the lubricant composition at a total concentration by weight of 0 to 20 %.
  • concentration ranges for the additives may be independent of each other. Alternatively, combinations of such concentration ranges may be used for any particular lubricant composition.
  • liquid lubricant compositions of the present invention may be used as a 2- stroke marine diesel engine cylinder oil, 2-stroke marine' diesel engine system oil or 4-stroke marine diesel engine crankcase lubricant composition.
  • concentration ranges for additives for such lubricant compositions according to the present invention are given in the Table II below. Such concentration ranges may be independent of each other. Alternatively, combinations of such concentration ranges may be used for any particular lubricant composition.
  • Concentration ranges are expressed in % by weight of the liquid lubricant composition.
  • hydroprocessed base stock was a Group II base stock comprising at least 97 % by weight saturated hydrocarbons was used.
  • the aromatic extract was a low PCA brightstock extract (less than 3 % polycyclic aromatics, brightstock furfural extract) provided by Shell. Properties of these components are given in Table III below.
  • Base oil compositions were prepared by blending the aromatic extract (AE) with various amounts of the Group II base stock. Properties of the base oil compositions are given in Table IV below.
  • Experiment A is not according to the present invention because it does not contain any aromatic extract.
  • the results of the change in carbon ( ⁇ carbon) and viscosity ratio at the different concentrations of aromatic extract in the base oil are also shown in Figure 1.
  • the results of the ⁇ carbon and viscosity ratio show that the aromatic extract provides an improvement in ⁇ carbon at a concentration of aromatic extract up to about 12 % by weight and an improvement in viscosity ratio at a concentration of aromatics extract of up to 30 % by weight.
  • Lubricant compositions suitable for use in a marine 4-stroke engine using heavy fuel were prepared using a salicylate-rich additive package and base oils comprising different amounts of aromatic extract.
  • Oxidation properties of the lubricant compositions were measured. The results are shown in Table VII below. Table VII.

Landscapes

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

Abstract

A liquid lubricant base oil composition comprising (i) a base stock comprising at least 95 % by weight saturated hydrocarbons such as for example a Group II base stock, a Group III base stock and/or a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material and (ii) 0.2 to 30 % by weight of an aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % may be made by blending the components together and may be used with one or more additives in a lubricant composition which may be used in applications such as marine engine lubricants.

Description

LUBRICANT BASE OILS AND LUBRICANT COMPOSITIONS AND METHODS
FOR MAKING THEM
This invention relates to compositions and methods and in particular to lubricant base oils and lubricant compositions and to methods for making them.
Lubricant compositions generally comprise a base oil and one or more additives. According to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", November 2004 version 15th edition Appendix E, base stocks which are used for base oils are defined as belonging to one of five Groups as set out in Table I below.
Table I
Group I base stocks are generally preferred to Group II base stocks for the manufacture of lubricant compositions for marine 2-stroke and 4-stroke engines, particularly for engines operating on heavy fuel oil. However, Group II base stocks are becoming increasingly more readily available because older manufacturing capacity for Group I basestock is being closed and new manufacturing capacity tends to manufacture Group II base stock.
Group II base stocks may have some performance disadvantages compared to Group I base stocks when used in some lubricant compositions, for example in marine lubricants. These disadvantages may include poorer dispersancy, poorer seal swell performance, poorer solubility of additives, lower compatibility with fuel oil in marine engine applications (which can lead to deposit formation, for example in cool parts of the engine) and/or in some aspects, poorer oxidative stability. Hydroprocessed base stocks may have advantages and disadvantages (Deckman, D.E. et al., Hart's Lubricants World, July 1997, pages 46 - 50) when used in industrial lubricant applications (Deckman D. E. et al., Hart's Lubricants World, Sept 1997, pages 20-26) and in commercial, personal vehicle and marine engine oils (Deckman D. E. et al., Hart's Lubricants World, Sept 1997, pages 27 - 28).
According to Deckman D. E. et al., in Hart's Lubricants World, Sept 1997, pages 27 - 28, "Because hydrocracking results in a viscosity loss of the base stocks, marine oils cannot generally be formulated solely with hydrocracked base stocks, but require the use of significant amounts of bright stock. However, the use of bright stock is not desirable because of the presence of oxidatively unstable aromatics" .
Base stocks which are made by hydroprocessing, including Group II and Group III base stocks, have lower aromatics content and lower sulphur content than Group I base stocks.
Base stocks which are polyalphaolefins (Group IV) may also have a high degree of saturation.
Base stocks derived from Fischer-Tropsch synthesised, waxy, paraffmic hydrocarbon materials also have a low aromatics content and so may also exhibit at least some of the poorer performance of Group II and Group III base stocks compared to Group I base stocks. WO 00/14187 and WO 2005/066314 relate to lubricant compositions comprising Fischer Tropsch derived base stock.
There remains a need for a base oil composition which overcomes, or at least mitigates these problems.
It has now been found that the use of 0.2 to 30 % by weight of an aromatic extract in a base oil comprising base stock, which base stock comprises at least 95 % by weight saturated hydrocarbons, can overcome or at least mitigate these problems.
Thus, according to one aspect of the present invention, there is provided a liquid lubricant base oil composition comprising (i) a base stock comprising at least 95 % by weight saturated hydrocarbons and (ii) 0.2 to 30 % by weight, preferably 0.2 to 18 % or 1 to 30 % by weight, more preferably 1.0 to 18 % by weight, of an aromatic extract, in which the aromatic extract has a dimethyl sulphoxide extractable poly cyclic aromatics content of less than 3 weight %.
According to a second aspect of the present invention, there is provided a method of making a liquid lubricant base oil composition as hereindefined which method comprises blending a base stock comprising at least 95 % by weight saturated hydrocarbons with sufficient aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % to make a liquid lubricant base oil composition as hereindefined.
According to a third aspect of the present invention there is provided a liquid lubricant composition comprising a lubricant base oil composition as hereindefined and one or more additives, preferably selected from the group consisting of detergents, dispersants, anti-wear additives, anti-oxidants, anti-foams, corrosion inhibitors, pour point depressants, friction modifiers, tackifiers and viscosity index improvers.
The present invention solves the problem defined above by the use of 0.2 to 30 % by weight of an aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % in a liquid lubricant base oil composition which base oil comprises a base stock comprising at least 95 % by weight saturated hydrocarbons. This provides a lubricant base oil which overcomes or at least mitigates, at least some of the deficiencies which may be associated with such base stocks.
The lubricant base oil composition of the present invention comprises 0.2 to 30 % by weight of an aromatic extract. Preferably, the lubricant base oil composition of the present invention comprises 0.2 to 18 % or 1.0 to 30 % by weight of the aromatic extract. More preferably, the lubricant base oil composition of the present invention comprises 1.0 to 18 % by weight aromatic extract.
Preferably, the base stock comprising at least 95 % by weight saturated hydrocarbons comprises a hydroprocessed base stock and/or a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material. The present invention provides a lubricant base oil which overcomes or at least mitigates, at least one of the deficiencies which may be associated with such base stocks, for example those deficiencies selected from the group consisting of poor dispersancy (for example, of soot and/or deposits), poor seal swell performance, poor solubility of additives and low compatibility with fuel oil in marine engine applications (which can lead to deposit formation, for example in cool parts of the engine), and also in some aspects, poor oxidative stability.
Thus, according to a further aspect of the present invention there is provided the use of 0.2 to 30 % by weight of an aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % in a liquid lubricant base oil composition which base oil comprises a base stock comprising at least 95 % by weight saturated hydrocarbons, to mitigate at least one of the deficiencies of the base stock selected from the group consisting of poor dispersancy, poor seal swell performance, poor solubility of additives and low compatibility with fuel oil in marine engine applications.
In particular, the present invention provides a method which uses a defined amount of aromatic extract, to make a base oil using a hydroprocessed base stock which may comprise for example, a Group II base stock and/or a Group III base stock, and/or using a base stock which may comprise a polyalphaolefin and/or using a base stock derived from Fischer-Tropsch synthesised, waxy, paraffmic hydrocarbon material. This base oil can be used in applications where a Group I base stock has conventionally been used, such as for example, in marine engine applications, for example in 2-stroke marine diesel engine cylinder oils, 2-stroke marine diesel engine system oils and 4-stroke marine diesel engine crankcase lubricant compositions.
The aromatic extract is preferably made by the treatment of at least one refinery process stream in a solvent extraction process. Suitable solvent extraction process include contacting the at least one refinery process stream with a solvent such as furfural, n- methylpyrrolidone, sulphur dioxide, Duo-Sol™ or phenol to selectively extract from the refinery stream, aromatic and heterocyclic materials and to form a solution of these materials in the solvent. The solvent is then recovered from the solution for recycle to the extraction process; the resultant product being the aromatic extract.
The manufacture of aromatic extracts is known in the art and is described for example in "Lubricant base oil and wax processing" A. Sequeira, pages 81-118, pub. Marcel Dekker Inc. New York, 1994.
The aromatic extract may be a residual aromatic extract, which may be made by treatment in an extraction process, of solvent deasphalted vacuum residue (also known as DAO) made using Duo-Sol™, propane, butane or mixtures thereof as the solvent for the deasphalting. The aromatic extract may be a distillate aromatic extract (DAE) which is an aromatic extract made by treatment in an extraction process, of a distillate stream from a vacuum distillation process. Preferably, the distillate aromatic extract is a treated distillate aromatic extract which is a distillate aromatic extract which has been subjected to at least one further treatment. Suitably, the at least one further treatment is selected from the group consisting of hydrotreatment, hydrogenation, hydrodesulphurisation, clay treatment, acid treatment and further solvent extraction. The aromatic extract may have an aromatics content of 60 to 85 weight %, which may be measured by ASTM D 2007.
The aromatic extract may have properties such as those described in Concawe Product Dossier 92/101 "Aromatic Extracts".
The distillate aromatic extract may have a boiling point in the range 250 - 680 °C, which may be measured according to ASTM D 2887. The distillate aromatic extract may have a kinematic viscosity at 40 °C in the range 5 - 18000 mm2/s, which may be measured according to ASTM D 445. The distillate aromatic extract may have a kinematic viscosity at 100 0C in the range 3 - 60 mm2/s, which may be measured according to ASTM D 445. The distillate aromatic extract may have an average molecular mass in the range 300 - 580, which may be measured according to ASTM D 2887. The distillate aromatic extract may have a carbon number range in the range C15 - C54, which may be measured according to ASTM D 2887. The distillate aromatic extract may have an aromatic content in the range 65 - 85 weight %, which may be measured according to ASTM D 2007.
The residual aromatic extract may have a boiling point of greater than 380 °C, which may be measured according to ASTM D 2887. The residual aromatic extract may have a kinematic viscosity at 40 0C of greater than 4000 mm2/s, which may be measured according to ASTM D 445. The residual aromatic extract may have a kinematic viscosity at 100 °C in the range 60 - 330 mm2/s, which may be measured according to ASTM D 445. The residual aromatic extract may have an average molecular mass of greater than 400, which may be measured according to ASTM D 2887. The residual aromatic extract may have a carbon number range of greater than C25, which may be measured according to ASTM D 2887. The residual aromatic extract may have an aromatic content in the range 60 - 85 weight %, which may be measured according to ASTM D 2007.
Aromatic extracts may comprise polycyclic aromatic compounds (PACs) some of which are carcinogens. The amount of material (weight %) which can be extracted into dimethyl sulphoxide (DMSO) is used as an indication of the amount of unacceptable material (including polycyclic aromatic compounds) in the aromatic extracts. IP 346 (Institute of Petroleum Test Method 346) is a method used for determining weight % DMSO extract. Aromatic extracts with greater that 3 weight % dimethyl sulphoxide extractable polycyclic aromatics content are classed as carcinogenic and give rise to requirements in several jurisdictions that the material be labelled with certain symbols and risk phrases to identify health, safety and environmental hazards. For this reason at least, the aromatic extract has less than 3 weight % dimethyl sulphoxide extractable polycyclic aromatics content (low PCA extract). More preferably, the aromatic extract is a residual aromatic extract or a treated distillate aromatic extract, with less than 3 weight % dimethyl sulphoxide extractable polycyclic aromatics content. Preferably, the aromatic extract does not contain any significant amount of wax, because if present, wax may deposit in use.
The base stock of the present invention comprising at least 95 % by weight saturated hydrocarbons may comprise both a hydroprocessed base stock and a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material. Suitably, base stock of the present invention comprising at least 95 % by weight saturated hydrocarbons may comprise a hydroprocessed base stock or a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material.
The hydroprocessed base stock is preferably a Group II and/or Group III base stock, such as defined according to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", November 2004 version 15th edition Appendix E. The base stock comprising at least 95 % by weight saturated hydrocarbons preferably comprises a Group II and/or Group III base stock, such as defined according to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", November 2004 version 15th edition Appendix E, comprising at least 95% by weight saturated hydrocarbons.
Preferably, the Group II base stock or Group III base stock is a hydroprocessed base stock which may be made by hydroprocessing, preferably of vacuum distillate or deasphalted vacuum residue, or by hydroisomerising the bottoms stream from a clean fuels hydrocracker. The manufacture of base stock by hydroprocessing is known in the art and is described for example in "Lubricant base oil and wax processing" A. Sequeira, pages 119 - 152, pub. Marcel Dekker Inc. New York, 1994.
The base stock comprising at least 95 % by weight saturated hydrocarbons may comprise one or more polyalphaolefin.
The base stock derived from a Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material may be made by any suitable known process for the manufacture of base stock from Fischer Tropsch process. Processes for the manufacture of a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material which may be used, are described for example in US4943672, EP-A-0668342 and EP-A- 0776959, the contents of which are hereby incorporated by reference. Thus, the base stock may be made by the steps of (i) producing Syngas, (ii) Fischer-Tropsch synthesis of hydrocarbons from the Syngas, (iii) hydrocracking of the hydrocarbons to produce naphtha and diesel/kerosene fuel process streams together with a waxy paraffinic residue and (iv) hydroisomerising the waxy residue to produce the base stock.
The liquid lubricant base oil composition according to the present invention may be made by blending a base stock comprising at least 95 % by weight saturated hydrocarbons with sufficient an aromatic extract to make the lubricant base oil composition. The blending may be performed in a batch blending process or in a continuous blending process. Batch blending may be performed by introducing the base stock and aromatic extract into a blend kettle whilst stirring and/or agitating the blending components. Continuous blending may be performed using an in-line mixer to blend the base stock and aromatic extract. Heating may be necessary during the blending to facilitate handling of the aromatics extracts.
Preferably, the liquid lubricant base oil composition of the present invention has a viscosity in the range 7 to 40 cSt at 100° C.
The liquid lubricant base oil composition of the present invention is particularly useful for the manufacture of 2-stroke marine diesel engine cylinder oils, 2-stroke marine diesel engine system oils or 4-stroke marine diesel engine crankcase lubricant compositions.
The liquid lubricant composition according to the present invention comprises a liquid lubricant base oil composition as hereindefined and one or more additives, preferably selected from the group consisting of detergents, dispersants, anti-wear additives, anti-oxidants, anti-foams, corrosion inhibitors, pour point depressants, friction modifiers, tackifiers and viscosity index improvers.
The concentrations of additives in the lubricant composition according to the present invention depend upon the use for which the lubricant composition is intended.
One or more anti-oxidants may be present in the lubricant composition at a total concentration by weight of 0 to 1 %, usually at a concentration by weight of not greater than 0.5 %.. One or more anti-wear additives may be present in the lubricant composition at a total concentration by weight of 0 to 2 %, usually at a concentration by weight of not greater than 1 %.
One or more high over-based detergents may be present in the lubricant composition at a total concentration by weight of 0 to 40 %. One or more low base detergents may be present in the lubricant composition at a total concentration by weight of 0 to 10 %.
One or more neutral detergents may be present in the lubricant composition at a total concentration by weight of 0 to 2 %:
One or more dispersants may be present in the lubricant composition at a total concentration by weight of 0 to 10%.
One or more anti-foams may be present in the lubricant composition at a total concentration by weight of 0 to 0.1 %.
One or more corrosion inhibitors may be present in the lubricant composition at a total concentration by weight of 0 to 1 %. One or more pour point depressants may be present in the lubricant composition at a total concentration by weight of 0 to 1 %.
One or more friction modifiers may be present in the lubricant composition at a total concentration by weight of 0 to 5%.
One or more tackifiers may be present in the lubricant composition at a total concentration by weight of 0 to 15 %.
One or more viscosity index improvers may be present in the lubricant composition at a total concentration by weight of 0 to 20 %.
The concentration ranges for the additives may be independent of each other. Alternatively, combinations of such concentration ranges may be used for any particular lubricant composition.
The liquid lubricant compositions of the present invention may be used as a 2- stroke marine diesel engine cylinder oil, 2-stroke marine' diesel engine system oil or 4-stroke marine diesel engine crankcase lubricant composition.
The concentration ranges for additives for such lubricant compositions according to the present invention are given in the Table II below. Such concentration ranges may be independent of each other. Alternatively, combinations of such concentration ranges may be used for any particular lubricant composition.
Table II.
Concentration ranges are expressed in % by weight of the liquid lubricant composition.
The invention will now be described by way of example only and with reference to Figure 1 which is a graph of the performance of base oil with various amounts of aromatic extract.
In these experiments a hydroprocessed base stock was a Group II base stock comprising at least 97 % by weight saturated hydrocarbons was used. The aromatic extract was a low PCA brightstock extract (less than 3 % polycyclic aromatics, brightstock furfural extract) provided by Shell. Properties of these components are given in Table III below.
Table III General properties of components
The base stock and aromatic extract were shown not to contain any significant amounts of waxy materials. Base oil compositions were prepared by blending the aromatic extract (AE) with various amounts of the Group II base stock. Properties of the base oil compositions are given in Table IV below.
Table IV
Further base oils were prepared using the Group II base stock and the aromatic extract in other amounts. Oxidation properties of the base oils were tested according to the Institute of Petroleum procedure IP48 and the results are given in Table V below : Table V.
Experiment A is not according to the present invention because it does not contain any aromatic extract. The results of the change in carbon (Δ carbon) and viscosity ratio at the different concentrations of aromatic extract in the base oil are also shown in Figure 1.
The results of the Δ carbon and viscosity ratio show that the aromatic extract provides an improvement in Δ carbon at a concentration of aromatic extract up to about 12 % by weight and an improvement in viscosity ratio at a concentration of aromatics extract of up to 30 % by weight.
These results show the beneficial effect of the presence of 0.2 to 30 % by weight of aromatic extract in a base oil composition comprising a base stock comprising at least 95 weight % saturated hydrocarbons.
Lubricant compositions suitable for use in a marine 4-stroke engine using heavy fuel were prepared using a salicylate-rich additive package and base oils comprising different amounts of aromatic extract.
Properties of the formulated lubricant compositions are shown in Table VI below. Table VI.
Oxidation properties of the lubricant compositions were measured. The results are shown in Table VII below. Table VII.
The results in Table VII show some improvement is observed within the Panel Coker Test using steel panels undertaken according to the in-house method at 12 and 24 % by weight aromatic extract indicating an improvement within the solvency of the lubricant composition when aromatic extract is used.
Wear properties of the lubricant compositions were measured using a Cameron Plint test. The results are shown in Table VIII below. Table VIII.
The wear properties were compared against reference lubricant formulations with good and bad wear performance. The results show an exceptionally good wear performance for a lubricant composition with a base oil comprising 12 % by weight aromatic extract. However, at the higher concentration of 24 % by weight aromatics extract in the base oil, there is no significant improvement in wear performance compared to the composition with 100% Group II base oil. This data implies that there is an optimum concentration of aromatic extract for wear performance.

Claims

Claims :
1. A liquid lubricant base oil composition comprising (i) a base stock comprising at least 95 % by weight saturated hydrocarbons and (ii) 0.2 to 30 % by weight, preferably 0.2 to 18 % or 1 to 30 % by weight, more preferably 1.0 to 18 % by weight, of an aromatic extract, in which the aromatic extract has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight %.
2. A liquid lubricant base oil composition as claimed in claim 1 in which the base stock comprising at least 95 % by weight saturated hydrocarbons comprises a hydroprocessed base stock and/or a base stock derived from Fischer-Tropsch synthesised, waxy, paraffinic hydrocarbon material.
3. A liquid lubricant base oil composition as claimed in claim 2 in which the hydroprocessed base stock is a Group II base stock and/or a Group III base stock.
4. A liquid lubricant base oil composition as claimed in claim 1 in which the base stock comprises a Group II base stock and/or a Group III base stock.
5. A liquid composition as claimed in any one of claims 1 to 4 in which the base stock comprises at least one polyalphaolefin.
6. A method of making a liquid lubricant base oil composition as claimed in any one of claims 1 to 5 which method comprises blending a base stock comprising at least 95 % by weight saturated hydrocarbons with sufficient aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % to make a liquid lubricant base oil composition as claimed in any one of claims 1 to 5.
7. A liquid lubricant composition comprising a liquid lubricant base oil composition as claimed in any one of claims 1 to 5 and one or more additives, preferably selected from the group consisting of detergents, dispersants, anti-wear additives, anti-oxidants, anti- foams, corrosion inhibitors, pour point depressants, friction modifiers, tackifϊers and viscosity index improvers.
8. A liquid lubricant composition as claimed in claim 7 when used as a 2-stroke marine diesel engine cylinder oil, 2-stroke marine diesel engine system oil or 4-stroke marine diesel engine crankcase lubricant composition.
9. The use of 0.2 to 30 % by weight of an aromatic extract which has a dimethyl sulphoxide extractable polycyclic aromatics content of less than 3 weight % in a liquid lubricant base oil composition which base oil comprises a base stock comprising at least 95 % by weight saturated hydrocarbons, to mitigate at least one of the deficiencies of the base stock selected from the group consisting of poor dispersancy, poor seal swell performance, poor solubility of additives and low compatibility with fuel oil in marine engine applications.
EP08709441.3A 2007-02-21 2008-02-18 Method for making a lubricant base oil and its use Active EP2113021B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08709441.3A EP2113021B1 (en) 2007-02-21 2008-02-18 Method for making a lubricant base oil and its use

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07250739A EP1967571A1 (en) 2007-02-21 2007-02-21 Compositions and methods
EP08709441.3A EP2113021B1 (en) 2007-02-21 2008-02-18 Method for making a lubricant base oil and its use
PCT/GB2008/000554 WO2008102114A1 (en) 2007-02-21 2008-02-18 Lubricant base oils and lubricant compositions and methods for making them

Publications (2)

Publication Number Publication Date
EP2113021A1 true EP2113021A1 (en) 2009-11-04
EP2113021B1 EP2113021B1 (en) 2019-06-12

Family

ID=38481264

Family Applications (2)

Application Number Title Priority Date Filing Date
EP07250739A Ceased EP1967571A1 (en) 2007-02-21 2007-02-21 Compositions and methods
EP08709441.3A Active EP2113021B1 (en) 2007-02-21 2008-02-18 Method for making a lubricant base oil and its use

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP07250739A Ceased EP1967571A1 (en) 2007-02-21 2007-02-21 Compositions and methods

Country Status (8)

Country Link
US (1) US20100323936A1 (en)
EP (2) EP1967571A1 (en)
JP (1) JP5666139B2 (en)
KR (1) KR101545756B1 (en)
CN (1) CN101617032A (en)
CA (1) CA2678700C (en)
MY (1) MY154529A (en)
WO (1) WO2008102114A1 (en)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010066860A1 (en) * 2008-12-12 2010-06-17 Shell Internationale Research Maatschappij B.V. Lubricating compositions
EP2398872B1 (en) * 2009-02-18 2013-11-13 Shell Internationale Research Maatschappij B.V. Use of a lubricating composition with gtl base oil to reduce hydrocarbon emissions
US9127229B2 (en) 2009-07-24 2015-09-08 Cherron Oronite Technology B.V. Trunk piston engine lubricating oil compositions
WO2011077811A1 (en) * 2009-12-24 2011-06-30 Ｊｘ日鉱日石エネルギー株式会社 System lubricant oil composition for crosshead-type diesel engine
JP5414513B2 (en) * 2009-12-24 2014-02-12 Ｊｘ日鉱日石エネルギー株式会社 System lubricant composition for crosshead type diesel engine
JP5483330B2 (en) * 2009-12-24 2014-05-07 Ｊｘ日鉱日石エネルギー株式会社 System lubricant composition for crosshead type diesel engine
US8728999B2 (en) 2010-02-01 2014-05-20 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8748362B2 (en) 2010-02-01 2014-06-10 Exxonmobile Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
US8759267B2 (en) 2010-02-01 2014-06-24 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8642523B2 (en) 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8598103B2 (en) 2010-02-01 2013-12-03 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
US8318643B2 (en) 2010-06-29 2012-11-27 Cherron Oronite Technology B.V. Trunk piston engine lubricating oil compositions
US9273266B2 (en) * 2010-09-24 2016-03-01 Dow Global Technologies Llc Non-aromatic based antioxidants for lubricants
KR20140035357A (en) * 2011-04-05 2014-03-21 셰브런 오로나이트 컴퍼니 엘엘씨 Low viscosity marine cylinder lubricating oil compositions
CN102757837B (en) * 2011-04-29 2014-04-30 中国石油化工股份有限公司 Lubricating oil base oil composition
JP2013209569A (en) * 2012-03-30 2013-10-10 Jx Nippon Oil & Energy Corp Lubricating oil composition
WO2014057640A1 (en) * 2012-10-10 2014-04-17 Ｊｘ日鉱日石エネルギー株式会社 Lubricating oil composition for trunk-piston-type diesel engine
WO2014057683A1 (en) * 2012-10-10 2014-04-17 Ｊｘ日鉱日石エネルギー株式会社 Cylinder lubricating oil composition for crosshead-type diesel engine
JP6046156B2 (en) * 2012-10-10 2016-12-14 Ｊｘエネルギー株式会社 System lubricant composition for crosshead type diesel engine
SG10201704490XA (en) 2012-12-27 2017-07-28 Jx Nippon Oil & Energy Corp System lubricant composition for crosshead diesel engines
JP6514881B2 (en) * 2014-11-28 2019-05-15 シェルルブリカンツジャパン株式会社 Lubricating oil composition
WO2021225662A2 (en) * 2020-03-31 2021-11-11 Exxonmobil Research And Engineering Company Hydrocarbon compositions useful as lubricants for improved oxidation stability

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1745771C3 (en) * 1963-10-08 1974-05-30 Oelwerke Julius Schindler Gmbh, 2000 Hamburg Use of products obtained from spindle and machine oil fractions as a means of improving the aging resistance of electrical insulating oils
FR1592085A (en) * 1968-02-14 1970-05-11
GB1237292A (en) * 1968-02-14 1971-06-30 Inst Francais Du Petrole Oils stable to oxidation
GB1572794A (en) * 1975-12-16 1980-08-06 Shell Int Research Baseoil compositions
CA1090275A (en) * 1975-12-16 1980-11-25 Jacobus H. Breuker Base-oil compositions
NL193379C (en) * 1980-09-09 1999-08-03 Shell Int Research Basic lubricating oil composition.
US4444567A (en) * 1982-07-01 1984-04-24 Phillips Petroleum Company Motor fuel composition containing an ashless antiknock agent
US4777307A (en) * 1987-12-14 1988-10-11 Exxon Research And Engineering Company Method for improving the oxidation stability of refined hydrocarbon oils
US4943672A (en) * 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
CA2025416C (en) * 1990-09-14 1999-06-22 Stephen Cedric Cohen Lubricating oil compositions containing novel combination of stabilizers (no. 2)
ATE102243T1 (en) * 1991-01-11 1994-03-15 Mobil Oil Corp LUBRICANT COMPOSITIONS.
EP0709447A1 (en) * 1994-10-25 1996-05-01 Exxon Research And Engineering Company Multiring aromatics for enhanced deposit control
US5911874A (en) * 1996-06-28 1999-06-15 Exxon Research And Engineering Co. Raffinate hydroconversion process
DE69729526T2 (en) * 1996-10-31 2005-08-18 Repsol Petroleo S.A. Process for the preparation of oils with a content of polycyclic aromatics of less than 3%, usable as process oils
US6103808A (en) * 1997-06-27 2000-08-15 Bridgestone Corporation High aromatic oil and rubber composition and oil extended synthetic rubber using the same
US6399697B1 (en) * 1999-02-26 2002-06-04 Idemitsu Kosan Co., Ltd. Process oil, process for producing the same and rubber composition
AR032930A1 (en) * 2001-03-05 2003-12-03 Shell Int Research PROCEDURE TO PREPARE AN OIL BASED OIL AND GAS OIL
US20030168382A1 (en) * 2001-05-21 2003-09-11 Jois Yajnanarayana Halmuthur Process for making non-carcinogentic, high aromatic process oil
US6806237B2 (en) * 2001-09-27 2004-10-19 Chevron U.S.A. Inc. Lube base oils with improved stability
US7601253B2 (en) * 2001-10-02 2009-10-13 Japan Energy Corporation Process oil and process for producing the same
US6627779B2 (en) * 2001-10-19 2003-09-30 Chevron U.S.A. Inc. Lube base oils with improved yield
US20030191032A1 (en) * 2002-01-31 2003-10-09 Deckman Douglas E. Mixed TBN detergents and lubricating oil compositions containing such detergents
FR2838129B1 (en) 2002-04-09 2004-07-09 Totalfinaelf France HYDROCARBON MIXTURES COMPRISING MODIFIED POLYCYCLIC AROMATIC HYDROCARBONS
US20040129603A1 (en) * 2002-10-08 2004-07-08 Fyfe Kim Elizabeth High viscosity-index base stocks, base oils and lubricant compositions and methods for their production and use
US7083713B2 (en) * 2003-12-23 2006-08-01 Chevron U.S.A. Inc. Composition of lubricating base oil with high monocycloparaffins and low multicycloparaffins
JP4171726B2 (en) * 2004-10-19 2008-10-29 新日本石油株式会社 Lubricating oil composition and method for producing the same
WO2006043606A1 (en) * 2004-10-19 2006-04-27 Nippon Oil Corporation Lubricant composition and antioxidant composition
TWI252413B (en) * 2004-12-10 2006-04-01 Hon Hai Prec Ind Co Ltd System and method for updating remote computer files

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008102114A1 *

Also Published As

Publication number Publication date
JP2010519376A (en) 2010-06-03
US20100323936A1 (en) 2010-12-23
MY154529A (en) 2015-06-30
CN101617032A (en) 2009-12-30
EP2113021B1 (en) 2019-06-12
KR20090113856A (en) 2009-11-02
JP5666139B2 (en) 2015-02-12
CA2678700A1 (en) 2008-08-28
WO2008102114A1 (en) 2008-08-28
EP1967571A1 (en) 2008-09-10
CA2678700C (en) 2014-12-02
KR101545756B1 (en) 2015-08-19

Similar Documents

Publication Publication Date Title
WO2008102114A1 (en) Lubricant base oils and lubricant compositions and methods for making them
EP2484746B1 (en) Lubricant oil composition
Speight et al. Refining used lubricating oils
AU7299300A (en) Novel hydrocarbon base oil for lubricants with very high viscosity index
CN101426762A (en) Process for improving the lubricating properties of base oils using isomerized petroleum product
CN108473887A (en) Bright stock is produced by deasphalted oil
US8480879B2 (en) Process for improving lubricating qualities of lower quality base oil
JP5898691B2 (en) Lubricating composition
CA2511198A1 (en) Upgrading asphaltene containing oils
CN102639683B (en) Functional fluid composition
WO2016117566A1 (en) Vapor film-rupturing agent, and thermal treatment oil composition
CN115667468A (en) Lubricant with improved low temperature, oxidation and deposit control properties
CN101896588A (en) Method for forming finished lubricants
EP3475398B1 (en) Lubricating composition
Büyüknisan Analysis of The Effects of Different Additives on Base Oils
Rizvi | Petroleum-Derived Hydrocarbon Base Oils
Adhvaryu et al. Application of quantitative 13C nuclear magnetic resonance spectroscopy to the characterisation of solvent‐refined aromatic‐rich lubricant base oils
LUBRICANTS Mineral Oil
EP4245829A1 (en) Refrigerator oil, and working fluid composition for refrigerator
WO2021225662A2 (en) Hydrocarbon compositions useful as lubricants for improved oxidation stability
Rossi Lube manufacturing technology and engine oil pumpability
Deer Park et al. 170 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

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: 20090814

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK 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: 20170130

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: 20190104

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1142539

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008060326

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190612

Ref country code: SE

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: 20190612

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: 20190612

Ref country code: LT

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: 20190612

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: 20190912

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: 20190612

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190913

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: 20190612

Ref country code: BG

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: 20190912

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1142539

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190612

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

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: 20190612

Ref country code: PT

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: 20191014

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: 20190612

Ref country code: RO

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: 20190612

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: 20190612

Ref country code: EE

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: 20190612

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: 20191012

Ref country code: IT

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: 20190612

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008060326

Country of ref document: DE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190612

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: PL

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: 20190612

Ref country code: DK

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: 20190612

26N No opposition filed

Effective date: 20200313

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: 20200224

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: 20190612

PG2D Information on lapse in contracting state deleted

Ref country code: IS

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: 20191112

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20200218

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200229

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190612

Ref country code: LU

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

Effective date: 20200218

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

Ref country code: CH

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

Effective date: 20200229

Ref country code: LI

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

Effective date: 20200229

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: 20200218

Ref country code: IE

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

Effective date: 20200218

Ref country code: FR

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

Effective date: 20200229

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: 20200229

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

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: 20190612

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: 20190612

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230526

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008060326

Country of ref document: DE

Representative=s name: KRAUS & LEDERER PARTGMBB, DE

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

Ref country code: NL

Payment date: 20240226

Year of fee payment: 17

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

Ref country code: DE

Payment date: 20240228

Year of fee payment: 17