EP1896556B1 - Oxidationsstabile ölformulierung - Google Patents

Oxidationsstabile ölformulierung Download PDF

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Publication number
EP1896556B1
EP1896556B1 EP06777414.1A EP06777414A EP1896556B1 EP 1896556 B1 EP1896556 B1 EP 1896556B1 EP 06777414 A EP06777414 A EP 06777414A EP 1896556 B1 EP1896556 B1 EP 1896556B1
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Prior art keywords
base oil
oil
formulation according
formulation
additive
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French (fr)
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EP1896556A1 (de
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Volker Klaus Null
Andree Hilker
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing 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
    • 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
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic 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
    • 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
    • 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
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/083—Dibenzyl sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly 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
    • C10N2040/14—Electric or magnetic purposes
    • 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
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • 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
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/17—Electric or magnetic purposes for electric contacts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the invention is related to an oxidation stable oil formulation comprising a base oil composition and additives.
  • US-A-6790386 describes a dielectric fluid comprising an iso-paraffin base oil and additives.
  • the iso-paraffin base oil is prepared by hydrotreating, hydroisomerisation and hydrogenation of a paraffinic vacuum feedstock.
  • US-A-6214776 describes a formulation comprising a paraffinic base oil and an additive package containing a hindered phenol antioxidant and a metal deactivator, for use as load tap changer or transformer oil.
  • base oils having a kinematic viscosity at 40 °C of between 5 and 20 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
  • US-A-5241003 discloses a combination of a sulfur-containing antiwear additive and a carboxylic derivative dispersant for use as additive package for lubricants.
  • US-A-5773391 describes a composition comprising a polyol ester base oil, an aliphatic monocarboxylic acid mixture, and an additive package comprising an antioxidant and a metal deactivator.
  • the document further discloses phosphorodithionates as antiwear additives.
  • WO-A-02070629 describes a process to make isoparaffinic base oils from a wax as made in a Fischer-Tropsch process.
  • base oils having a kinematic viscosity at 100 °C of between 2 and 9 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
  • US-A-5912212 describes oxidative stable oil lubricating formulations consisting of a hydrocracked paraffinic mineral base oil and 0.1 to 5 wt% of a sulphur or phosphorus containing compound.
  • a formulation consisting of a base oil and 3-methyl-5-tert-butyl-4-hydroxy propionic acid ester, dioctylamino-methyltolyltriazole and 0.4 wt% of dilaurylthio-dipropionate.
  • the oil had a high oxidative stability.
  • US3338877 describes co-polymers of ethylene and stilbene useful as lubricating oils with excellent oxidative and thermal stability. A number of anti-scuffing agents are taught as suitable for addition thereto.
  • a mineral-derived base oil has the meaning within the context of this specification that the base oil was obtained from a mineral oil source.
  • Polysulfide compounds are represented by the formula (I) R 1 -(S) a -R 2 (I) wherein:
  • the copper passivator or electrostatic discharge depressant is the optionally substituted benzotriazole compound represented by the formula (III) wherein R 4 may be hydrogen or a group represented by the formula (IV) or by the formula (V) wherein:
  • Preferred compounds are 1-[bis(2-ethylhexyl)-aminomethyl]benzotriazole, methylbenzotriazole, dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole and mixtures thereof.
  • Other preferred compounds include (N-Bis(2-ethylhexyl)-aminomethyl-tolutriazole, non-substituted benzotriazole, and 5-methyl-1H-benzotriazole. Examples of copper passivator additives as described above are described in US-A-5912212 , EP-A-1054052 and in US-A-2002/0109127 .
  • Copper passivator additives as those described above are commercially available under the product names BTA, TTA, IRGAMET 39, IRGAMET30 and IRGAMET 38S from CIBA Ltd Basel Switzerland, also traded under the trade name Reomet by CIBA.
  • the content of the above copper passivator in the oil formulation is between 5 and 1000 mg/kg.
  • a practical upper limit may vary depending on the specific application of the oil formulation. For example, when desiring improved dielectric discharge tendencies of the oil for use as electrical oil it may be desired to add a high concentration of the copper passivator additive. Applicants found that the advantages of the invention can be achieved at concentrations below 1000 mg/kg and more preferably below 300 mg/kg, even more preferably below 50mg/kg.
  • the oil formulation preferably also comprises an anti-oxidant additive. It has been found that, especially in case the base oil is a mineral paraffinic base oil, the sludge formed and total acidity both measured after the IEC 61125 C oxidation test, which properties are indicators for good oxidation stable oils, are considerably reduced when also an anti-oxidant is present.
  • the anti-oxidant may be a so-called hindered phenolic or amine antioxidant, for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenyl-amines or ionol derived hindered phenols.
  • hindered phenolic or amine antioxidant for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenyl-amines or ionol derived hindered phenols.
  • Sterically hindered phenolic antioxidants of particular interest are selected from the group consisting of 2,6-di-tert-butylphenol (IRGANOX TM L 140, CIBA), di tert-butylated hydroxotoluene (BHT), methylene-4,4'-bis-(2.6-tert-butylphenol), 2,2'-methylene bis-(4,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-hydroxyhydrocinnamate) (IRGANOX TM L109, CIBA), ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)thio) acetic acid, C 10 -C 14 isoalkyl esters (IRGANOX TM L118, CIBA), 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C 7 -C 9 alkyl
  • amine antioxidants are aromatic amine anti-oxidants for example N,N'-Di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylene-diamine, N,N'-bis(1-methyl-heptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylene-diamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(naphthyl-2-)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbuty
  • p,p'-di-tert-octyldiphenylamine 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethyl-aminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di(phenylamino)ethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,3-di-(phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3
  • the content of the anti oxidant additive is preferably less than 2 wt% and more preferably less than 1 wt%.
  • the content is preferably less than 0,6 wt% in certain applications, such as when the oil formulation is used as an electrical oil.
  • the content of antioxidant is preferably greater than 10 mg/kg.
  • the oil formulation preferably has a sulphur content of below 0,5 wt% and even more preferably below 0,15 wt%.
  • the source of the majority of the sulphur in the oil formulation will be the sulphur as contained in the base oil component of the oil formulation according the invention.
  • the base oil composition preferably has a kinematic viscosity at 100 °C of less than 50 mm 2 /sec, more preferably between 2 and 25 mm 2 /sec, most preferably between 2 and 15 mm 2 /sec.
  • the base oil composition preferably has a kinematic viscosity at 40 °C of between 1 and 200 mm 2 /sec, more preferably between 3.5 and 100 mm 2 /sec, most preferably between 5 and 12 mm 2 /sec.
  • the viscosity of the base oil composition will also depend on the particular use of the oil formulation. If the oil formulation is used as an electrical oil its kinematic viscosity at 40 °Cis preferably between 1 and 50 mm 2 /sec.
  • this electrical oil formulation is a transformer oil
  • the base oil will preferably have a kinematic viscosity at 40 °C of between 5 and 15 mm 2 /sec. If the electrical oil is a low temperature switch gear oil the base oil viscosity at 40°C is preferably between 1 and 15 and more preferably between 1 and 4 mm 2 /sec.
  • the flash point of the base oil composition as measured by ASTM D92 may be greater than 90 °C, preferably greater than 120 °C, yet more preferably greater than 140 °C, and even more preferably greater than 170 °C.
  • the higher flash points are desirable for applications where peak temperatures can exceed the average oil temperature, for instance in applications under high temperature and/or with restricted heat transmission potential. Examples are electric transformers and electric engines.
  • the base oil composition may comprise one or more base oils selected from mineral-derived naphthenic base oils and/or mineral-derived paraffic base oils.
  • the base oil composition may this comprise a mineral-derived base oil of the so-called paraffinic type or naphthenic type.
  • Such base oils are obtained by refinery processes starting from paraffinic and naphthenic crude feeds.
  • Mineral-derived naphthenic base oils for the purpose of this invention are defined as having a pour point of below -20 °C and a viscosity index of below 70.
  • Mineral-derived paraffin base oils are defined by a viscosity index of greater than 70, preferably greater than 90.
  • Mineral-derived naphthenic and paraffin base oils are well known and described in more detail in " Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 28-35 .
  • the base oil composition preferably comprises a base oil comprising a series of iso-paraffins having n, n+1, n+2, n+3 and n+4 carbon atoms and wherein n is a number between 20 and 35.
  • the paraffin content in the base oil composition is greater than 80 wt%, more preferably greater than 90 wt%, yet more preferably greater than 95%, and again more preferably greater than 98%.
  • the base oil composition furthermore may preferably have a content of naphthenic compounds of between 1 and 20 wt%. It has been found that these base oils have a good additive response to the additives listed above when aiming to improve oxidation stability.
  • the content of naphthenic compounds and the presence of such a continuous series of iso-paraffins may be measured by Field desorption/Field Ionisation (FD/FI) technique. In this technique the oil sample is first separated into a polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPLC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states.
  • HPLC high performance liquid chromatography
  • the saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI (a "soft” ionisation technique) is used for the determination of hydrocarbon types in terms of carbon number and hydrogen deficiency.
  • FI Field desorption/Field Ionisation
  • the type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: C n H 2n+z . Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different iso-paraffins having the same stoichiometry or n-number.
  • the results of the mass spectrometer are processed using commercial software (poly 32; available from Sierra Analytics LLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type.
  • the base oil composition having the continuous isoparaffinic series as described above are preferably obtained by hydroisomerisation of a paraffinic wax, yet more preferably followed by some type of dewaxing, such as solvent or catalytic dewaxing.
  • the above described base oil composition may preferably be obtained by hydroisomerisation of a paraffinic wax, preferably followed by a dewaxing treatment, such as a solvent or catalytic dewaxing treatment.
  • the paraffinic wax may be a highly paraffinic slack wax.
  • the oil formulation may comprise a single type of base oil or blends of the above-described base oils as base oil composition.
  • the base oil composition comprises at least 80% by weight of the total formulation of a mineral-derived naphthenic base oil; and to formulations wherein the base oil comprises at least 80% by weight of a mineral-derived paraffinic base oil.
  • base oils and other synthetic base oil components may be present in the oil formulation, such as for example esters, poly alpha olefins, as preferably obtained by oligomerisation of an olefinic compound, poly alkylene glycols and the like.
  • additives next to the ones described above may also be present in the formulation.
  • the type of additives will depend on the specific application. Without intending to be limiting, examples of possible additives are dispersants, detergents, viscosity modifying polymers, hydrocarbon or oxygenated hydrocarbon type pour point depressants, emulsifiers, demulsifiers, antistaining additives and friction modifiers. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526 .
  • the dispersant is an ashless dispersant, for example polybutylene succinimide polyamines or Mannic base type dispersants.
  • the detergent is an over-based metallic detergent, for example the phosphonate, sulfonate, phenolate or salicylate types as described in the above referred to General Textbook.
  • the viscosity modifier is a viscosity modifying polymer, for example polyisobutylenes, olefin copolymers, polymethacrylates and polyalkylstyrenes and hydrogenated polyisoprene star polymer (Shellvis).
  • suitable antifoaming agents are polydimethylsiloxanes and polyethylene glycol ethers and esters.
  • the oil formulation may find use as turbine oil, gasoline engine oil, diesel engine oil, automotive and industrial gear oils, for example automatic and manual transmission and differential oils, hydraulic machine oil, refrigerator oil, plastic processing oil for rolling, press, forging, sqeezing, draw, punch and the like operations, thermal treating oil, discharge processing oil, slide guide oil, rust proofing oil and heat medium.
  • a preferred use of the oil formulation is as electrical oil. Examples of applications are switch gears, transformers, regulators, circuit breakers, power plant reactors, cables and other electrical equipment.
  • a problem often encountered when using an electrical oil based on a naphthenic base oil is that the kinematic viscosity at -30 °C is too high.
  • Another preferred mixture of aromatic compounds is comprised in a mixture of 2,6-di-t-butyl phenol and 2,6-di-t-butyl cresol.
  • the oil formulation comprises between 0.1 and 3 wt% of 2,6-di-t-butyl phenol and 0.1 to 2 wt% of 2,6-di-t-butyl cresol in a weight ratio of between 1:1 and 1:1.5.
  • the oil formulation preferably comprising the anti-wear additive, is preferably subjected to an additional clay treatment.
  • Clay treatment is a well know treatment to remove polar compounds from the oil formulation. It is performed in order to further improve the color, chemical and thermal stability of the oil formulation. It may be performed prior to adding the additives mentioned in this description on a, partly, formulated oil formulation. Clay treatment processes are for example described in Lubricant base oil and wax processing, Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 229-232 .
  • the copper passivator and optional anti-oxidant are added after the clay treatment.
  • the electrical oil as described above may find use in applications which have to start up regularly, especially more than 10 times per year at a temperature of below 0 °C, more preferably below -5 °C, wherein the temperature of the oil when the application is running is above 0 °C.
  • Examples of such applications are as low temperature switch gear oils, transformers, regulators, circuit breakers, power plant reactors, switch gear, cables, electrical equipment.
  • Such applications are well known to the skilled person and described for example in Lubricants and related products, Dieter Klamann, Verlag Chemie GmbH, Weinhem, 1984, pages 330-339 .
  • the invention will be illustrated with the following non-limiting examples.
  • One Fischer-Tropsch derived base oil referred to as GTL BO
  • two naphthenic type of base oils referred to as naphthenic-1 and naphthenic-2
  • a mineral paraffinic base oil referred to as mineral paraffinic base oil. The properties of these base oils are listed in Table 1.
  • Example 1 two formulations A and B were prepared of which the base oil component consisted of 95 wt% of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil. To these mixtures 10 mg/kg of 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole (Reomet38S) was added. To mixture A 200 mg/kg of Dibenzyldisulfide was added and to mixture B 200 mg/kg of Di-n-dodecyldisulfid was added. Oil mixtures A and B were tested with the IEC 61125 C Oxidation test 164h/120 °C test to measure the acidity of the oil phase.
  • the base oil component consisted of 95 wt% of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil.
  • Reomet38S 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole
  • the acidity of the oil phase of mixture A was 0.26 mg KOH/g and the acidity of the oil phase of mixture B was 0.94 mg KOH/g. Both values are very low and illustrate an excellent oxidative stability.
  • the values for Mixture A show that even more excellent results are obtained when the preferred Dibenzyldisulfide additive is used as the an organic polysulphide anti-wear additive. It is surprising that the choice of a particular anti-wear additive can improve the oxidation stability in the manner here illustrated.
  • Table 3 Total Acidity formation according to IEC 61125 C Additivation scheme 1 2 3 4 5 Dibenzyldisulfide mg/kg - - 200 200 200 1-[bis(2-ethylhexyl)aminomethyl]-benzotriazole mg/kg - 10 - 10 10
  • Antioxidant BHT Wt% - - - - 0,08 Total acidity according to IEC 61125 C Naphthenic base oil-1 Mg KOH/g 4,14 3,87 1,59 0,83 1,02 Paraffinic base oil-1 Mg KOH/g 9,12 6,78 0,78 0,38 0,02 GTL Base Oil-1 Mg KOH/g 13,67 10,55 12,65 12,57 0,10
  • oil mixtures were prepared according to the scheme as presented in Table 4. Two oil mixtures were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Muenchen (D). The anti-oxidant and copper passivator additives were added after the clay treatment. The properties of the oil mixtures were measured and the oil mixtures were subjected to the IEC OXIDATION TEST at 500h/120 °C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Insulating Materials (AREA)

Claims (13)

  1. Oxidationsstabile Ölformulierung, die eine Grundöl-Zusammensetzung umfasst, wobei die Grundöl-Zusammensetzung wenigstens 80 Gewichts-% eines naphthenischen Grundöls mineralischer Herkunft oder wenigstens 80 Gewichts-% eines paraffinischen Grundöls mineralischer Herkunft umfasst, wobei ein Gehalt von zwischen 5 und 1000 mg/kg eines Kupferpassivierungsmittels ausgewählt ist aus wahlweise substituierten Benzotriazolverbindungen, die dargestellt werden durch die Formel (III)
    Figure imgb0007
     wobei R4 Wasserstoff ist oder eine Gruppe, die dargestellt wird durch die Formel (IV)
    Figure imgb0008
     oder durch die Formel (V)
    Figure imgb0009
     wobei:
    c 0, 1, 2 oder 3 ist,
    R3 eine gerade oder verzweigte C1-4-Alkylgruppe ist, R5 eine Methylen- oder Ethylengruppe ist, R6 und R7 Wasserstoff oder die gleichen oder unterschiedliche gerade oder verzweigte Alkylgruppen von 1 bis 18 Kohlenstoffatomen, vorzugsweise eine verzweigte Alkylgruppe von 1 bis 12 Kohlenstoffatomen, sind, R8 und
    R9 die gleichen oder unterschiedliche Alkylgruppen von 3 bis 15 Kohlenstoffatomen sind,
    wobei von 0,001 Gew,-% bis zu weniger als 0,1 Gew.-% eines Verschleißschutzzusatzes ausgewählt sind aus organischen Polysulfiden, die dargestellt werden durch die Formel

            R1-(S)a-R2     (I),

    wobei:
    a 2, 3, 4 oder 5 ist,
    R1 und R2 unabhängig ausgewählt sind aus der Gruppe, die aus wahlweise substituierten, geraden oder verzweigten, aromatischen oder aliphatischen C1-C25-Kohlenwasserstoffgruppen besteht.
  2. Formulierung nach Anspruch 1, wobei R1 und R2 unabhängig ausgewählt sind aus der Gruppe, die aus wahlweise substituierten, geraden oder verzweigten, aromatischen oder aliphatischen C4-C20-, vorzugsweise C6-C16-Kohlenwasserstoffgruppen besteht.
  3. Formulierung nach Anspruch 1 oder 2, wobei R1 und R2 unabhängig ausgewählt sind aus geradem oder verzweigtem Dodecyl und Benzyl.
  4. Formulierung nach einem oder mehreren der vorhergehenden Ansprüche, wobei der Gehalt an Verschleißschutzzusatz in der Formulierung geringer als 800 mg/kg, insbesondere geringer als 400 mg/kg, ist.
  5. Formulierung nach einem der vorhergehenden Ansprüche, wobei R3 Methyl oder Ethyl ist und C 1 oder 2 ist.
  6. Formulierung nach einem der Ansprüche 1 bis 5, wobei die Formulierung einen Schwefelgehalt von unter 0,5 Gew.-% hat.
  7. Formulierung nach einem der Ansprüche 1 bis 6, wobei die Formulierung außerdem mehr als 10 mg/kg bis weniger als 0,6 Gew.-% eines Antioxidationsmittelzusatzes enthält, wobei der Antioxidationsmittelzusatz ein Phenol- oder Amin-Antioxidationsmittel ist.
  8. Formulierung nach Anspruch 7, wobei der Antioxidationsmittelzusatz Di-tert-Butylhydroxotoluol ist.
  9. Formulierung nach einem der Ansprüche 1 bis 8, wobei die kinematische Viskosität der Grundöl-Zusammensetzung bei 40°C zwischen 1 und 4 mm2/s beträgt.
  10. Formulierung nach einem der Ansprüche 1 bis 8, wobei die kinematische Viskosität der Grundöl-Zusammensetzung bei 40°C zwischen 5 und 15 mm2/s beträgt.
  11. Verfahren zur Bereitung einer Formulierung nach einem der Ansprüche 1 bis 6, wobei ein Gemisch der Grundöl-Zusammensetzung und des organischen Schwefel-Verschleißschutzzusatzes einer Bleicherdebehandlung unterzogen wird und wobei das Kupferpassivierungsmittel nach dem Durchführen der Bleicherdebehandlung zugegeben wird.
  12. Verwendung der Formulierung nach einem der vorhergehenden Ansprüche als Elektroöl.
  13. Verwendung der Formulierung nach Anspruch 12 als Transformatorenöl.
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