CN101385095A - Electrical insulation oil composition - Google Patents

Electrical insulation oil composition Download PDF

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Publication number
CN101385095A
CN101385095A CNA2007800056679A CN200780005667A CN101385095A CN 101385095 A CN101385095 A CN 101385095A CN A2007800056679 A CNA2007800056679 A CN A2007800056679A CN 200780005667 A CN200780005667 A CN 200780005667A CN 101385095 A CN101385095 A CN 101385095A
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Prior art keywords
oil
electric insulation
composition
oil composition
insulation oil
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Y·马场
H·高桥
H·寺井
N·田中
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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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
    • 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
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    • 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
    • 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
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • 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
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C10M2203/1085—Residual fractions, e.g. bright stocks 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
    • C10M2205/02—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
    • 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
    • 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
    • C10N2030/12—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
    • 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

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

Abstract

An electrical insulating oil having a flash point (PMCC) of 130 DEG C or more and a pour point of -40 DEG C or lower, which composition comprises hydrorefined mineral oil and/or synthetic hydrocarbon oil and in the range of from 0.5 to 10 wt .% of bright stock oil, based on the total weight of the electrical insulating oil composition.

Description

Electric insulation oil composition
Technical field
The present invention relates to electric insulation oil (e1ectrical insulating oil) composition.
Background technology
Before using, transformer, primary cut-out and other high-voltage electric device are filled with electric insulation oil composition.Yet these electric devices must can not need be safeguarded the long-term use in ground after the running beginning.Similarly, require this based composition can long term maintenance stable physical performance and electrical property.
As everyone knows, when electric insulation oil composition used for a long time, their deteriorations descended and decreasing insulating because the formation of the raising of the acid number of electric insulation oil composition and sludge causes corrosion resistance.Therefore, along with high-voltage electric device towards high pressure more, more large scale and the trend development of long life more, it is more important that the stability of use therein electric insulation oil composition has become.
IEC (International Electrotechnical Commission, International Electrotechnical Commission) stipulated for being used to fill the desired performance of electric insulation oil composition of transformer, primary cut-out and other electric device and for the desired performance of mineral oil dielectric oil composition that can stand long-term use according to standard IEC 296 and IEC60296.
Simultaneously, along with mineral oil refining development of technology, hydrofinishing process is adopted widely, the feasible oil that can obtain wherein to have removed fully polynuclear aromatic compound, unsaturated component, nitrogen content and sulphur content.At first, thought once that electric insulation oil composition did not comprise nitrogen or the sulphur content is reasonable.
Subsequently, yet Japan special permission publication application number 2000-345177 A discloses for oxidation stability and others, and it is preferred that electric insulation oil composition comprises a certain amount of these components.Therefore, JP 2000-345177 A proposes by the resin content in the electric insulation oil composition is reduced to＜100ppm, and sulfide type sulfur content and the total nitrogen content of introducing few quantity, improved the stability of electric insulation oil composition, and the increase of electric charge is inhibited.
In fact, it is extremely difficult by oil refining process crude oil refining being reached the state that is suitable for electric insulation oil composition to wherein nitrogen content or sulfur content.
Therefore, at present, though the suitable junction compound that has the additive of nitrogen content or sulfur content or an analog by interpolation attempts to regulate component wherein in the highly purified refined oil, but still exist and operable additive relative restrictions, this depends on the electric insulation oil specification, in addition, also there are cost problem and production management complications.
Therefore the electric insulation oil composition that can obtain to have the balance of excellent electric performance, cryogenic property, thermo oxidative stability and corrosion resistance by economic and simple method is highly desirable.
Summary of the invention
In the present invention, it has surprisingly been found that, by adding a little light gloss varnish in hydrorefined mineral oils and/or synthetic hydrocarbon oil, might be simply and improve thermo oxidative stability economically and obtain to satisfy in IEC standard 296 and the IEC standard 60296 electric insulation oil composition to all kinds of performances of electric insulation oil composition requirement.
Therefore, the invention provides electric insulation oil composition with 130 ℃ or higher flash-point (PMCC) and-40 ℃ or lower pour point, said composition comprises hydrorefined mineral oils and/or synthetic hydrocarbon oil and 0.5-10wt% bright stock, in the total weight of this electric insulation oil composition.
In an embodiment preferred of the present invention, electric insulation oil composition has-45 ℃ or lower pour point.
In an embodiment preferred of the present invention, electric insulation oil composition has 135 ℃ or higher flash-point (PMCC).
The hydrorefined mineral oils that may reside in the electric insulation oil composition of the present invention can be by making with extra care mineral oil hydrogenation.The example of the hydrorefined mineral oils that can use aptly comprises hydrofinishing naphthenic mineral oil and hydrorefined paraffinic mineral oils.
Via the hydrofinishing of mineral oil, polycyclic aromatic material, unsaturated component, sulphur compound and nitrogen compound have been removed.Compare with hydrorefined paraffinic mineral oils, the hydrofinishing naphthenic mineral oil can have better low temperature flow and lower oxidation stability, on the contrary, compare with the hydrofinishing naphthenic mineral oil, hydrorefined paraffinic mineral oils can have poor low temperature flow, but thermo oxidative stability is better.
The example that can be used for the synthetic hydrocarbon oil of electric insulation oil composition of the present invention aptly comprises polypropylene, polybutene, polypenthylene and other different alkane synthetic hydrocarbon oil, belong to API (American Petroleum Institute (API)) base oil that following table 1 provides the classify poly alpha olefin (PAO) and Gas toLiquid (GTL) artificial oil (natural gas system artificial oil, Gas to Liquid) of IV class.
Can use the synthetic hydrocarbon base oil of selling with trade name ＂ XHVI ＂ by She11 group aptly.
Japan special permission publication application 52-072706A and Japan special permission publication application 07-228876 have described the manufacture method that can be used for the synthetic hydrocarbon oil of electric insulation oil composition of the present invention aptly.
Can use individually at hydrorefined mineral oils of preceding mentioning and synthetic hydrocarbon oil.Yet, can regulate pour point, kinematic viscosity, thermo oxidative stability of electric insulation oil composition of the present invention etc. best by the suitable combination of some materials.
Hydrorefined mineral oils of using in the electric insulation oil composition of the present invention and/or synthetic hydrocarbon oil have separately at 40 ℃ of following 8.0-24mm 2The preferred movement viscosity of/s.
Preferred hydrorefined mineral oils can be selected from hydrofinishing naphthenic mineral oil and/or API base oil classify II class or III class hydrorefined paraffinic mineral oils.
Preferred synthetic hydrocarbon oil can be selected from different alkane artificial oil, GTL artificial oil and belong to API base oil the classify poly alpha olefin (PAO) or their mixture of IV class.
Because the kinematic viscosity of bright stock is compared higher with hydrorefined mineral oils and/or synthetic hydrocarbon oil, if so hydrorefined mineral oils or synthetic hydrocarbon oil use with bright stock individually, then especially preferred hydrorefined mineral oils and/or the proper motion viscosity (intrinsic kinematic viscosity) of synthetic hydrocarbon oil under 40 ℃ are 16mm 2/ s or lower, more preferably 12mm 2/ s or lower.
If use the bond of hydrorefined mineral oils and synthetic hydrocarbon oil with bright stock, then the corresponding kinematic viscosity of hydrorefined mineral oils and synthetic hydrocarbon oil is separately preferably at 8.0-24.0mm 2/ s, more preferably 8.0-20.0mm 2In the scope of/s.
Table 1
Figure A200780005667D00071
The bright stock that adds in hydrorefined mineral oils of preceding mentioning and/or synthetic hydrocarbon oil can followingly obtain: when under normal pressure during from the crude distillation paraffinic mineral oil, under reduced pressure further distill the normal pressure relict mineral oil that is obtained, and this decompression residual oil is carried out depitching, solvent extraction and solvent dewaxing process.Just, described bright stock can be the heavy mineral oil base oil fraction of following acquisition: will be from the remaining paraffinic mineral oil decompression distillation of the air-distillation of crude oil, and the Residual oil that is obtained is carried out depitching, solvent extraction and solvent dewaxing handle.
The bright stock that uses among the present invention preferably belongs to the classify base oil of I class of API base oil, total sulfur content with 0.4-2.0wt%, 100wt.ppm or mercaptan sulfur content still less, 0.5wt% or sulfide type sulfur content still less, 100-500wt.ppm total nitrogen content, 300wt.ppm or the polar compound total content (IP368) of basic n content still less and 30-70wt%.
By distillation and solvent extraction technology various sulphur compounds and nitrogen compound are concentrated in the described bright stock.Total weight in electric insulation oil composition of the present invention, by in described electric insulation oil composition, using 0.5-10wt%, the preferred described bright stock of 0.5-8.0wt% is introduced in this electric insulation oil composition with suitable amount at sulphur content of preceding mentioning and nitrogen content.Therefore might improve their thermo oxidative stability significantly.If become too high at mercaptan sulfur of preceding mentioning and sulfide type sulfur content, then corrosivity may become higher, and this is undesirable.In addition, if basic n content surpasses 300wt.ppm, then oxidation stability performance may reduce.
Electric insulation oil composition of the present invention has 8.0-16.0mm under 40 ℃ 2The preferred movement viscosity of/s, more preferably 8.0-12.0mm 2/ s.Under 40 ℃, have less than 8.0mm 2The kinematic viscosity of/s possibly can't obtain gratifying flash-point.If surpass 16.0mm 40 ℃ of following kinematic viscosity 2/ s, then the cycle efficieny of electric insulation oil composition in transformer may reduce, and it is insufficient that cooling effect may become, and overheated may the generation.
Electric insulation oil composition of the present invention can comprise one or more anti-oxidant additives.The antioxidant that can use aptly is phenols or amine antioxidants.
The example that can be used for the phenol antioxidant of electric insulation oil composition of the present invention aptly comprises 4,4 '-di-2-ethylhexylphosphine oxide (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 4,4 '-Ding fork base two (3 methy 6 tert butyl phenol), 4,4 '-isopropylidene two (2, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene-bis(4-methyl-6-nonyl phenol), 2,2 '-isobutyl fork base two (4, the 6-xylenol), 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2, the 6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethyl-phenol, 2,4-dimethyl-6-tert-butyl phenol, 2,6-di-t-butyl-alpha-alpha-dimethyl amino-paracresol, 2,6-di-t-butyl-4-(N, N '-dimethylaminomethyl phenol), 4,4 '-thiobis (2-methyl-6-tert butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), two (3-methyl-4-hydroxyl-5-tert-butyl group benzyl) thioether, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether, 2,2 '-[3-(3 for the sulfo-di ethylene bis, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], tridecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, [3-(3 for pentaerythrite-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octyl group-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, octyl group-3-(3-methyl-5-tert-butyl-hydroxy phenyl) propionic ester.
In the total weight of electric insulation oil composition, the content of described one or more anti-oxidant additives is more preferably less than 1wt% preferably less than 2wt%, even is more preferably less than 0.6wt%, most preferably less than 0.4wt%.
In an embodiment preferred of the present invention, in the total weight of electric insulation oil composition, this electric insulation oil composition comprises the 0.01-0.4wt% phenol antioxidant.
In other embodiments of the present invention, in the total weight of electric insulation oil composition, preferably this electric insulation oil composition comprises 0.01-0.08wt% or 0.08-0.4wt% phenol antioxidant.
Can also be present in the application-specific that other additive in the electric insulation oil composition of the present invention depends on electric insulation oil composition.
By adding bright stock in hydrorefined mineral oils of preceding mentioning and/or synthetic hydrocarbon oil, can obtain to meet IEC (International Electrotechnical Commission) standard 296, the electric insulation oil composition of II class, promptly in IEC oxidation stability test method 61125A, descend maintenance after 168 hours at 100 ℃, sludge form be 0.1wt% or still less and acid number be 0.4mgKOH/g or lower.
Therefore, in a preferred embodiment, the invention provides and have 130 ℃ or higher flash-point (PMCC) and-40 ℃ or lower, more preferably-45 ℃ or the electric insulation oil composition of lower pour point, said composition comprises hydrorefined mineral oils and/or synthetic hydrocarbon oil and 0.5-10wt% bright stock, and said composition meets IEC (International Electrotechnical Commission) standard 296, the II class, promptly in IEC oxidation stability test method 61125A at 100 ℃ after following 168 hours, sludge form be 0.1% or still less and acid number be 0.4mgKOH/g or lower.
In addition, by adding bright stock in hydrorefined mineral oils of preceding mentioning and/or synthetic hydrocarbon oil, can obtain to meet IEC standard 60296, the electric insulation oil composition of U type, promptly in IEC oxidation stability test method 61125C, descend maintenance after 164 hours at 120 ℃, sludge form be 0.8wt% or still less and acid number be 1.2mgKOH/g or lower.
Therefore, in a preferred embodiment, the present invention further provides and have 130 ℃ or higher, more preferably 135 ℃ or higher flash-point (PMCC) and-40 ℃ or lower, more preferably-45 ℃ or the electric insulation oil composition of lower pour point, said composition comprises hydrorefined mineral oils and/or synthetic hydrocarbon oil and 0.5-10wt% bright stock, and said composition meets IEC standard 60296, the U type, promptly in IEC oxidation stability test method 61125C at 120 ℃ after following 164 hours, sludge form be 0.8wt% or still less and acid number be 1.2mgKOH/g or lower.
In addition, in a preferred embodiment, by adding bright stock, and further add 0.01-0.4wt%, more preferably 0.08-0.4wt% antioxidant, preferred phenol antioxidant is in hydrorefined mineral oils of preceding mentioning and/or synthetic hydrocarbon oil, can obtain to meet the electric insulation oil composition of IEC standard 60296I type, promptly in IEC oxidation stability test method 61125C, descend maintenance after 500 hours at 120 ℃, sludge form be 0.8wt% or still less and acid number be 1.2mgKOH/g or lower.
Therefore, in a preferred embodiment, the present invention further provides and have 130 ℃ or higher, more preferably 135 ℃ or higher flash-point (PMCC) and-40 ℃ or lower, more preferably-45 ℃ or the electric insulation oil composition of lower pour point, said composition comprises hydrorefined mineral oils and/or synthetic hydrocarbon oil, 0.5-10wt% bright stock and 0.01-0.4wt%, more preferably 0.08-0.4wt% antioxidant, preferred phenol antioxidant, and said composition meets IEC standard 60296, the I type, promptly in IEC oxidation stability test method 61125C at 120 ℃ after following 500 hours, sludge form be 0.8wt% or still less and acid number be 1.2mgKOH/g or lower.
In addition, similarly, by adding bright stock, and further add 0.01-0.4wt%, more preferably 0.01-0.08wt% antioxidant, preferred phenol antioxidant is in hydrorefined mineral oils of preceding mentioning and/or synthetic hydrocarbon oil, can obtain to meet the electric insulation oil composition of IEC standard 60296T type, promptly in IEC oxidation stability test method 61125C 120 ℃ down keep 332 hours after, sludge form be 0.8wt% or still less and acid number be 1.2mgKOH/g or lower.
Therefore, in a preferred embodiment, the present invention further provides and have 130 ℃ or higher, more preferably 135 ℃ or higher flash-point (PMCC) and-40 ℃ or lower, more preferably-45 ℃ or the electric insulation oil composition of lower pour point, said composition comprises hydrorefined mineral oils and/or synthetic hydrocarbon oil, 0.5-10wt% bright stock and 0.01-0.4wt%, more preferably 0.01-0.08wt% antioxidant, preferred phenol antioxidant, and said composition meets IEC standard 60296, the T type, promptly in IEC oxidation stability test method 61125C at 120 ℃ after following 332 hours, sludge form be 0.8wt% or still less and acid number be 1.2mgKOH/g or lower.
Promptly, the invention provides electric insulation oil composition, said composition is observed one or more in the following standard: IEC (International Electrotechnical Commission) standard 296 (II class), IEC standard 60296 (U type), IEC standard 60296 (I type) and IEC standard 60296 (T type).
The application that the present invention further provides above-described electric insulation oil composition is to observe in the following standard one or more: IEC (International Electrotechnical Commission) standard 296 (II class), IEC standard 60296 (U type), IEC standard 60296 (I type) and IEC standard 60296 (T type).
The present invention further provides above-described composition and be applied to one or more purposes in transformer, adjuster, circuit breaker, power plant reactor, shunt reactor, switchgear, cable and the electric equipment as electric insulation oil.
With reference to following examples the present invention is described, in any case these embodiment intention of the scope of the invention without limits.
Embodiment
As hydrorefined mineral oils, mineral oil and synthetic hydrocarbon oil, base oil A-J and bright stock that preparation has performance shown in table 2, table 3 and the table 4.
Base oil A-J and bright stock
The performance of base oil A-J and bright stock provides in table 2, table 3 and table 4 according to following benchmark.
(1) flash-point: according to JIS K 2265 (PMCC:Pensky-Martens closed-cup method and COC:Cleveland open agar diffusion method).
(2) kinematic viscosity (40 ℃), kinematic viscosity (100 ℃): according to ASTM D445.
(3) pour point: according to ASTM D97.
(4) acid number: according to ASTM D974.
(5) PCA (PCA content): according to BS2000P-346.
Figure A200780005667D00121
Figure A200780005667D00131
Table 4
Figure A200780005667D00141
Use prepares embodiment 1-7 at base oil A-J and the bright stock preceding mentioned according to the composition shown in table 5 and the table 6, and they are the electric insulation oil compositions that do not contain antioxidant according to of the present invention.
In addition, prepare embodiment 8-11 according to the composition shown in the table 7, they are the electric insulation oil compositions that contain antioxidant according to of the present invention.
In addition, for at the embodiment that preceding mentions relatively, prepare comparative example 1-15 according to the composition shown in the table 8-10.
The ＂ clay treatment ＂ that relates among the 5-10 for table uses activated clay and they was mixed in 15 minutes by stirring down at 30-40 ℃ by the specified rate with respect to oil ingredient, and separates oil reservoir by press filtration.By the general process for purification of electric insulation oil composition process in case to electric insulation oil composition decolour, deodorization, dehydration and stability improvement.
Table 5
Form Ex.1 Ex.2 Ex.3 Ex.4 Ex.5
Base oil A (wt.%) 80 80 80 60 80
Base oil B (wt.%) 16 - 17 - -
Base oil C (wt.%) - 16 - - -
Base oil D (wt.%) - - - 25 5
Base oil H (wt.%) - - - 13 13
Bright stock (wt.%) 4 4 3 2 2
Clay treatment * 1％ 1％ 1％ 1％ 1％
*Wt% is with respect to the amount of the oil ingredient that uses.
Table 6
Form Ex.6 Ex.7
Base oil A (wt.%) 70.8 71.6
Base oil I (wt.%) 25.5 -
Base oil J (wt.%) - 24.5
Bright stock (wt.%) 3.7 3.9
Clay treatment * 1％ 1％
*Wt% is with respect to the amount of the oil ingredient that uses.
Table 7
Form Ex.8 Ex.9 Ex.10 Ex.11
Base oil A (wt.%) 80 80 80 80
Base oil B (wt.%) 16 － 16 －
Base oil C (wt.%) － 16 － 16
Bright stock (wt.%) 3.9 3.9 3.95 3.95
Antioxidant 〃 BHT " (wt.%) 0.1 0.1 0.05 0.05
Clay treatment * 1％ 1％ 1％ 1％
Footnote: antioxidant ＂ BHT ＂ is a 2,6 di tert butyl 4 methyl phenol
*Wt% is with respect to the amount of the oil ingredient that uses.After clay treatment, ＂ BHT ＂ is added in the oil ingredient.
Table 8
Form The comparative example 1 The comparative example 2 The comparative example 3 The comparative example 4 The comparative example 5
Base oil A (wt.%) 100 - - 80 80
Base oil B (wt.%) - - - 20 -
Base oil C (wt.%) - - - - -
Base oil D (wt.%) - - 100 - -
Base oil E (wt.%) - - - - 20
Base oil F (wt.%) - - - - -
Base oil G (wt.%) - 100 - - -
Base oil H (wt.%) - - - - -
Bright stock (wt.%) - - - - -
Clay treatment * 1％ 1％ 1％ 1％ 1％
*Wt% is with respect to the amount of the oil ingredient that uses.
Table 9
Form The comparative example 6 The comparative example 7 The comparative example 8 The comparative example 9 The comparative example 10
Base oil A (wt.%) 80 80 80 80 60
Base oil B (wt.%) - - - - -
Base oil C (wt.%) - - - - -
Base oil D (wt.%) - - - 20 40
Base oil E (wt.%) - - - - -
Base oil F (wt.%) 20 - - - -
Base oil G (wt.%) - 20 30 - -
Base oil H (wt.%) - - - - -
Bright stock (wt.%) - - - - -
Clay treatment * 1％ 1％ 1％ 1％ 1％
*Wt% is with respect to the amount of the oil ingredient that uses.
Table 10
Form The comparative example 11 The comparative example 12 The comparative example 13 The comparative example 14 The comparative example 15
Base oil A (wt.%) 70 70 60 80 90
Base 7 plinth oil B (wt.%) - - - - -
Base oil C (wt.%) - - - - -
Base oil D (wt.%) - - - - -
Base oil E (wt.%) 15 20 27 - -
Base oil F (wt.%) - - - - -
Base oil G (wt.%) - - - - -
Base oil H (wt.%) 15 10 13 20 10
Bright stock (wt.%) - - - - -
Clay treatment * 1％ 1％ 1％ 1％ 1％
*Wt% is with respect to the amount of the oil ingredient that uses.
The IEC standard value is as the canonical reference value of the performance of electric insulation oil composition.If satisfy these canonical reference values, think that then long-term stable use is possible in wide temperature range.
Therefore, at the embodiment 1 and 2 that preceding mentions (not containing antioxidant), measure the value of electric insulation oil performance, and with those results and IEC standard 296, the canonical reference value of II class is together shown in the table 11.
In addition, at the embodiment 1,2,6 and 7 (not containing antioxidant) that preceding mentions, measure the value of electric insulation oil performance, and with those results and IEC standard 60296, the canonical reference value of U type is together shown in the table 12.
As follows to measurement regulation in the value of the described performance of the base oil of preceding mentioning (except that (1)-(5)).
(6) surface tension: according to ASTM D971.
(7) active sulfur: according to ASTM D1275.
(8) water content: according to ASTM D1533.
(9) oxidation test (168 hours, 100 ℃): according to IEC method 61125A.
(10) oxidation test (164 hours, 120 ℃): according to IEC method 61125C.
(11) breakdown voltage: according to ASTM1816 (VDE).
For at the embodiment 3-5 that preceding mentions (not containing antioxidant), density measurement and according to above-mentioned IEC standard 296, the II class (100 ℃ following 168 hours, IEC method 61125A) the value of oxidation stability, and with those results shown in the table 13.
For at the embodiment 8 and 9 (containing antioxidant) that preceding mentions, measure the value of electric insulation oil performance, and with those results and IEC standard 60296, the standard value of I type is together shown in the table 14.
As follows to measurement regulation in the value of base oil of preceding mentioning and the described performance of embodiment (not containing antioxidant) (except that (1)-(11)).
(12) oxidation test (500 hours, 120 ℃): according to IEC method 61125C.
Embodiment 10 and 11 (containing antioxidant) has than embodiment 8 and 9 lower oxidation preventive contents, measures the value of their electric insulation oil performance, and with those results and IEC standard 60296, the standard value of T type is together shown in the table 15.
As follows to measurement regulation in the value of oil of preceding mentioning and the described performance of embodiment (not containing antioxidant) (except that (1)-(11)).
(13) oxidation test (332 hours, 120 ℃): according to IEC method 61125C.
For comparative example 1-15, according in the IEC standard of preceding mentioning 296, the II class (100 ℃ following 168 hours, IEC method 61125A) measure in the oxidation stability of preceding mentioning, and with those results shown in the table 16-18.
Discuss
The electric insulation oil composition that does not contain antioxidant for embodiment 1-7, the value (think important characteristic value) relevant with oxidation stability (IEC oxidation test) is significantly less than IEC standard 296, II class standard reference value (maximum) or IEC standard 60296, U type canonical reference value (maximum), and to pass judgment on described composition be excellent as electric insulation oil composition.
For embodiment 1 and 2, the value of carrying out oxidation test and carrying out oxidation test by the IEC method 61125C in the IEC standard 60296 (following 164 hours at 120 ℃) by the IEC method 61125A in the IEC standard 296 (following 168 hours at 100 ℃) is significantly less than the canonical reference value (maximum) in arbitrary standard of these standards, and said composition is excellent.
In addition, for embodiment 1,2,6 and 7, all characteristic values that provide in table 11 and the table 12, especially kinematic viscosity, pour point and the acid number under 40 ℃ and-30 ℃ all reaches favourable outcome, and all compositions satisfy IEC standard 296, II type and/or IEC standard 60296, the canonical reference value of U type.
In addition, the electric insulation oil composition that contains antioxidant for embodiment 8 and 9, with IEC standard 60296, in relevant IEC method 61125C (the following 500 hours) oxidation test of I type at 120 ℃, the value relevant with oxidation stability (thinking important characteristic value) is separately significantly less than therein canonical reference value (maximum), and they are judged as excellent electric insulation oil composition.In addition, the further feature value, the especially kinematic viscosity that provide in the table 14 also reach favourable outcome, and these two kinds of compositions satisfy IEC standard 60296, the canonical reference value of I type.
In addition, the electric insulation oil composition that contains small amount of antioxidant for embodiment 10 and 11, with IEC standard 60296, in relevant IEC method 61125C (the following 332 hours) oxidation test of T type at 120 ℃, the value relevant with oxidation stability (thinking important characteristic value) is separately significantly less than therein canonical reference value, and described composition is judged as excellent electric insulation oil composition.The further feature value, the especially kinematic viscosity that provide in the table 15 also reach favourable outcome, and these two kinds of compositions satisfy IEC standard 60296, the canonical reference value of T type.
Yet, material for the comparative example 1-15 that does not wherein use bright stock, in IEC method 61125A (at the 100 ℃ following 168 hour) oxidation test relevant with the IEC standard preceding mentioned 296, composition does not satisfy IEC standard 296, the canonical reference value of II class.In other words, comparative example 1-9 and 15 the material reference value (maximum) that is above standard significantly, and judge that Comparative composition is not suitable for use in electric insulation oil composition.In addition, though the composition of comparative example 10-14 satisfies the canonical reference value aspect acid number, described composition does not satisfy the canonical reference value aspect sludge, and judges that described Comparative composition can not be as the electric insulation oil composition that is fit to.
Figure A200780005667D00201
Figure A200780005667D00211
Figure A200780005667D00221
Figure A200780005667D00231
Figure A200780005667D00251
Figure A200780005667D00261
Figure A200780005667D00271
Figure A200780005667D00291

Claims (10)

1. electric insulation oil composition, it has 130 ℃ or higher flash-point (PMCC) and-40 ℃ or lower pour point, and said composition comprises hydrorefined mineral oils and/or synthetic hydrocarbon oil and 0.5-10wt% bright stock, in the total weight of this electric insulation oil composition.
2. according to the electric insulation oil composition of claim 1, wherein said composition has-45 ℃ or lower pour point.
3. according to the electric insulation oil composition of claim 1 or 2, wherein said composition has 135 ℃ or higher flash-point (PMCC).
4. according to each electric insulation oil composition among the claim 1-3, wherein said composition comprises the 0.01-0.4wt% phenol antioxidant, in the total weight of this electric insulation oil composition.
5. according to each electric insulation oil composition among the claim 1-4, wherein said composition comprises the 0.01-0.08wt% phenol antioxidant, in the total weight of this electric insulation oil composition.
6. according to each electric insulation oil composition among the claim 1-4, wherein said composition comprises the 0.08-0.4wt% phenol antioxidant, in the total weight of this electric insulation oil composition.
7. according to each electric insulation oil composition among the claim 1-6, wherein this hydrorefined mineral oils has 8.0-24mm under 40 ℃ 2The kinematic viscosity of/s and be selected from the hydrofinishing naphthenic mineral oil and/or API base oil classify II class or III class hydrorefined paraffinic mineral oils.
8. according to each electric insulation oil composition among the claim 1-7, wherein this synthetic hydrocarbon oil has 8.0-24mm under 40 ℃ 2The kinematic viscosity of/s and be selected from different alkane artificial oil, GTL artificial oil, belong to API base oil the classify poly alpha olefin (PAO) or their mixture of IV class.
9. according to each electric insulation oil composition among the claim 1-8, wherein this bright stock is the heavy mineral oil base oil fraction of following acquisition: will be from the remaining paraffinic mineral oil decompression distillation of the air-distillation of crude oil, and the Residual oil that is obtained is carried out depitching, solvent extraction and solvent dewaxing handle.
10. according to each electric insulation oil composition among the claim 1-9, said composition is observed one or more in the following standard: IEC (International Electrotechnical Commission) standard 296 (II class), IEC standard 60296 (U type), IEC standard 60296 (I type) and IEC standard 60296 (T type).
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