WO2007093631A1 - Electrical insulation oil composition - Google Patents

Electrical insulation oil composition Download PDF

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Publication number
WO2007093631A1
WO2007093631A1 PCT/EP2007/051484 EP2007051484W WO2007093631A1 WO 2007093631 A1 WO2007093631 A1 WO 2007093631A1 EP 2007051484 W EP2007051484 W EP 2007051484W WO 2007093631 A1 WO2007093631 A1 WO 2007093631A1
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WIPO (PCT)
Prior art keywords
oil
electrical insulating
insulating oil
composition
range
Prior art date
Application number
PCT/EP2007/051484
Other languages
French (fr)
Inventor
Yoshiharu Baba
Hiroyuki Takahashi
Hideto Terai
Norimitsu Tanaka
Original Assignee
Shell Internationale Research Maatschappij B.V.
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Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP07704608A priority Critical patent/EP1984927B1/en
Priority to AT07704608T priority patent/ATE533166T1/en
Priority to BRPI0708062-0A priority patent/BRPI0708062A2/en
Priority to ES07704608T priority patent/ES2373577T3/en
Publication of WO2007093631A1 publication Critical patent/WO2007093631A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication 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
    • C10M111/02Lubrication 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication 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
    • C10M111/04Lubrication 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20Insulators 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
    • H01B3/22Insulators 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • C10M2203/1025Aliphatic fractions used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106Naphthenic fractions
    • C10M2203/1065Naphthenic fractions used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108Residual fractions, e.g. bright stocks
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108Residual fractions, e.g. bright stocks
    • C10M2203/1085Residual fractions, e.g. bright stocks used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic 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
    • C10M2205/0285Organic 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17Fisher Tropsch reaction products
    • C10M2205/173Fisher Tropsch reaction products used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/14Electric or magnetic purposes
    • C10N2040/16Dielectric; Insulating oil or insulators

Definitions

  • the present invention relates to an electrical insulating oil composition.
  • Transformers, high-pressure circuit breakers and other high-pressure electrical devices are filled with electrical insulating oil compositions before use.
  • the IEC International Electrotechnical Commission
  • the IEC International Electrotechnical Commission
  • the hydrorefining method has been widely adopted, making it possible to obtain oils from which polycyclic aromatics, unsaturated components, nitrogen content and sulphur content have been adequately removed.
  • JP 2000-345177 A discloses that with regard to oxidation stability and other aspects it was preferable for electrical insulating oil compositions to contain a certain amount of these components.
  • JP 2000-345177 A proposes that by reducing the resin content in an electrical insulating oil composition to ⁇ 100 ppm, and also incorporating minute amounts of sulphide-type sulphur content and total nitrogen content, the stability of the electrical insulating oil composition is increased, and increases in electric charge are inhibited.
  • the present invention provides an electrical insulting oil composition having a flash point (PMCC) of 13O 0 C or more and a pour point of -40 0 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 .
  • PMCC flash point
  • -40 0 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 .
  • the electrical insulating oil composition has a pour point of -45 0 C or lower. In a preferred embodiment of the present invention, the electrical insulating oil composition has a flash point (PMCC) of 135 0 C or more.
  • the hydrorefined mineral oil that may be present in the electrical insulating oil composition of the present invention may be refined by hydrogenating mineral oil. Examples of hydrorefined mineral oils that may be conveniently used include hydrorefined naphthenic mineral oil and hydrorefined paraffinic mineral oil.
  • the hydrorefined naphthenic mineral oils may have better low temperature flow properties and lower oxidation stability, and, conversely, compared to the hydrorefined naphthenic mineral oils, the hydrorefined paraffinic mineral oils may have inferior low temperature flow properties, but better thermal oxidation stability.
  • Examples of synthetic hydrocarbon oils that may be conveniently used in the electrical insulating oil composition of the present invention include polypropylene, polybutene, polypentene and other isoparaffinic synthetic hydrocarbon oils, poly- ⁇ -olefins (PAO) falling within Group IV in the API (American Petroleum Institute) base oil classification stated below in Table 1, and Gas to Liquid (GTL) synthetic oils.
  • Synthetic hydrocarbon base oils sold by the Shell group under the trade designation "XHVI" may be conveniently used.
  • Japanese Laid-Open Patent Application 52-072706 A and Japanese Laid-Open Patent Application 07-228876 describe methods of manufacturing synthetic hydrocarbon oils that may be conveniently used in the electrical insulating oil composition of the present invention.
  • the afore-mentioned hydrorefined mineral oils and synthetic hydrocarbon oils may be used alone.
  • the pour point, kinematic viscosity, thermal oxidation stability and the like of the electrical insulating oil composition of the present invention may be optimally adjusted by appropriate combination of several substances .
  • the hydrorefined mineral oil and/or synthetic hydrocarbon oil used in the electrical insulating oil composition of the present invention each have a preferred kinematic viscosity at 4O 0 C in the range of from 8.0 to 24 mm 2 /s.
  • Preferred hydrorefined mineral oils may be selected from hydrorefined naphthenic mineral oils and/or API base oil classification Group II or Group III hydrorefined paraffinic mineral oils .
  • Preferred synthetic hydrocarbon oils may be selected from isoparaffinic synthetic oils, GTL synthetic oils and poly- ⁇ -olefins (PAO) belonging to API base oil classification Group IV or mixtures thereof.
  • PAO poly- ⁇ -olefins
  • the intrinsic kinematic viscosity of the hydrorefined mineral oil and/or synthetic hydrocarbon oil at 40°C is 16 mm 2 /s or less, more preferably 12 mm 2 /s or less if hydrorefined mineral oil or synthetic hydrocarbon oil is used alone with bright stock oil.
  • the respective kinematic viscosity of the hydrorefined mineral oil and the synthetic hydrocarbon oil is each preferably in the range of from 8.0 to 24.0 mm 2 /s, more preferably in the range of from 8.0 to 20.0 mm 2 /s.
  • the bright stock oil added to the afore-mentioned hydrorefined mineral oil and/or synthetic hydrocarbon oil may be obtained by further distilling under reduced pressure the atmospheric pressure residual mineral oil obtained when paraffinic mineral oil is distilled at atmospheric pressure from crude oil, and performing deasphalting, solvent extraction and solvent dewaxing processes on that reduced pressure residual oil.
  • said bright stock oil may be a heavy mineral oil base oil fraction obtained by reduced pressure distillation of the residual paraffinic mineral oil from atmospheric distillation of crude oil, and deasphalting, solvent extraction and solvent dewaxing treatment of the residual oil obtained.
  • the bright stock oil used in the present invention is preferably a base oil belong to API base oil classification Group I, with total sulphur content in the range of from 0.4 to 2.0 wt . % , mercaptan sulphur content of 100 wt. ppm or less, sulphide-type sulphur content of 0.5 wt .% or less, total nitrogen content in the range of from 100 to 500 wt . ppm, basic nitrogen content of 300 wt. ppm or less, and total content of polar components (IP368) in the range of from 30 to 70 wt . % .
  • IP368 total content of polar components
  • Various sulphur compounds and nitrogen compounds are concentrated in said bright stock oil by the distillation and solvent extraction processes.
  • the afore-mentioned sulphur content and nitrogen content are incorporated in appropriate quantities in the electrical insulating oil composition.
  • the electrical insulating oil composition of the present invention has a preferred kinematic viscosity at 40 0 C in the range of from 8.0 to 16.0 mm 2 /s, more preferably in the range of from 8.0 to 12.0 mm 2 /s. With a kinematic viscosity at 40°C of less than 8.0 mm 2 /s, a satisfactory flash point may not be obtained.
  • the electrical insulating oil composition of the present invention may comprise one or more antioxidant additives.
  • Antioxidants that may be conveniently used are phenolic or aminic antioxidants .
  • phenolic antioxidants examples include 4,4'- methylenebis (2, 6-di-tert . -butylphenol ) , 4, 4' -bis (2, 6-di- tert .-butylphenol) , 4,4' -bis (2-methyl-6-tert . - butylphenol) , 2,2' -methylenebis (4-ethyl-6-tert.- butylphenol) , 2,2' -methylenebis ( 4-methyl-6-tert . - butylphenol), 4 , 4 ' -butylidenebis ( 3-methyl-6-tert .
  • the content of the one or more antioxidant additives is preferably less than 2 wt.%, more preferably less than 1 wt. %, even more preferably less than 0.6 wt . % and most preferably less than 0.4 wt.%, based on the total weight of the electrical insulating oil composition.
  • the electrical insulating oil composition comprises in the range of from 0.01 to 0.4 wt.% of phenolic antioxidant, based on the total weight of the electrical insulating oil composition.
  • the electrical insulating oil composition comprises in the range of from 0.01 to 0.08 wt.% or in the range of from 0.08 to 0.4 wt.% of phenolic antioxidant, based on the total weight of the electrical insulating oil composition.
  • Further additives that may also be present in the electrical insulating oil composition of the present invention are dependent upon the specific application of the electrical insulating oil composition.
  • the present invention provides an electrical insulating oil composition having a flash point (PMCC) of 130°C or more and a pour point of -40 0 C or lower, more preferably of -45°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, and which composition conforms with IEC (International Electrotechnical Commission) Standard 296, Class II, in that after 168 hrs at 100 0 C in IEC oxidation stability test method 61125A, sludge formation is 0.1% or less, and the acid value is 0.4 mg KOH/g or less.
  • PMCC flash point
  • -40 0 C or lower more preferably of -45°C or lower
  • IEC International Electrotechnical Commission
  • the present invention further provides an electrical insulating oil composition having a flash point (PMCC) of 130 0 C or more, more preferably of 135°C or more and a pour point of -40 0 C or lower, more preferably of -45°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, and which composition conforms with IEC Standard 60296, Type U, in that after 164 hrs at 120°C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt . % or less, and the acid value is 1.2 mg KOH/g or less.
  • PMCC flash point
  • the present invention further provides an electrical insulating oil composition having a flash point (PMCC) of 130 0 C or more, more preferably of 135 0 C or more and a pour point of -40 0 C or lower, more preferably of -45 0 C or lower, which composition comprises hydrorefined mineral oil and/or synthetic hydrocarbon oil, in the range of from 0.5 to 10 wt .% of bright stock oil and in the range of from 0.01 to 0.4 wt.%, more preferably in the range of from 0.08 to 0.4 wt.% of an antioxidant, preferably a phenolic antioxidant and which composition conforms with IEC Standard 60296, Type I, in that after 500 hrs at 120 0 C in IEC oxidation stability test method 61125C, • sludge formation is 0.8 wt.% or less, and the acid value is 1.2 mg KOH/g or less.
  • PMCC flash point
  • the present invention further provides an electrical insulating oil composition having a flash point (PMCC) of 130 0 C or more, more preferably of 135°C or more and a pour point of -40 0 C or lower, more preferably of -45 0 C or lower, which composition comprises hydrorefined mineral oil and/or synthetic hydrocarbon oil, in the range of from 0.5 to 10 wt .% of bright stock oil and in the range of from 0.01 to 0.4 wt.%, more preferably in the range of from 0.01 to 0.08 wt.% of an antioxidant, preferably a phenolic antioxidant and which composition conforms with IEC Standard 60296, Type T, in that after 332 hrs at 120 0 C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt.% or less, and the acid value is 1.2 mg KOH/g or less.
  • PMCC flash point
  • the present invention provides an electrical insulating oil composition which conforms to one or more of the following standards:- IEC (International Electrotechnical Commission) Standard 296 (Class II), IEC Standard 60296 (Type U), IEC Standard 60296 (Type I) and IEC Standard 60296 (Type T) .
  • IEC International Electrotechnical Commission
  • the present invention further provides for the use of an electrical insulating oil composition as hereinbefore described in order to conform with one or more of IEC (International Electrotechnical Commission) Standard 296 (Class II), IEC Standard 60296 (Type U), IEC Standard 60296 (Type I) and IEC Standard 60296 (Type T) .
  • the present invention further provides the use of the composition as hereinbefore described as an electrical insulting oil for application in one or more of transformers, regulators, circuit breakers, power plant reactors, shunt reactors, switch gears, cables and electrical equipment.
  • the base oils A-J and bright stock oil having the properties shown in Table 2, Table 3 and Table 4 were prepared.
  • Base Oils A-J and Bright Stock Oil having the properties shown in Table 2, Table 3 and Table 4 were prepared.
  • Examples 1-7 which were electrical insulating oil compositions according to the present invention which not containing antioxidants, were prepared in accordance with the compositions shown in Table 5 and Table 6.
  • Examples 8-11 which are electrical insulating oil compositions according to the present invention containing antioxidants, were prepared in accordance with the compositions shown in Table 7.
  • Comparative Examples 1-15 were prepared in accordance with the compositions shown in Tables 8-10.
  • antioxidant "BHT” is 2 , 6-di-tert . -butyl-4- methylphenol
  • IEC standard values were used as the standard reference values for the performance of the electrical insulating oil compositions. If these standard reference values were satisfied, then it was considered that long- term stable use over a wide temperature range was possible .
  • Insulation breakdown voltage as per ASTM 1816 (VDE) .
  • VDE Insulation breakdown voltage
  • Examples 10 and 11 had lower antioxidant contents than Examples 8 and 9, and the values of their electrical insulating oil properties were measured, and those results are shown in Table 15 together with the standard values for IEC Standard 60296, Type T. The measurement of the values of the properties, other than (1) to (11), described for the afore-mentioned oils and Examples (not containing antioxidants), was as stated below.
  • the values relating to oxidation stability were substantially lower than the IEC Standard 296, Class II, standard reference values (maximum values) or the IEC Standard 60296, Type U standard reference values (maximum values), and said compositions were judged to be excellent as electrical insulating oil compositions.
  • compositions of Comparative Examples 10-14 satisfied the standard reference values as regards acid value, said compositions did not satisfy the standard reference values as regards sludge, and it was judged that said comparative compositions could not be used as suitable electrical insulating oil compositions.

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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°C or more and a pour point of -40°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

ELECTRICAL INSULATING OIL COMPOSITION
The present invention relates to an electrical insulating oil composition.
Transformers, high-pressure circuit breakers and other high-pressure electrical devices are filled with electrical insulating oil compositions before use.
However, it must be possible for such electrical devices to be used maintenance-free for long periods after the start of operation. Similarly, such compositions are required to maintain stable physical properties and electrical properties over a long period.
It is known that when electrical insulating oil compositions are used for a long period, they deteriorate, causing a decrease in anti-corrosion properties and a decrease in insulating properties due to an increase in the acid value of the electrical insulating oil compositions and the formation of sludge. Hence, with the trend towards higher pressure, larger size and longer service life for high pressure electrical devices, the stability of electrical insulating oil compositions used therein has become more important.
The IEC (International Electrotechnical Commission) has specified the required performance for electrical insulating oil compositions used for filling transformers, high pressure circuit breakers and other electrical devices, and the performance required for mineral oil insulating oil compositions capable of withstanding long-term use as the standards IEC 296 and IEC 60296. Meanwhile, with the advances in mineral oil refining technology, the hydrorefining method has been widely adopted, making it possible to obtain oils from which polycyclic aromatics, unsaturated components, nitrogen content and sulphur content have been adequately removed. At first, it had been considered that it was better for electrical insulating oil composition to contain no nitrogen or sulphur content.
Subsequently, however, Japanese Laid-Open Patent Application No. 2000-345177 A disclosed that with regard to oxidation stability and other aspects it was preferable for electrical insulating oil compositions to contain a certain amount of these components. Thus, it has been proposed in JP 2000-345177 A that by reducing the resin content in an electrical insulating oil composition to ≤ 100 ppm, and also incorporating minute amounts of sulphide-type sulphur content and total nitrogen content, the stability of the electrical insulating oil composition is increased, and increases in electric charge are inhibited.
In fact, it is extremely difficult to refine a crude oil by petroleum refining processes to a state wherein the nitrogen content or sulphur content are such as to be suitable for use in an electrical insulating oil composition.
Accordingly, at present, although there have been attempts to adjust the components therein by adding an appropriate combination of additives or the like having a nitrogen content or sulphur content to highly purified refined oils, there are restrictions as to the additives which can be used, depending on the electrical insulating oil specification, moreover, there are cost problems, and production management complications .
It is therefore highly desirable to be able to obtain an electrical insulating oil composition having a balance of excellent electrical properties, low temperature performance, thermal oxidation stability and anti-corrosion properties by an economical and simple method .
In the present invention it has been surprisingly found that, through the addition of small quantities of bright stock oil to hydrorefined mineral oil and/or synthetic hydrocarbon oil, it is possible simply and economically to increase the thermal oxidation stability and obtain electrical insulating oil compositions which are capable of fulfilling the various types of performance required of electrical insulating oil compositions in the IEC Standard 296 and the IEC Standard 60296.
Accordingly, the present invention provides an electrical insulting oil composition having a flash point (PMCC) of 13O0C or more and a pour point of -400C 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 .
In a preferred embodiment of the present invention, the electrical insulating oil composition has a pour point of -450C or lower. In a preferred embodiment of the present invention, the electrical insulating oil composition has a flash point (PMCC) of 1350C or more. The hydrorefined mineral oil that may be present in the electrical insulating oil composition of the present invention may be refined by hydrogenating mineral oil. Examples of hydrorefined mineral oils that may be conveniently used include hydrorefined naphthenic mineral oil and hydrorefined paraffinic mineral oil.
Through the hydrorefining of mineral oils, polycyclic aromatic substances, unsaturated components, sulphur compounds and nitrogen compounds are removed. Compared to the hydrorefined paraffinic mineral oils, the hydrorefined naphthenic mineral oils may have better low temperature flow properties and lower oxidation stability, and, conversely, compared to the hydrorefined naphthenic mineral oils, the hydrorefined paraffinic mineral oils may have inferior low temperature flow properties, but better thermal oxidation stability.
Examples of synthetic hydrocarbon oils that may be conveniently used in the electrical insulating oil composition of the present invention include polypropylene, polybutene, polypentene and other isoparaffinic synthetic hydrocarbon oils, poly-α-olefins (PAO) falling within Group IV in the API (American Petroleum Institute) base oil classification stated below in Table 1, and Gas to Liquid (GTL) synthetic oils. Synthetic hydrocarbon base oils sold by the Shell group under the trade designation "XHVI" may be conveniently used.
Japanese Laid-Open Patent Application 52-072706 A and Japanese Laid-Open Patent Application 07-228876 describe methods of manufacturing synthetic hydrocarbon oils that may be conveniently used in the electrical insulating oil composition of the present invention. The afore-mentioned hydrorefined mineral oils and synthetic hydrocarbon oils may be used alone. However, the pour point, kinematic viscosity, thermal oxidation stability and the like of the electrical insulating oil composition of the present invention may be optimally adjusted by appropriate combination of several substances .
The hydrorefined mineral oil and/or synthetic hydrocarbon oil used in the electrical insulating oil composition of the present invention each have a preferred kinematic viscosity at 4O0C in the range of from 8.0 to 24 mm2/s.
Preferred hydrorefined mineral oils may be selected from hydrorefined naphthenic mineral oils and/or API base oil classification Group II or Group III hydrorefined paraffinic mineral oils .
Preferred synthetic hydrocarbon oils may be selected from isoparaffinic synthetic oils, GTL synthetic oils and poly-α-olefins (PAO) belonging to API base oil classification Group IV or mixtures thereof.
Since the kinematic viscosity of bright stock oil is relatively high compared to hydrorefined mineral oils and/or synthetic hydrocarbon oils, it is particularly preferred that the intrinsic kinematic viscosity of the hydrorefined mineral oil and/or synthetic hydrocarbon oil at 40°C is 16 mm2/s or less, more preferably 12 mm2/s or less if hydrorefined mineral oil or synthetic hydrocarbon oil is used alone with bright stock oil.
If combinations of hydrorefined mineral oil and synthetic hydrocarbon oil are used with bright stock oil, the respective kinematic viscosity of the hydrorefined mineral oil and the synthetic hydrocarbon oil is each preferably in the range of from 8.0 to 24.0 mm2/s, more preferably in the range of from 8.0 to 20.0 mm2/s.
TABLE 1
Figure imgf000007_0001
The bright stock oil added to the afore-mentioned hydrorefined mineral oil and/or synthetic hydrocarbon oil may be obtained by further distilling under reduced pressure the atmospheric pressure residual mineral oil obtained when paraffinic mineral oil is distilled at atmospheric pressure from crude oil, and performing deasphalting, solvent extraction and solvent dewaxing processes on that reduced pressure residual oil. That is to say, said bright stock oil may be a heavy mineral oil base oil fraction obtained by reduced pressure distillation of the residual paraffinic mineral oil from atmospheric distillation of crude oil, and deasphalting, solvent extraction and solvent dewaxing treatment of the residual oil obtained.
The bright stock oil used in the present invention is preferably a base oil belong to API base oil classification Group I, with total sulphur content in the range of from 0.4 to 2.0 wt . % , mercaptan sulphur content of 100 wt. ppm or less, sulphide-type sulphur content of 0.5 wt .% or less, total nitrogen content in the range of from 100 to 500 wt . ppm, basic nitrogen content of 300 wt. ppm or less, and total content of polar components (IP368) in the range of from 30 to 70 wt . % .
Various sulphur compounds and nitrogen compounds are concentrated in said bright stock oil by the distillation and solvent extraction processes. Through the use of in the range of from 0.5 to 10 wt . % of said bright stock oil in the electrical insulating oil composition of the present invention, preferably in the range of from 0.5 to 8.0 wt. %, based on the total weight of said electrical insulating oil composition, the afore-mentioned sulphur content and nitrogen content are incorporated in appropriate quantities in the electrical insulating oil composition. Hence, it is possible to markedly improve the thermal oxidation stability thereof. If the afore- mentioned mercaptan sulphur and sulphide-type sulphur contents become too high, then the corrosivity may become higher, which is undesirable. Further, if the basic nitrogen content exceeds 300 wt . ppm, then the oxidation stability performance may decrease. The electrical insulating oil composition of the present invention has a preferred kinematic viscosity at 400C in the range of from 8.0 to 16.0 mm2/s, more preferably in the range of from 8.0 to 12.0 mm2/s. With a kinematic viscosity at 40°C of less than 8.0 mm2/s, a satisfactory flash point may not be obtained. If the kinematic viscosity at 400C exceeds 16.0 mm2/s, then the circulation efficiency of the electrical insulating oil composition in a transformer may decrease, the cooling effect may become inadequate, and overheating may occur. The electrical insulating oil composition of the present invention may comprise one or more antioxidant additives. Antioxidants that may be conveniently used are phenolic or aminic antioxidants .
Examples of phenolic antioxidants that may be conveniently used in the electrical insulating oil composition of the present invention include 4,4'- methylenebis (2, 6-di-tert . -butylphenol ) , 4, 4' -bis (2, 6-di- tert .-butylphenol) , 4,4' -bis (2-methyl-6-tert . - butylphenol) , 2,2' -methylenebis (4-ethyl-6-tert.- butylphenol) , 2,2' -methylenebis ( 4-methyl-6-tert . - butylphenol), 4 , 4 ' -butylidenebis ( 3-methyl-6-tert . - butylphenol) , 4, 4' -isopropylidenebis (2, 6-di-tert. -butylphenol), 2 , 2 ' -methylenebis (4-methyl-6-nonylphenol) , 2,2'- isobutylidenebis ( 4 , 6-dimethyl-phenol) , 2,2'- methylenebis ( 4-methyl-6-cyclohexylphenol) , 2, 6-di-tert. - butyl-4-methylphenol, 2, 6-di-tert . -butyl-4-ethylphenol, 2, 4-dimethyl- 6-tert .-butylphenol, 2, 6-di-tert . -butyl-α- dimethylamino-p-cresol , 2, 6-di-tert.-butyl-4 (N, N' - dimethylaminomethylphenol) , 4,4'-thio-bis ( 2-methyl-6- tert. -butylphenol), 4,4'-thiobis (3-methy1-6-tert . - butylphenol), 2 , 2 ' -thiobis- ( 4-methyl-6-tert . - butylphenol), bis (3-methyl-4-hydroxy-5-tert . -butylbenzyl) sulphide, bis (3, 5-di-tert . -butyl-4-hydroxybenzyl) sulphide, 2,2' -thio-diethylenebis [3- (3, 5-di-tert . -butyl- 4-hydroxyphenyl) propionate], tridecyl-3- (3, 5-di-tert .- bύtyl-4-hydroxyphenyl ) propionate, pentaerythrityl- tetrakis[3-(3, 5-di-tert . -butyl-4-hydroxyphenyl) propionate] , octy1-3- (3, 5-di-tert .-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3, 5-di-tert . -butyl-4- hydroxyphenyl) propionate, octyl-3- (3-methyl-5-tert . - butyl-4-hydroxyphenyl) propionate.
The content of the one or more antioxidant additives is preferably less than 2 wt.%, more preferably less than 1 wt. %, even more preferably less than 0.6 wt . % and most preferably less than 0.4 wt.%, based on the total weight of the electrical insulating oil composition.
In a preferred embodiment of the present invention, the electrical insulating oil composition comprises in the range of from 0.01 to 0.4 wt.% of phenolic antioxidant, based on the total weight of the electrical insulating oil composition.
In other embodiments of the present invention, it is preferred that the electrical insulating oil composition comprises in the range of from 0.01 to 0.08 wt.% or in the range of from 0.08 to 0.4 wt.% of phenolic antioxidant, based on the total weight of the electrical insulating oil composition. Further additives that may also be present in the electrical insulating oil composition of the present invention are dependent upon the specific application of the electrical insulating oil composition.
Through the addition of bright stock oil to the afore-mentioned hydrorefined mineral oil and/or synthetic hydrocarbon oil, it is possible to obtain electrical insulating oil compositions conforming with IEC (International Electrotechnical Commission) Standard 296, Class II, in that on maintaining for 168 hrs at 1000C in IEC oxidation stability test method 61125A, sludge formation is 0.1 wt.% or less, and the acid value is 0.4 mg KOH/g or less.
Accordingly, in a preferred embodiment, the present invention provides an electrical insulating oil composition having a flash point (PMCC) of 130°C or more and a pour point of -400C or lower, more preferably of -45°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, and which composition conforms with IEC (International Electrotechnical Commission) Standard 296, Class II, in that after 168 hrs at 1000C in IEC oxidation stability test method 61125A, sludge formation is 0.1% or less, and the acid value is 0.4 mg KOH/g or less.
Further, through the addition of bright stock oil to the afore-mentioned hydrorefined mineral oil and/or synthetic hydrocarbon oil, it is possible to obtain electrical insulating oil compositions conforming with IEC Standard 60296, Type U, in that on maintaining for 164 hrs at 120°C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt . % or less, and the acid value is 1.2 mg KOH/g or less.
Accordingly, in a preferred embodiment, the present invention further provides an electrical insulating oil composition having a flash point (PMCC) of 1300C or more, more preferably of 135°C or more and a pour point of -400C or lower, more preferably of -45°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, and which composition conforms with IEC Standard 60296, Type U, in that after 164 hrs at 120°C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt . % or less, and the acid value is 1.2 mg KOH/g or less.
Moreover, in a preferred embodiment through the addition of bright stock oil, and the further addition of in the range of from 0.01 to 0.4 wt.%, more preferably in the range of from 0.08 to 0.4 wt.% of an antioxidant, preferably a phenolic antioxidant, to the afore-mentioned hydrorefined mineral oil and/or synthetic hydrocarbon oil, it is possible to obtain electrical insulating oil compositions conforming with IEC Standard 60296, Type I, in that on maintaining for 500 hrs at 120°C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt .% or less, and the acid value is 1.2 mg KOH/g or less .
Accordingly, in a preferred embodiment, the present invention further provides an electrical insulating oil composition having a flash point (PMCC) of 1300C or more, more preferably of 1350C or more and a pour point of -400C or lower, more preferably of -450C or lower, which composition comprises hydrorefined mineral oil and/or synthetic hydrocarbon oil, in the range of from 0.5 to 10 wt .% of bright stock oil and in the range of from 0.01 to 0.4 wt.%, more preferably in the range of from 0.08 to 0.4 wt.% of an antioxidant, preferably a phenolic antioxidant and which composition conforms with IEC Standard 60296, Type I, in that after 500 hrs at 1200C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt.% or less, and the acid value is 1.2 mg KOH/g or less.
Further, in the same way, through the addition of bright stock oil, and the further addition of in the range of from 0.01 to 0.4 wt.%, more preferably in the range of from 0.01 to 0.08 wt.% of an antioxidant, preferably a phenolic antioxidant, to the afore-mentioned hydrorefined mineral oil and/or synthetic hydrocarbon oil, it is possible to obtain electrical insulating oil compositions conforming with IEC Standard 60296, Type T, in that on maintaining for 332 hrs at 1200C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt .% or less, and the acid value is 1.2 mg KOH/g or less . Accordingly, in a preferred embodiment, the present invention further provides an electrical insulating oil composition having a flash point (PMCC) of 1300C or more, more preferably of 135°C or more and a pour point of -400C or lower, more preferably of -450C or lower, which composition comprises hydrorefined mineral oil and/or synthetic hydrocarbon oil, in the range of from 0.5 to 10 wt .% of bright stock oil and in the range of from 0.01 to 0.4 wt.%, more preferably in the range of from 0.01 to 0.08 wt.% of an antioxidant, preferably a phenolic antioxidant and which composition conforms with IEC Standard 60296, Type T, in that after 332 hrs at 1200C in IEC oxidation stability test method 61125C, sludge formation is 0.8 wt.% or less, and the acid value is 1.2 mg KOH/g or less. That is to say, the present invention provides an electrical insulating oil composition which conforms to one or more of the following standards:- IEC (International Electrotechnical Commission) Standard 296 (Class II), IEC Standard 60296 (Type U), IEC Standard 60296 (Type I) and IEC Standard 60296 (Type T) .
The present invention further provides for the use of an electrical insulating oil composition as hereinbefore described in order to conform with one or more of IEC (International Electrotechnical Commission) Standard 296 (Class II), IEC Standard 60296 (Type U), IEC Standard 60296 (Type I) and IEC Standard 60296 (Type T) . The present invention further provides the use of the composition as hereinbefore described as an electrical insulting oil for application in one or more of transformers, regulators, circuit breakers, power plant reactors, shunt reactors, switch gears, cables and electrical equipment.
The present invention will be described with reference to the following Examples which are not intended to limit the scope of the invention in any way. EXAMPLES
As the hydrorefined mineral oils, mineral oils and synthetic hydrocarbon oils, the base oils A-J and bright stock oil having the properties shown in Table 2, Table 3 and Table 4 were prepared. Base Oils A-J and Bright Stock Oil
The properties of the base oils A-J and the bright stock oil are stated in Table 2, Table 3 and Table 4 on the basis of the following criteria.
(1) Flash point: as per JIS K 2265 (PMCC: Pensky- Martens closed method, and COC: Cleveland open method) .
(2) Kinematic viscosity (400C) , kinematic viscosity (1000C) : as per ASTM D445.
(3) Pour point: as per ASTM D97.
(4) Acid value: as per ASTM D974. (5) PCA (PCA content): as per BS2000P-346.
TABLE 2
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
TABLE 4
Figure imgf000018_0001
Using the afore-mentioned base oils A-J and bright stock oil, Examples 1-7, which were electrical insulating oil compositions according to the present invention which not containing antioxidants, were prepared in accordance with the compositions shown in Table 5 and Table 6.
Furthermore, Examples 8-11, which are electrical insulating oil compositions according to the present invention containing antioxidants, were prepared in accordance with the compositions shown in Table 7.
Further, for comparison with the afore-mentioned examples, Comparative Examples 1-15 were prepared in accordance with the compositions shown in Tables 8-10.
With regard to the "clay treatment" referred to in Tables 5-10, activated clay in the stated quantity relative to the oil component was used and these were mixed together by stirring for 15 mins at 30-40°C, and the oil layer separated by pressure filtration. Processing was performed by the usual refining methods for electrical insulating oil compositions for the decolourisation, deodorisation, dewatering and stability improvement of electrical insulating oil compositions.
TABLE 5
Figure imgf000019_0001
* wt. % relative to amount of oil components used.
TABLE 6
Figure imgf000019_0002
wt . % relative to amount of oil components used
TABLE 7
Figure imgf000020_0001
Note: The antioxidant "BHT" is 2 , 6-di-tert . -butyl-4- methylphenol
* wt . % relative to amount of oil components used. "BHT' added to oil components after clay treatment.
TABLE 8
Figure imgf000020_0002
* wt . % relative to amount of oil components used. TABLE 9
Figure imgf000021_0001
wt . % relative to amount of oil components used. IEC standard values were used as the standard reference values for the performance of the electrical insulating oil compositions. If these standard reference values were satisfied, then it was considered that long- term stable use over a wide temperature range was possible .
Accordingly, for the afore-mentioned Examples 1 and 2 (not containing antioxidants), the values of the electrical insulating oil properties were measured, and those results are shown in Table 11 together with the standard reference values for IEC Standard 296, Class II.
Further, for the afore-mentioned Examples 1, 2, 6 and 7 (not containing antioxidants), the values of the electrical insulating oil properties were measured, and those results are shown in Table 12 together with the standard reference values for IEC Standard 60296, Type U.
The measurement of the values of the properties, other than (1) to (5), described for the afore-mentioned base oils, was as stated below.
(6) Surface tension: as per ASTM D971.
(7) Corrosive sulphur: as per ASTM D1275.
(8) Water content: as per ASTM D1533.
(9) Oxidation test (168 hrs at 1000C) : as per IEC method 61125A.
(10) Oxidation test (164 hrs at 1200C) : as per IEC method 61125C.
(11) Insulation breakdown voltage: as per ASTM 1816 (VDE) . For the afore-mentioned Examples 3-5 (not containing antioxidants), the values of the density and oxidation stability on the basis of the aforesaid IEC Standard 296, Class II (168 hrs at 1000C, IEC method 61125A) were measured, and those results are shown in Table 13.
For the afore-mentioned Examples 8 and 9 (containing antioxidants), the values of the electrical insulating oil properties were measured, and those results are shown in Table 14 together with the standard values for IEC Standard 60296, Type I.
The measurement of the values of the properties, other than (1) to (11), described for the afore-mentioned base oils and Examples (not containing antioxidants), was as stated below.
(12) Oxidation test (500 hrs at 12O0C) : as per IEC method 61125C.
Examples 10 and 11 (containing antioxidants) had lower antioxidant contents than Examples 8 and 9, and the values of their electrical insulating oil properties were measured, and those results are shown in Table 15 together with the standard values for IEC Standard 60296, Type T. The measurement of the values of the properties, other than (1) to (11), described for the afore-mentioned oils and Examples (not containing antioxidants), was as stated below.
(13) Oxidation test (332 hrs at 1200C) : as per IEC method 61125C.
For Comparative Examples 1-15, the afore-mentioned oxidation stability on the basis of the afore-mentioned IEC Standard 296, Class II (168 hrs at 1000C, IEC method 61125A) was measured, and those results are shown in Tables 16-18. Discussion
For the non-antioxidant-containing electrical insulating oil compositions of Examples 1-7, the values relating to oxidation stability (IEC oxidation test) , which is regarded as an important characteristic value, were substantially lower than the IEC Standard 296, Class II, standard reference values (maximum values) or the IEC Standard 60296, Type U standard reference values (maximum values), and said compositions were judged to be excellent as electrical insulating oil compositions.
With Examples 1 and 2, the values from the oxidation test by the IEC method 61125A (168 hrs at 1000C) in the IEC Standard 296 and from the oxidation test by the IEC method 61125C (164 hrs at 1200C) in the IEC Standard 60296 were substantially lower than the standard reference values (maximum values) in either of these standards, and the compositions were excellent.
Further, for Examples 1, 2, 6 and 7, favourable results were obtained for all of the characteristic values stated in Table 11 and Table 12, in particular the kinematic viscosity at 4O0C and -30°C, the pour point and acid value, and all compositions satisfied the standard reference values for IEC Standard 296, Type II and/or IEC Standard 60296, Type U. Moreover, for the antioxidant-containing electrical insulating oil compositions of Examples 8 and 9, in the IEC method 61125C (500 hrs at 1200C) oxidation test relating to IEC Standard 60296, Type I, the values relating to oxidation stability, which is regarded as an important characteristic value, were each substantially lower than the standard reference values (maximum values) therein, and they were judged to be excellent electrical insulating oil compositions. Further, favourable results were also obtained for the other characteristic values stated in Table 14, in particular the kinematic viscosity, with both compositions satisfying the standard reference values for IEC Standard 60296, Type I.
Furthermore, with the electrical insulating oil compositions of Examples 10 and 11, which contained small quantities of antioxidant, in the IEC method 61125C (332 hrs at 12O0C) oxidation test relating to IEC Standard 60296, Type T, the values relating to oxidation stability, which is regarded as an important characteristic value, were each substantially lower than the standard reference values therein, and said compositions were judged to be excellent electrical insulating oil compositions. Favourable results were also obtained for the other characteristic values stated in Table 15, in particular the kinematic viscosity, and both compositions satisfied the standard reference values for IEC Standard 60296, Type T. However, with the substances of Comparative Examples 1-15, in which bright stock oil was not used, in the IEC method 61125A (168 hrs at 1000C) oxidation test relating to the afore-mentioned IEC Standard 296, none of the compositions satisfied the standard reference values for IEC Standard 296, Class II. In other words, the substances of Comparative Examples 1-9 and 15 substantially exceeded the standard reference values (maximum values), and it was judged that the comparative compositions were unsuitable for use as electrical insulating oil compositions. Further, although the compositions of Comparative Examples 10-14 satisfied the standard reference values as regards acid value, said compositions did not satisfy the standard reference values as regards sludge, and it was judged that said comparative compositions could not be used as suitable electrical insulating oil compositions.
TABLE 11
K)
Figure imgf000027_0001
TABLE 12
KJ -4
Figure imgf000028_0001
TABLE 12 continued
CC
Figure imgf000029_0001
TABLE 13
K)
Figure imgf000030_0001
TABLE 14
O
Figure imgf000031_0001
TABLE 14 continued
Figure imgf000032_0001
TABLE 15
Figure imgf000033_0001
TABLE 15 continued
Figure imgf000034_0001
TABLE 16
Figure imgf000035_0001
TABLE 17
Figure imgf000035_0002
TABLE 18
Figure imgf000036_0001
Ul

Claims

C L A I M S
1. An electrical insulating oil having a flash point
(PMCC) of 13O0C or more and a pour point of -4O0C 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.
2. Electrical insulating oil composition according to Claim 1, wherein said composition has a pour point of -450C or lower.
3. Electrical insulating oil composition according to Claim 1 or 2, wherein said composition has a flash point (PMCC) of 135°C or more.
4. Electrical insulating oil composition according to any one of Claims 1 to 3, wherein said composition comprises in the range of from 0.01 to 0.4 wt . % of phenolic antioxidant, based on the total weight of the electrical insulating oil composition.
5. Electrical insulating oil composition according to any one of Claims 1 to 4, wherein said composition comprises in the range of from 0.01 to 0.08 wt . % of phenolic antioxidant, based on the total weight of the electrical insulating oil composition.
6. Electrical insulating oil composition according to any one of Claims 1 to 4, wherein said composition comprises in the range of from 0.08 to 0.4 wt . % of phenolic antioxidant, based on the total weight of the electrical insulating oil composition.
7. Electrical insulating oil composition according to any of Claims 1 to 6, wherein the hydrorefined mineral oil has a kinematic viscosity in the range of from 8.0 to 24 mm2/s at 400C and is selected from a hydrorefined naphthenic mineral oil and/or an API base oil classification Group II or Group III hydrorefined paraffinic mineral oil.
8. Electrical insulating oil composition according to any one of Claims 1 to 7, wherein the synthetic hydrocarbon oil has a kinematic viscosity in the range of from 8.0 to 24 mm2/s at 4O0C and is selected from an isoparaffinic synthetic oil, a GTL synthetic oil, a poly-α-olefin (PAO) belonging to API base oil classification Group IV or a mixture thereof.
9. Electrical insulating oil composition according to any one of Claims 1 to 8, wherein the bright stock oil is a heavy mineral oil base oil fraction obtained by reduced pressure distillation of the residual paraffinic mineral oil from atmospheric distillation .of crude oil, and deasphalting, solvent extraction and solvent dewaxing treatment of the residual oil obtained.
10. Electrical insulating oil composition according to any one of Claims 1 to 9, which composition conforms to one or more of the following Standards:- IEC (International Electrotechnical Commission) Standard 296 (Class II), IEC Standard 60296 (Type U), IEC Standard 60296 (Type I) and IEC Standard 60296 (Type T) .
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CN101385095A (en) 2009-03-11
EP1984927B1 (en) 2011-11-09
US20070208205A1 (en) 2007-09-06
ATE533166T1 (en) 2011-11-15

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