EP1984927A1 - Electrical insulation oil composition - Google Patents
Electrical insulation oil compositionInfo
- Publication number
- EP1984927A1 EP1984927A1 EP07704608A EP07704608A EP1984927A1 EP 1984927 A1 EP1984927 A1 EP 1984927A1 EP 07704608 A EP07704608 A EP 07704608A EP 07704608 A EP07704608 A EP 07704608A EP 1984927 A1 EP1984927 A1 EP 1984927A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- electrical insulating
- insulating oil
- composition
- oil composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 238000010292 electrical insulation Methods 0.000 title 1
- 239000010735 electrical insulating oil Substances 0.000 claims abstract description 81
- 239000003921 oil Substances 0.000 claims abstract description 74
- 239000002480 mineral oil Substances 0.000 claims abstract description 44
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 27
- 239000002199 base oil Substances 0.000 claims description 16
- 239000002530 phenolic antioxidant Substances 0.000 claims description 10
- 229920013639 polyalphaolefin Polymers 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 229940097789 heavy mineral oil Drugs 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 description 31
- 238000007254 oxidation reaction Methods 0.000 description 31
- 238000000034 method Methods 0.000 description 28
- 239000003963 antioxidant agent Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 239000005864 Sulphur Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000010802 sludge Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000013112 stability test Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- 241000428199 Mustelinae Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; 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
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006039407A JP5102452B2 (en) | 2006-02-16 | 2006-02-16 | Electrical insulation oil |
| PCT/EP2007/051484 WO2007093631A1 (en) | 2006-02-16 | 2007-02-15 | Electrical insulation oil composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1984927A1 true EP1984927A1 (en) | 2008-10-29 |
| EP1984927B1 EP1984927B1 (en) | 2011-11-09 |
Family
ID=37947651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07704608A Not-in-force EP1984927B1 (en) | 2006-02-16 | 2007-02-15 | Electrical insulation oil composition |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20070208205A1 (en) |
| EP (1) | EP1984927B1 (en) |
| JP (1) | JP5102452B2 (en) |
| CN (1) | CN101385095A (en) |
| AT (1) | ATE533166T1 (en) |
| BR (1) | BRPI0708062A2 (en) |
| ES (1) | ES2373577T3 (en) |
| WO (1) | WO2007093631A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025040640A1 (en) * | 2023-08-23 | 2025-02-27 | Arlanxeo Netherlands B.V. | Oil-extended ethylene copolymers |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100279904A1 (en) * | 2007-07-31 | 2010-11-04 | Chevron U.S.A. Inc. | Electrical insulating oil compositions and preparation thereof |
| JP5165307B2 (en) * | 2007-08-23 | 2013-03-21 | Jx日鉱日石エネルギー株式会社 | Electrical insulating oil and method for producing the same |
| CN101796593B (en) * | 2007-11-21 | 2012-05-23 | 株式会社日本能源 | Electric insulating oil and process for producing the same |
| EP2254126A1 (en) * | 2009-05-20 | 2010-11-24 | Nexans | Organogel for electrical cable insulating layer |
| CN105051831B (en) * | 2013-03-25 | 2017-07-14 | 出光兴产株式会社 | Electrical insulating oil composition |
| JP2016009553A (en) * | 2014-06-23 | 2016-01-18 | 出光興産株式会社 | Electrical insulating oil composition |
| FI128090B (en) * | 2016-12-22 | 2019-09-13 | Neste Oyj | Hydraulic fluid composition |
| CN108587723B (en) * | 2018-06-29 | 2020-12-22 | 天津中海海疆能源科技有限公司 | Mineral insulating oil and preparation method thereof |
| ES2943957T3 (en) | 2019-06-12 | 2023-06-16 | Lubrizol Corp | Organic heat transfer system, method and fluid |
| EP3754674B1 (en) * | 2019-06-17 | 2023-06-07 | Hitachi Energy Switzerland AG | Insulating liquid and inductive arrangement comprising a container with insulating liquid |
| JP7506018B2 (en) * | 2021-03-31 | 2024-06-25 | 出光興産株式会社 | Electrical insulating oil composition |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3541015A (en) * | 1965-12-20 | 1970-11-17 | Gaf Corp | Lubricating oil containing methyl vinyl ether copolymers |
| BE754957R (en) * | 1969-08-18 | 1971-02-18 | Sun Oil Co Pennsylvania | HYDRORAFFINED TRANSFORMER OIL AND PROCESS FOR THE |
| US4069166A (en) * | 1975-06-20 | 1978-01-17 | Nippon Oil Company, Ltd. | Electrical insulating oils |
| US4082866A (en) * | 1975-07-28 | 1978-04-04 | Rte Corporation | Method of use and electrical equipment utilizing insulating oil consisting of a saturated hydrocarbon oil |
| GB1514068A (en) * | 1975-07-30 | 1978-06-14 | Nippon Oil Co Ltd | Electrical insulating oil |
| US4324933A (en) * | 1976-05-01 | 1982-04-13 | Nippon Oil Co., Ltd. | Electrical insulating oil compositions |
| US4956105A (en) * | 1988-05-31 | 1990-09-11 | Mobil Oil Corporation | Lubricant composition containing phenolic/phosphorodithioate borates as multifunctional additives |
| JPH06187829A (en) * | 1992-12-17 | 1994-07-08 | Nippon Oil Co Ltd | Electric insulating oil and its manufacture |
| BR9509879A (en) * | 1994-12-08 | 1997-09-16 | Exxon Chemical Patents Inc | Biodegradable ester branched synthetic base compounds and lubricants formed from them |
| US6083889A (en) * | 1999-02-05 | 2000-07-04 | Exxon Research And Engineering Company | High temperature, high efficiency electrical and transformer oil |
| US7655132B2 (en) * | 2004-05-04 | 2010-02-02 | Chevron U.S.A. Inc. | Process for improving the lubricating properties of base oils using isomerized petroleum product |
| US7682499B2 (en) * | 2005-08-31 | 2010-03-23 | Shell Oil Company | Mineral insulating oil, a process for preparing a mineral insulating oil, and a process for using a mineral insulating oil |
| US7666295B2 (en) * | 2005-10-20 | 2010-02-23 | Ergon Refining, Inc. | Uninhibited electrical insulating oil |
-
2006
- 2006-02-16 JP JP2006039407A patent/JP5102452B2/en not_active Expired - Lifetime
-
2007
- 2007-02-15 CN CNA2007800056679A patent/CN101385095A/en active Pending
- 2007-02-15 AT AT07704608T patent/ATE533166T1/en active
- 2007-02-15 EP EP07704608A patent/EP1984927B1/en not_active Not-in-force
- 2007-02-15 US US11/675,503 patent/US20070208205A1/en not_active Abandoned
- 2007-02-15 BR BRPI0708062-0A patent/BRPI0708062A2/en not_active IP Right Cessation
- 2007-02-15 WO PCT/EP2007/051484 patent/WO2007093631A1/en not_active Ceased
- 2007-02-15 ES ES07704608T patent/ES2373577T3/en active Active
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2007093631A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025040640A1 (en) * | 2023-08-23 | 2025-02-27 | Arlanxeo Netherlands B.V. | Oil-extended ethylene copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0708062A2 (en) | 2011-05-17 |
| ATE533166T1 (en) | 2011-11-15 |
| WO2007093631A1 (en) | 2007-08-23 |
| EP1984927B1 (en) | 2011-11-09 |
| JP2007220468A (en) | 2007-08-30 |
| ES2373577T3 (en) | 2012-02-06 |
| US20070208205A1 (en) | 2007-09-06 |
| JP5102452B2 (en) | 2012-12-19 |
| CN101385095A (en) | 2009-03-11 |
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