CN101796593A - Electric insulating oil and process for producing the same - Google Patents

Electric insulating oil and process for producing the same Download PDF

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Publication number
CN101796593A
CN101796593A CN200880105085A CN200880105085A CN101796593A CN 101796593 A CN101796593 A CN 101796593A CN 200880105085 A CN200880105085 A CN 200880105085A CN 200880105085 A CN200880105085 A CN 200880105085A CN 101796593 A CN101796593 A CN 101796593A
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electric insulating
quality
base oil
equal
insulating oil
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CN101796593B (en
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森岛欣之
伊藤岳史
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Eneos Corp
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Japan Energy Corp
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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
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02Specified values of viscosity or viscosity index
    • 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
    • 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
    • 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
    • C10N2020/017Specific gravity or density
    • 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
    • C10N2030/02Pour-point; 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
    • C10N2030/10Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/40Low content or no content compositions
    • C10N2030/43Sulfur free or low sulfur content compositions
    • 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

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

Abstract

A useful electric insulating oil which retains satisfactory oxidative stability and further has such excellent electrical properties that it can maintain a low degree of electrification over long and which excels in practical performance. The electric insulating oil is characterized by having (A1) a pour point of -27.5 DEG C or lower, (A2) a dynamic viscosity (40 DEG C) of 5-12 mm2/s, (A3) a density (15 DEG C) of 0.840-0.860 g/cm3, (A4) a sulfur content of 0.20 mass% or lower, (A5) a nitrogen content of 20 mass ppm or lower, and (A6) a refractive index of 1.460-1.480.

Description

Electric insulating oil and manufacture method thereof
Technical field
The present invention relates to a kind of electric insulating oil (electric insulating oil) and manufacture method thereof, it is good particularly to relate to a kind of oxidation stability, and the rising of the charged degree in the use is inhibited the electric insulating oil of excellence on Practical Performance.
Background technology
Electric insulating oil is to be filled in transformer (transformer), high-tension cable (high voltagecable), primary cut-out (high voltage circuit breaker), the capacitor high voltage electric equipments such as (condenser) to use, and require these machines in a single day to put in the commercial running, can need not keep in repair (maintenance free) for a long time and use.Therefore, but electric insulating oil must the stable electrical property of long term maintenance.
On the other hand, transformers etc. are in order to distribute the heat that coil (coil) etc. is produced, and be designed to forcibly or utilize free convection to make the electric insulating oil cooling that circulates, but there is following situation: the separation that produces electric charge along with the internal circulating load increase of electric insulating oil, can be owing to discharge causes insulation breakdown, that is, be short-circuited and damage.Therefore, recently, the charged degree problem of electric insulating oil comes into one's own, and is known: if particularly use for a long time, then electric insulating oil is with deterioration, and charged degree will rise.
And, carry out large capacity transmission in order to consider from the economy aspect, be accompanied by the EHV transmission The Application of Technology of 500,000 volts of (volt)~3,000,000 volt, seek high-pressure trend, the high capacity (maximization) of high voltage electric equipment, we can say that the high-pressure trend of high voltage electric equipments such as EHV transformer, high capacity have further encouraged described problem.
At described problem, the applicant had proposed a kind of electric insulating oil of resin (resin) content smaller or equal to the refined mineral oil of 100 ppm by weight that used in the past, was preferably and then the sulfide sulfur composition of this mineral oil is 50~1000 ppm by weight and full nitrogen component smaller or equal to the electric insulating oil of 1 ppm by weight (with reference to No. the 3679272nd, Japan Patent).
Yet, though in No. the 3679272nd, the Japan Patent disclosed invention charged degree is remained lower aspect excellence, aspect oxidation stability because the generations of greasy filth (sludge) etc. are former thereby may not necessarily be fully satisfactory.
Summary of the invention
Therefore, problem of the present invention is to provide a kind of electric insulating oil of usefulness, and it not only keeps good oxidation stability, but and have the excellent electrical of long term maintenance than the low strap electric degree concurrently, outstanding on Practical Performance.
The present inventor has carried out making great efforts research in order to solve described problem, found that: the electric insulating oil that (1) pour point (pour point), kinematic viscosity (kinematic viscosity) (40 ℃), density (15 ℃), sulphur composition, nitrogen component and refractive index are in particular range not only keeps good oxidation stability, but and the lower charged degree of long term maintenance; In addition, (2) described electric insulating oil is to be that base oil is mixed and obtains by making with extra care two kinds of different mineral oil of degree; Thereby finish the present invention.
That is, electric insulating oil of the present invention is characterised in that:
(A1) pour point is smaller or equal to-27.5 ℃,
(A2) kinematic viscosity (40 ℃) is 5~12mm 2/ s,
(A3) density (15 ℃) is 0.840~0.860g/cm 3,
(A4) the sulphur composition is smaller or equal to 0.20 quality %,
(A5) nitrogen component is smaller or equal to 20 quality ppm, and
(A6) refractive index is 1.460~1.480.Herein, the sulphur composition of the preferred oxide morphology of electric insulating oil of the present invention is 0.01~0.02 quality %.
In addition, the manufacture method of electric insulating oil of the present invention is the manufacture method of described electric insulating oil, it is characterized in that: comprise the step that base oil 1 is mixed with base oil 2,
Wherein, described base oil 1
(B1) pour point is smaller or equal to-27.5 ℃,
(B2) kinematic viscosity (40 ℃) is 5~12mm 2/ s,
(B3) the sulphur composition is smaller or equal to 0.20 quality %,
(B4) nitrogen component is smaller or equal to 20 quality ppm, and
(B5) aromatic component is more than or equal to 5 quality % and less than 30 quality %;
Described base oil 2
(C1) the sulphur composition is smaller or equal to 0.001 quality %,
(C2) nitrogen component is smaller or equal to 5 quality ppm, and
(C3) aromatic component is less than 3 quality %.Herein, described base oil 1 is preferably counted 90/10~40/60 scope with mass ratio (base oil 1/ base oil 2) with the allotment ratio of described base oil 2.In addition, the density (15 ℃) that is preferably described base oil 1 is higher than 0.860g/cm 3, and the density of described base oil 2 (15 ℃) is less than 0.840g/cm 3And the sulphur composition of described base oil 1 preferred oxide morphology is 0.01~0.05 quality %.
According to the present invention, a kind of useful electric insulating oil can be provided, it not only keeps good oxidation stability, but and have the excellent electrical of long term maintenance than the low strap electric degree concurrently, outstanding on Practical Performance.In addition, the present invention can provide a kind of manufacture method of described electric insulating oil.
Description of drawings
Fig. 1 represents to be obtained in order to base oil 1 mixes with base oil 2 the suitable refining scope of electric insulating oil of the present invention.
Embodiment
Below further describe the present invention.Electric insulating oil of the present invention is characterised in that: (A1) pour point, (A2) kinematic viscosity (40 ℃), (A3) density (15 ℃), (A4) sulphur composition, (A5) nitrogen component and (A6) refractive index be in specific scope; In addition, it is that base oil is mixed and makes that electric insulating oil of the present invention preferably will be made with extra care two kinds of different mineral oil of degree, more preferably with (B1) pour point, (B2) kinematic viscosity (40 ℃), (B3) sulphur composition, (B4) nitrogen component and (B5) aromatic component be in the base oil 1 of particular range, with (C1) sulphur composition, (C2) nitrogen component and (C3) the aromatic component base oil 2 that is in particular range mixed and made.
Electric insulating oil of the present invention is because kinematic viscosity (40 ℃) is 5~12mm 2/ s, and the sulphur composition is smaller or equal to 0.20 quality %, but the therefore lower charged degree of long term maintenance; In addition, electric insulating oil of the present invention since the sulphur composition smaller or equal to 0.20 quality %, nitrogen component is smaller or equal to 20 quality ppm, and refractive index is 1.460~1.480, therefore has the excellent electrical of the oxidation stability that can keep good concurrently.
(A1) pour point of electric insulating oil of the present invention is smaller or equal to-27.5 ℃, preferably smaller or equal to-32.5 ℃.When the pour point of electric insulating oil surpasses-27.5 ℃, in low-temperature region, may cause solidifying or the increase of extreme kinematic viscosity, thereby can't use at cold district.
(A2) kinematic viscosity (40 ℃) of electric insulating oil of the present invention is 5~12mm 2/ s is preferably 5~9mm 2/ s.When the kinematic viscosity (40 ℃) of electric insulating oil greater than 12mm 2During/s, have mobile the deterioration and situation about on the cooling characteristics of transformer etc., having problems, on the other hand, when kinematic viscosity (40 ℃) less than 5mm 2During/s, might cause flash-point (flash point) to reduce.
(A3) density (15 ℃) of electric insulating oil of the present invention is 0.840~0.860g/cm 3, be preferably 0.850~0.860g/cm 3When the density (15 ℃) of electric insulating oil less than 0.840g/cm 3The time, the problem that causes flash-point to reduce generation.On the other hand, when the density (15 ℃) of electric insulating oil greater than 0.860g/cm 3The time, situation, the ice that has a moisture freezes of the inside be blended into transformer etc. floats up and produces the situation of destroying faults (trouble) such as insulation.
(A4) sulphur composition of electric insulating oil of the present invention is smaller or equal to 0.20 quality %, preferably smaller or equal to 0.05 quality %.When the sulphur composition of electric insulating oil during greater than 0.20 quality %, might cause the corrosion of the copper members such as coil of transformer etc., in addition, might become the high-band electric degree.In addition, electric insulating oil of the present invention is not particularly limited, and with regard to the viewpoint of oxidation stability, preferred sulphur composition is more than or equal to 0.01 quality %, and more specifically, the sulphur composition of preferred oxide morphology is 0.01~0.02 quality %.
(A5) nitrogen component of electric insulating oil of the present invention is smaller or equal to 20 quality ppm, preferably smaller or equal to 5 quality ppm.When the nitrogen component of electric insulating oil during, will produce the problem that oxidation stability reduces greater than 20 quality ppm.
(A6) refractive index of electric insulating oil of the present invention is 1.460~1.480, is preferably 1.465~1.475.When the refractive index of electric insulating oil less than 1.460 the time because overrefining and can't obtain good oxidation stability, on the other hand, when refractive index greater than 1.480 the time, for obtaining long term maintenance than refining and insufficient for the excellent electrical of low strap electric degree.
Electric insulating oil of the present invention is not particularly limited, and the optimization aromatic composition is more than or equal to 5 quality % and less than 30 quality %.When the aromatic component of electric insulating oil during, when perhaps aromatic component is more than or equal to 30 quality %, will produce the problem that oxidation stability reduces less than 5 quality %.
Electric insulating oil of the present invention is not particularly limited, and (Pensky-Martens method (Pensky-Martens, PM)) is more than or equal to 135 ℃, more preferably greater than equaling 140 ℃ for preferred flash-point.When flash-point (PM) during, not good enough with regard to the viewpoint of in the keeping process of electric insulating oil or the secure context in the use, the aspect of taking precautions against natural calamities less than 135 ℃.
Preferably in the manufacturing of electric insulating oil of the present invention use two kinds of base oils, i.e. base oil 1 and base oil 2, as this base oil 1 and base oil 2, preferred mineral oil is base oil.Base oil 1 and base oil 2 are to be raw material with crude oil, after air-distillation, decompression distillation, make through hydrofinishing (hydrorefining), hydrocracking (hydrogenolysis), Hydrodewaxing processing such as (hydrodewaxing), both refining degree differences, base oil 2 is than the refining degree height of base oil 1.In addition, the sulphur composition of base oil 2 is low excessively, and aromatic component is low excessively, and therefore oxidation stability is low when using separately, and up to now also not as electric insulating oil, but base oil 2 can be used for electric insulating oil by mixing to become with base oil 1.
(B1) pour point of described base oil 1 is smaller or equal to-27.5 ℃, preferably smaller or equal to-32.5 ℃.When the pour point of base oil 1 during greater than-27.5 ℃, the pour point of the electric insulating oil of manufacturing can uprise, and may cause solidifying in low-temperature region or the increase of extreme kinematic viscosity, thereby can't use at cold district.
(B2) kinematic viscosity (40 ℃) of described base oil 1 is 5~12mm 2/ s is preferably 5~9mm 2/ s.When the kinematic viscosity (40 ℃) of base oil 1 greater than 12mm 2During/s, have mobile the deterioration and situation about on the cooling characteristics of transformer etc., having problems, on the other hand, when kinematic viscosity (40 ℃) less than 5mm 2During/s, might cause flash-point to reduce.
(B3) sulphur composition of described base oil 1 is smaller or equal to 0.20 quality %, preferably smaller or equal to 0.10 quality %.When the sulphur composition of base oil 1 during greater than 0.20 quality %, might cause the corrosion of the copper members such as coil of transformer etc., in addition, might become the high-band electric degree.In addition, base oil 1 is not particularly limited, and with regard to the viewpoint of oxidation stability, preferred sulphur composition is more than or equal to 0.01 quality %, and more specifically, the sulphur composition of preferred oxide morphology is 0.01~0.05 quality %.
(B4) nitrogen component of described base oil 1 is smaller or equal to 20 quality ppm, preferably smaller or equal to 5 quality ppm.When the nitrogen component of base oil 1 during, will produce the problem that oxidation stability reduces greater than 20 quality ppm.
(B5) aromatic component of described base oil 1 is preferably 15 quality %~25 quality % more than or equal to 5 quality % and less than 30 quality %.When the aromatic component of base oil 1 during, when perhaps aromatic series divides more than or equal to 30 quality %, will produce the problem that oxidation stability reduces less than 5 quality %.
Described base oil 1 is not particularly limited, and preferred flash-point (PM) is more than or equal to 140 ℃, and more preferably flash-point (PM) is more than or equal to 145 ℃.When flash-point (PM) during, not good enough with regard to the viewpoint of in the keeping process of electric insulating oil or the secure context in the use, the aspect of taking precautions against natural calamities less than 140 ℃.
Described base oil 1 is not particularly limited, and preferably in its distillation proterties, 20% recovered (distilled) temperature is more than or equal to 260 ℃, and more preferably 20% recovered (distilled) temperature is more than or equal to 270 ℃.When 20% recovered (distilled) temperature during less than 260 ℃, will cause flash-point to reduce, not good enough with regard to the viewpoint of in the keeping process of electric insulating oil or the secure context in the use, the aspect of taking precautions against natural calamities.
Described base oil 1 is not particularly limited, and preferred index is in 1.470~1.500 the scope, more preferably in 1.470~1.490 the scope.When refractive index less than 1.470 the time, base oil 1 with become overrefining after base oil 2 mixes, therefore can't obtain good oxidation stability, when refractive index greater than 1.500 the time, base oil 1 is with after base oil 2 mixes, for obtaining long term maintenance than refining and insufficient for the excellent electrical of low strap electric degree.
(C1) sulphur composition of described base oil 2 is smaller or equal to 0.001 quality %, preferably smaller or equal to 0.0005 quality %.By mix sulphur composition in described base oil 1 smaller or equal to the base oil of 0.001 quality %, but can obtain the excellent electrical of long term maintenance than the low strap electric degree, can prevent the high-band electric degreeization.
(C2) nitrogen component of described base oil 2 is smaller or equal to 5 quality ppm, preferably smaller or equal to 3 quality ppm.When the nitrogen component of base oil 2 during, will produce the problem that oxidation stability reduces greater than 5 quality ppm.
(C3) aromatic component of described base oil 2 is less than 3 quality %, preferably less than 1 quality %.Less than the base oil of 3 quality %, keep the effect of good oxidation stability to be not fully exerted by mixed aromatic composition in described base oil 1.
Described base oil 2 is not particularly limited, and preferred flash-point (PM) is more than or equal to 135 ℃, more preferably greater than equaling 140 ℃.When flash-point (PM) during, not good enough with regard to the viewpoint of in the keeping process of electric insulating oil or the secure context in the use, the aspect of taking precautions against natural calamities less than 135 ℃.
Described base oil 2 is not particularly limited, and preferably in its distillation proterties, 20% recovered (distilled) temperature is more than or equal to 270 ℃, and more preferably 20% recovered (distilled) temperature is more than or equal to 280 ℃.When 20% recovered (distilled) temperature during less than 270 ℃, will cause flash-point to reduce, not good enough with regard to the viewpoint of in the keeping process of insulating oil or the secure context in the use, the aspect of taking precautions against natural calamities.
Described base oil 2 is not particularly limited, and preferred index is in 1.440~1.470 the scope, more preferably in 1.450~1.470 the scope.When refractive index less than 1.440 the time, base oil 2 with become overrefining after base oil 1 mixes, therefore can't obtain good oxidation stability, when refractive index greater than 1.470 the time, base oil 2 is with after base oil 1 mixes, for obtaining long term maintenance than refining and insufficient for the excellent electrical of low strap electric degree.
As long as the electric insulating oil that generates satisfies described characteristic, then described base oil 1 is not particularly limited with the allotment ratio of described base oil 2, preferably counts 90/10~40/60 scope with mass ratio (base oil 1/ base oil 2).
In addition, base oil 1 is not particularly limited with base oil 2, and base oil 1 preferred density (15 ℃) is higher than 0.860g/cm 3, base oil 2 preferred density (15 ℃) are less than 0.840g/cm 3, and preferably the base oil 1 of described density is mixed with base oil 2 that to make density (15 ℃) be 0.840~0.860g/cm 3Electric insulating oil.
Expression obtains to have concurrently good oxidation stability and the long term maintenance suitably refining scope than the electric insulating oil of the excellent electrical of low strap electric degree in order to base oil 1 is mixed with base oil 2 in Fig. 1.
In addition, electric insulating oil of the present invention is used for additives such as the antioxidant, antistatic agent of electric insulating oil before can not containing, and brings into play good oxidation stability and the long term maintenance excellent electrical than the low strap electric degree.These additives itself or use when being changed to the deterioration thing owing to long-term exist health or environmental protection to the people to cause dysgenic problem.
The following special result of electric insulating oil performance of the present invention discussed above promptly, not only keeps good oxidation stability, but and the lower charged degree of long term maintenance.In addition, about oxidation stability, electric insulating oil of the present invention measure according to JIS C2101 at the greasy filth of 120 ℃ of following deteriorations after 75 hours preferably smaller or equal to 0.4 quality %, be more preferably less than and equal 0.1 quality %, total acid number (total acid number) is preferably smaller or equal to 0.6mgKOH/g, is more preferably less than to equal 0.3mgKOH/g.In addition, about charged degree, in the report " maintenance management of No. 5 (its 1) oil-filled transformer of electric collaborative research the 54th volume " of electric power from electric collaborative research association of civic organization with transformer maintenance management special commission, listed the transformer maintenance management benchmark of " charged degree is smaller or equal to 200pC/mL when transformer assembles; charged degree is smaller or equal to 500pC/mL when results of regular determination ", and the charged degree of electric insulating oil of the present invention is lower than described criterion, more specifically, electric insulating oil of the present invention with copper cash at the charged degree of 120 ℃ of following deteriorations after 168 hours preferably smaller or equal to 200pC/mL, be more preferably less than and equal 100pC/mL.
" example "
Below, further describe content of the present invention based on example.In addition, the present invention is not subjected to any restriction of these examples.
According to the allotment ratio shown in the top of table 1 (the allotment amount is to be the quality % of benchmark with the constituent total amount), use following base oil (base oil 1-1 and base oil 2-1), be prepared into the constituent of example 1~2 and comparative example 1~3.The measurement result of the characteristic of gained constituent is illustrated in the table 1.In addition, in table 1 also together expression be not comparative example 4~5 for the electric insulating oil of the combination of base oil 1-1 and base oil 2-1.The electric insulating oil of comparative example 4 is the oil that obtains through the blend step of hydrofinishing, solvent refining (solvent refining), multiple oil, the electric insulating oil of comparative example 5 is through hydrofinishing, solvent refining, solvent dewaxing (solvent dewaxing), clay treatment (clay treatment) and the oil that obtains, compare with example 1~2, comparative example 4, comparative example 5 are the refining relatively low electric insulating oil of degree.
<base oil 〉
Base oil 1-1[pour point :-32.5 ℃, kinematic viscosity (40 ℃): 7.725mm 2/ s, kinematic viscosity (100 ℃): 2.173mm 2/ s, the sulphur composition: 0.04 quality %, nitrogen component: less than 1 quality ppm, aromatic component: 23.1 quality %]
Base oil 2-1[pour point :-37.5 ℃, kinematic viscosity (40 ℃): 8.667mm 2/ S, kinematic viscosity (100 ℃): 2.395mm 2/ s, the sulphur composition: less than 0.001 quality %, nitrogen component: less than 1 quality ppm, aromatic component: 0.5 quality %]
<evaluation method 〉
(1) density
Measure according to JIS K2249.
(2) kinematic viscosity (40 ℃, 100 ℃)
Measure according to JIS K2283.
(3) pour point
Measure according to JIS K2269.
(4) refractive index
Measure according to JIS C2101.
(5) sulphur composition
Measure according to JIS K2541.
(6) nitrogen component
Measure according to JIS K2609.
(7) saturated composition, aromatic component and resinous principle
Measure according to ASTM D2007.
(8) oxidation stability
Measure according to JIS C2101.
(9) charged degree after the deterioration
Under air ambient, the test oil of 1000g and copper cash (diameter is 1mm, and length is 3.5m) as catalyst were kept 168 hours down at 120 ℃ together, prepare deterioration oil, and measure the charged degree after the deterioration.In addition, charged degree is to utilize miniature electrostatic tester (mini-static tester) (IEEE Transaction on Power Apparatus and Systems, PAS-103,1923 (1984)) to measure.
(10) flash-point (PM)
Measure according to JIS K2265.
(11) 20% recovered (distilled) temperatures
Measure according to JIS K2254.
(12) the sulphur composition of oxide morphology
Utilize method shown below to carry out quantitatively.To the lamellae of common employed thin-layered chromatography (thinlayer chromatography) usefulness (for example, the lamellae that the silica gel (silica gel) of coating 0.25mm left and right thickness forms on glass plate) the acid acetone water mixed liquid of hydrochloric acid of last spraying palladium bichloride 0.5 quality %, the sample oil of 2~4 μ L on the point of air-dry back, utilize carbon tetrachloride solution to make described sample oil launch about 10cm, and then utilize chloroform/methanol (volumetric ratio 9/1) mixed liquor further to launch about 5cm from putting attached position.By described operation, the sulphur compound of oxide morphology separates with hydrocarbon and other organosulfur compounds and shows as yellow color development point.Utilize the visible light of densitometer (densitometer) (for example, dual wavelength chromatogram scanner (dualwavelength chromatoscanner) the CS-910 type that Shimadzu Seisakusho Ltd. makes), obtain absorbance the irradiation 380nm of this color development point portion.When measuring sample oil, the sample that the oxide morphology sulphur concentration is known launches simultaneously, carries out same mensuration.Can the sulphur composition of the oxide morphology that contained in the sample be carried out quantitatively thus.In addition, the sulphur composition of oxide morphology is the total amount that constitutes by the sulphur of the represented organosulfur compound of following general formula (1) or following general formula (2):
R 1-S-R 1????????????(1)
[in the formula, R 1Represent independently that respectively carbon number is 10~15 alkyl (alkyl) or aromatic hydrocarbyl]
Figure GPA00001038494700081
[in the formula, R represents hydrogen atom or alkyl respectively independently, when having a plurality of R, each R can be identical also can be different].
Table 1
Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Base oil 1-1 quality % ??80 ??60 ??100 ??20 ??0 ??- ??-
Base oil 2-1 quality % ??20 ??40 ??0 ??80 ??100 ??- ??-
Density (15 ℃) g/cm 3 ??0.8591 ??0.8522 ??0.8661 ??0.8389 ??0.8323 ??0.8592 ??0.8560
Flash-point (PM) ℃ ??148 ??146 ??150 ??144 ??144 ??140 ??148
Kinematic viscosity (40 ℃) mm 2/s ??7.918 ??8.038 ??7.725 ??8.471 ??8.667 ??10.14 ??8.540
Kinematic viscosity (100 ℃) mm 2/s ??2.222 ??2.270 ??2.173 ??2.349 ??2.395 ??2.482 ??2.361
Pour point ℃ ??-32.5 ??-32.5 ??-32.5 ??-35.0 ??-37.5 ??-40.0 ??-32.5
Refractive index ??1.4729 ??1.4692 ??1.4768 ??1.4620 ??1.4586 ??1.4883 ??1.4796
20% recovered (distilled) temperature ℃ ??294 ??296 ??294 ??300 ??305 ??284 ??302
Sulphur composition quality % ??0.04 ??0.03 ??0.04 ??0.01 ??<0.001 ??0.04 ??0.21
The sulphur composition quality % of oxide morphology ??0.015 ??0.010 ??0.020 ??0.005 ??<0.005 ??0.010 ??0.070
Nitrogen component quality ppm ??<1 ??<1 ??<1 ??<1 ??<1 ??3 ??2
Saturated composition quality % ??81.4 ??86.0 ??76.9 ??95.2 ??99.5 ??73.8 ??71.6
Aromatic component quality % ??18.6 ??14.0 ??23.1 ??4.8 ??0.5 ??26.2 ??28.4
Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Resinous principle quality % ??<0.1 ??<0.1 ??<0.1 ??<0.1 ??<0.1 ??<0.1 ??<0.1
Oxidation stability (120 ℃, 75hr) greasy filth quality % total acid number mgKOH/g ??0.04??0.24 ??0.04??0.26 ??0.04??0.20 ??0.02??0.79 ??0.01??1.20 ??0.08??0.27 ??0.08??0.28
Charged degree pC/mL after the deterioration ??88 ??26 ??205 ??15 ??7 ??387 ??522
In the table 1 as can be known: pour point, kinematic viscosity (40 ℃), density (15 ℃), sulphur composition, nitrogen component and the refractive index of example 1 and 2 electric insulating oil are in scope given to this invention, in addition, described electric insulating oil all has good oxidation stability, more specifically, satisfy the oxidation stability specification value (greasy filth: of defined in No. 4, No. 2,1 class of JIS C2320 or 1 class smaller or equal to 0.4 quality %, total acid number: smaller or equal to 0.6mgKOH/g), and the charged degree after the deterioration remain fully low.
On the other hand as can be known: the density of the electric insulating oil of comparative example 1 (15 ℃) is too high, reaches 0.8661g/cm 3, and the charged degree after the deterioration is up to 205pC/mL, and can't the lower charged degree of long term maintenance.
In addition, the density of the electric insulating oil of comparative example 2 (15 ℃) is low excessively, is 0.8389g/cm 3The density of the electric insulating oil of comparative example 3 (15 ℃) is low excessively, is 0.8323g/cm 3, and refractive index is also low excessively, is 1.4586; The total acid number of the oxidation stability of the electric insulating oil of described comparative example 2 and comparative example 3 all is not suitable as electric insulating oil up to 0.79mgKOH/g, 1.20mgKOH/g.
The electric insulating oil of comparative example 4 so refractive index is too high, reaches 1.4883 because refining degree is insufficient, so the charged degree after the deterioration is up to 387pC/mL, can't the lower charged degree of long term maintenance, and relatively poor as electric insulating oil.
The electric insulating oil of comparative example 5 so the sulphur composition is too high, reaches 0.21 quality % because refining degree is insufficient, so the charged degree after the deterioration is up to 522pC/mL, can't the lower charged degree of long term maintenance, and relatively poor as electric insulating oil.

Claims (6)

1. electric insulating oil, it is characterized in that: (A1) pour point is smaller or equal to-27.5 ℃, and (A2) kinematic viscosity (40 ℃) is 5~12mm 2/ s, (A3) density (15 ℃) is 0.840~0.860g/cm 3, (A4) the sulphur composition is smaller or equal to 0.20 quality %, and (A5) nitrogen component is smaller or equal to 20 quality ppm, and (A6) refractive index is 1.460~1.480.
2. electric insulating oil according to claim 1 is characterized in that: the sulphur composition of oxide morphology is 0.01~0.02 quality %.
3. the manufacture method of an electric insulating oil, it makes electric insulating oil according to claim 1, and described manufacture method is characterised in that:
Comprise the step that base oil 1 is mixed with base oil 2, wherein, (B1) pour point of described base oil 1 is smaller or equal to-27.5 ℃, and (B2) kinematic viscosity (40 ℃) is 5~12mm 2/ s, (B3) the sulphur composition is smaller or equal to 0.20 quality %, (B4) nitrogen component is smaller or equal to 20 quality ppm, and (B5) aromatic component more than or equal to 5 quality % and less than 30 quality %; (C1) sulphur composition of described base oil 2 is smaller or equal to 0.001 quality %, and (C2) nitrogen component is smaller or equal to 5 quality ppm, and (C3) aromatic component less than 3 quality %.
4. the manufacture method of electric insulating oil according to claim 3 is characterized in that: described base oil 1 is counted 90/10~40/60 scope with the allotment ratio of described base oil 2 with mass ratio (base oil 1/ base oil 2).
5. the manufacture method of electric insulating oil according to claim 3, it is characterized in that: the density of described base oil 1 (15 ℃) is higher than 0.860g/cm 3, the density of described base oil 2 (15 ℃) is less than 0.840g/cm 3
6. the manufacture method of electric insulating oil according to claim 3, it is characterized in that: the sulphur composition of the oxide morphology of described base oil 1 is 0.01~0.05 quality %.
CN2008801050852A 2007-11-21 2008-10-08 Electric insulating oil and process for producing the same Expired - Fee Related CN101796593B (en)

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CN104250577A (en) * 2013-06-26 2014-12-31 中国石油化工股份有限公司 Electrical insulating oil and use thereof

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JP2542807B2 (en) * 1985-05-29 1996-10-09 出光興産 株式会社 Electrical insulating oil
US5167847A (en) * 1990-05-21 1992-12-01 Exxon Research And Engineering Company Process for producing transformer oil from a hydrocracked stock
JPH11263985A (en) * 1998-03-18 1999-09-28 Japan Energy Corp Production of electrical insulating oil
JP3679272B2 (en) * 1999-06-02 2005-08-03 株式会社ジャパンエナジー Electrical insulation oil
JP3690649B2 (en) * 2000-01-13 2005-08-31 株式会社ジャパンエナジー Electric insulating oil and base oil for electric insulating oil
JP2002260445A (en) * 2001-03-05 2002-09-13 Idemitsu Kosan Co Ltd Electrical insulating oil
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CN104250577A (en) * 2013-06-26 2014-12-31 中国石油化工股份有限公司 Electrical insulating oil and use thereof

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