EP3132010B1

EP3132010B1 - Dielectric liquids containing certain aromatic compounds as viscosity-reducing additives

Info

Publication number: EP3132010B1
Application number: EP15708914.5A
Authority: EP
Inventors: Martin Sterner; Cecilia WETTERHOLM; Ida CRUSELL
Original assignee: Nynas (publ) AB
Current assignee: Nynas (publ) AB
Priority date: 2014-02-11
Filing date: 2015-02-10
Publication date: 2022-02-02
Anticipated expiration: 2035-02-10
Also published as: WO2015122830A1; SE541839C2; PL3132010T3; SE1651123A1; CA2935913A1; EP3132010A1; CA2935913C; DK3132010T3

Description

Field of the invention

The present invention generally relates to dielectric fluids for transformers, and more particularly to such dielectric fluids having a reduced viscosity, and especially a reduced low-temperature viscosity.

Background

Magnetic and electrical fields create losses in a transformer. The energy of these losses is converted in the steel sheet core, the copper windings and other conductors and parts to so-called "loss heat" that leads to an increase of temperature in a transformer. The heat losses are different for different transformers. The high temperature in a transformer also stresses construction materials which are sensitive to high temperatures, particularly materials based on cellulose. According to IEC 60076 the design peak temperature is 98°C at the spots with highest temperature in the transformer in the case of a transformer with normal paper that is meant to last at least 40 years of service. Transformer cooling systems are engineered and designed to keep the temperature of the transformer below the design peek temperature under normal conditions. Normally transformer cooling systems are designed with a flowing dielectric liquid, commonly mineral oil. The effectiveness of the cooling depends on the transformer design, including i.a. oil volume, diameter of oil ducts and dimensions of the coolers and pumps. Beside design factors, the specific heat capacity, designated C_p, the viscosity of the oil at operating temperatures, and the flow properties (laminar/turbulent flow) also influence the cooling. Assuming that most mineral transformer oils have similar specific heat capacity, it is the viscosity that plays the most important role in the heat transfer and dissipation calculations, and hence low viscosity oils have an advantage.
In cold climate areas there can be special requirements, such as e.g. cold start-up specifications, on viscosity and pour point of the dielectric liquid at low temperatures. The viscosity must be low enough to enable the liquid to start flowing; otherwise parts of the transformer will heat up to dangerous temperatures while cooler parts are clogged with cold and highly viscous liquid. Having a clogged or slow flowing system at start up may lead to overheating and breakdown of the transformer.
Not only must a dielectric liquid be a good heat dissipater but it must also have good insulating properties. The constant development and optimization of transformer construction has led to compact structures with the conductors as close to each other as the physics allow without risk of discharges going from one conductor to the other. Oil and paper have been used as insulating material in oil filled electrical equipment for nearly a century. The main technical reason for this is that oil and paper are effective insulators, especially in combination.
In a transformer the oil can, in some cases, be exposed to partial discharges due to poor impregnation of the solid insulation, or if the insulation is wet. Design or assembly error may be other factors causing partial discharges. With partial discharges, some oil molecules will break and the fragments may combine to form hydrogen and methane, which dissolve in the oil. Some reactions in the oil can absorb dissolved hydrogen, this is tested with the industry standard gassing tendency IEC 60626 or ASTM D3300. In the gassing tendency standard the oil is saturated with hydrogen or nitrogen gas in a sealed container and exposed to discharges. The hydrogen absorbing reactions occur mainly when aromatic structures are present, and, to some degree, are dependent on the amount of aromatic structures. Insulating oils with high natural aromatic content absorb more hydrogen gas in the gassing tendency tests but this property can also be altered by certain additives.
The trend for power transformers is that they are built for higher voltages and run at higher average loads closer to their maximum capacity. All parts of the transformer need to be optimized and so must also the dielectric liquid. The dielectric liquid must also have excellent oxidation stability to last in the transformer for many years at high temperature. The dielectric liquid must also have good solubility properties to keep any impurities formed in solution where they will make no harm.
When choosing an insulating liquid for electrical equipment there are many material properties that need to be considered. The common requirements for mineral insulting oil are found in the specifications IEC60296 and ASTM D3487.
To fulfil all demands of modern high voltage transformers naphthenic super grade oil is most often chosen as the insulating liquid. The transformer design must take the oil properties into consideration and with high quality oil the design can be optimised better.
Today less refined oils are commonly used to obtain the desired low gassing tendency effect, since they contain more aromatic compounds. In other cases a well refined oil is used but with an additive. A commonly used additive is Tetralin (tetrahydronaphthalene), a volatile compound that also has some negative health issues, such as being suspected carcinogenic and being irritating to skin and eye.
The use of alkyl(C₁-C₄)naphthalene as an additive to mineral oil to impart to the oil higher gas-absorbing qualities is known from i.a. DE 24 53 863 and WO 93/21641 .
US 2010/0059725 teaches that addition up to 10 wt% of reformer distillate, containing 1- and 2-ring aromatic compounds, to a transformer oil improves the gassing tendency of the transformer oil. Suitable 1- and 2-ring aromatics are e.g. alkylated benzene, naphthalene, alkylated naphthalenes, indanes, biphenyls and diphenyls.
US 3 932 267 teaches that addition of up to 5 % by weight of certain aromatic compounds containing two or more six carbon membered fused or unfused rings at least one of which is a benzene ring, e.g. biphenyl, can improve the gassing properties of an uninhibited transformer oil, which oil has been produced according to a specific process disclosed therein.
US 4 493 943 teaches the use of a combination of at least one diarylalkane, and at least one of mono- and and/or diolefin having two condensed or noncondensed aromatic nuclei, for obtaining an electrical insulating oil having i.a. good hydrogen absorbing capacity. Preferred diarylalkanes are diarylmethane, 1,1-diarylethane, 1,2-diarylethane, and among these especially compounds having a benzene ring, which is not substituted with an alkyl group, e.g. arylphenylethane. Other conventional electrical insulating oils such as polybutene, mineral oils, alkylbenzenes, alkylnaphthalenes and alkylbiphenyls can be added to the oil.
US 4 967 039 teaches that a silicone base oil for use as impregnant in an electric power cable for fire hazard conditions is rendered non-gassing by the addition of about 2-8% of an aryl alkane having at least two benzene rings spaced apart by not less than one nor more than two aliphatic carbon atoms. According to US 4 967 039 the preferred additive is 1-phenyl 1-(3,4 dimethylphenyl) ethane, also known as PXE.
US 5 601 755 teaches a dielectric composition comprising benzyltoluene, benzylxylene, (methylbenzyl)toluene and (methylbenzyl)xylene. The composition can be mixed with mineral oils typically used in transformers.
WO 2012/169372 A1 discloses electrically insulation oil compositions comprising a specific diarylalkane mixture with excellent low temperature properties.

Summary of invention

The present inventor has surprisingly found that diphenylmethane, diphenylethane and similar compounds when added in a small amount to mineral oil will markedly reduce the viscosity of the oil. The extent of reduction of viscosity is unexpected. For example, at -40°C the viscosity of the fluid is almost reduced by 50% when 5% diphenylmethane is added thereto.
Diphenylmethane represent a compound not according to present invention.
Accordingly, the present invention relates to a dielectric liquid as specified in claim 1 containing an amount of 1-10 % by weight of an additive as specified in claim 1.
By means of the present invention, the cold start-up specification of a given dielectric liquid will be improved by the presence of the additive.
The dielectric liquid comprising the inventive additive can be used as having a cold start-up classification corresponding to a lower temperature as compared to the cold start-up specification of the dielectric liquid without the additive.
By virtue of the invention the viscosity dependent heat transfer coefficient of a transformer cooling system will also be improved, and hence also the overall heat transfer coefficient of the transformer cooling system.
By virtue of the reduced viscosity of the dielectric liquid the invention allows for cooling of the transformer to a lower temperature. A lower temperature of the transformer will in turn extend the service life of the transformer. The improved heat transfer coefficient of the transformer cooling system will further enhance the cooling performance of the inventive dielectric liquid.
Also, the lower the temperature can be kept in a transformer, the lower the power losses will be. The lower power losses at lower temperatures are due to i.a. a lower resistance in the metal conductors, and a lower dielectric dissipation factor in the oil at such lower temperatures.
A number of the compounds of the invention are known from the prior art to decrease the gassing tendency of an insulating oil. The compounds of the invention can thus be used as a multipurpose additive to dielectric fluids to decrease both gassing tendency and viscosity thereof.
In cold climate areas there is a need to have insulating oils with low viscosity at low temperatures in order to ensure safe start-ups. The additives of the present invention enables achievement of a combination of a low viscosity at a vide temperature range, e.g. from -40°C to +100°C, and a negative gassing tendency, without affecting flash point negatively or having health and safety issues.
The dielectric liquid of the present invention is especially intended for use in the power industry, particularly in power transformers. The cooling system of the transformer can e.g. be of ONAN, ONAF, OFAN, OFAF, OFWF, ODAN, ODAF, or ODWF type.
The terms "oil", "dielectric oil", "dielectric liquid", and "dielectric fluid" have been used interchangeably herein.
As used herein the term "cold start-up specification" of an oil is intended to primarily refer to the Lowest Cold Start Energizing Temperature (LCSET) as defined in IEC 60296 of the oil. In the table below the maximum viscosity, and the maximum pour point for different LCSETs are set out.

LCSET °C Maximum viscosity mm²/s Maximum pour point °C

0 1800 -10

-20 1800 -30

-30 1800 -40

-40 2 500 -50

Detailed description of the invention

In an attempt to support the modern transformers with top of the line insulating oil a multipurpose additive has been tested for the application of both decreasing viscosity and decreasing gassing tendency. As a result, the aromatic compounds as specified in claim 1 have been found to both decrease the viscosity and the gassing tendency of a dielectric liquid. The extent of the reduction of the viscosity is however unexpected.
For example, at 40°C addition of 5% by weight of the additive to a dielectric fluid will typically produce a decrease in viscosity about twice the expected decrease, e.g. as estimated using Refutas equation. The decrease in viscosity according to the invention will generally be even greater at lower temperatures. For example, at -40°C, the addition of 5% of the additive may even result in a reduction of the viscosity of the dielectric fluid by about 50%. Accordingly, the inventive additive is generally more efficient at lower temperatures, such as at 0°C, and below.
A reduced viscosity of a given dielectric liquid will correspond to an improved cold start-up specification of the dielectric liquid. The inventive dielectric liquid containing the additive can thus be used in new applications, requiring a cold start-up specification corresponding to a lower temperature than that of previous specifications of the dielectric liquid, to which applications the dielectric liquid previously has not been qualified.
As mentioned previously the function of an oil in a transformer is cooling and insulation. The oil flows through the transformer and removes heat and therefore it is not only viscosity but also the viscosity dependent heat transfer coefficient that is interesting to look at. Heat transfer works in different ways depending on the design of the system to be cooled (e.g. ONAN, ONAF, OFAN, OFAF, OFWF, ODAN, ODAF, or ODWF). According to the present invention, addition of 5% by weight of the additive to a dielectric fluid can e.g. improve the heat transfer coefficient of the system at 40°C with about 14%.
The compounds for use as an additive according to the invention are diphenylether, both isomers of diphenylethane, all isomers of methylbiphenyl, dimethylbiphenyl, ethylbiphenyl, trimethylnapthalene, ethylmethylnapthalene, propylnaphthalene, isopropylnapthalene, isopropylmethylnaphthalene and diethylnapthalene, or a mixture of any of the previous compounds. A preferred compound is diphenylether.
The viscosity decreasing effect has been found to be greater when compounds in the range of C₁₂-C₁₄ are being used.
The compounds used as additives according to the invention are non-halogenated.
The flash point is another important property of transformer oils, especially when fire hazard is a critical factor.
Compounds having a relatively high flash point are generally being preferred.
According to the invention the additive is mixed into an insulating fluid for the purpose of decreasing the viscosity, especially the low temperature viscosity, and to decrease the gassing tendency of the fluid. The insulating fluid is selected from naphthenic mineral oil, paraffinic mineral oil, natural ester, synthetic ester, synthetic iso-paraffin, or a mixture of any of said insulating fluids.
A generally preferred group of dielectric fluids according to the invention is the group comprising naphthenic mineral oil, paraffinic mineral oil, natural ester, synthetic ester, and mixtures thereof.
At low temperatures, e.g. at below 0°C, natural esters may be less suitable as the dielectric liquid, due the relatively low pour point.
Preferred insulating fluids for use at low temperatures are naphthenic mineral oil, paraffinic mineral oil, synthetic ester, and mixtures thereof.
The means of addition of the additive to the dielectric fluid and the mixing thereof is not critical as long as an adequate mixing of the components can be accomplished. For example, if the additive is solid when added to the dielectric fluid, the mixture should be heated to a temperature above the melting point of the additive, in order to enable adequate mixing. A suitable temperature of addition of the additive to the dielectric fluid is a temperature at which both additive and dielectric fluid are in a liquid state.
The additive should be added in an amount low enough in order that crystallization of the additive in the dielectric fluid is avoided also at the low temperature end of the intended service temperature range. If crystallization of the additive occurs, the dielectric solution may freeze, or become unduly high in viscosity.
The solubility of the additive may also vary for different oils. For example, a naphthenic oil will probably be able to dissolve more additive than a paraffinic oil.
Examples of specific compounds for use in the invention are diphenylether, 1,2-diphenylethane, and 1,1-diphenylethane.

In the table below values of certain properties for one compound used in the invention, viz. diphenylether, and for tetralin, respectively, are provided for comparison.

	Tetralin	Diphenylether
Ox. Stab. IEC61125C	500 h (1 % in naphthenic oil) - no impact on ox. stab.	500 h (5 % in naphthenic oil) - no impact on ox. stab.
Flash point p.m. ISO 2719	77°C	115°C
Boiling point Of pure substance	206-208°C	259°C
Effect on Gassing tendency when 1% added ASTM D2300	- 15 ml / min	- 17 ml / min
Hazard statements	- H351: Suspected of causing cancer	- H319: Causes serious eye irritation.
	- H315: Causes skin irritation.	- H411: Toxic to aquatic life with long lasting effects
	- H319: Causes serious eye irritation.
	- H411: Toxic to aquatic life with long lasting effects
	- H304: May be fatal if swallowed and enter airways

The more serious hazard statement of cancer suspicion that tetralin has is not stated for the compound used in the present invention.

The present invention will now be described in more detail by means of the following examples. In the Examples the following dielectric fluids were used.

Oil	Type	Pour Point, PP (ISO 3016)
A	Naphthenic Mineral Oil	-63
B	Naphthenic Mineral Oil	-57
C	Naphthenic Mineral Oil	-66
D	Paraffinic Mineral Oil	-45
E	Synthetic Ester	-63
F	Natural Ester	-21

Example 1- mixing procedure, addition of 5 % by weight of diphenylmethane (not a compound of the invention)

5 % by weight of diphenylmethane, which has a melting point of about 25°C, was added to 200 cm³ of naphthenic mineral oil (i.e. Oil A above) having a viscosity of 7.60 mm²/s at 40°C. The oil was heated to 40°C, and mixed using a magnetic stirrer.

Example 2 - diphenylether

In this example, using the mixing procedure in Example 1, the effect of diphenylether on the viscosity at different temperatures, and gassing tendency, respectively, were tested using Oils A, D, E, and F, respectively.

	Gassing Tendency ASTM D2300 (ml/min)	Visc -40°C ASTM D445 (cSt)	Visc -30°C ASTM D445 (cSt)	Visc -20°C ASTM D445 (cSt)	Visc 0°C ASTM D445 (cSt)	Visc 40°C ASTM D7042 (cSt)	Visc 100°C ASTM D7042 (cSt)
Oil A	33.5	2666	682.3	226.8	46.28	7.623	2.070
2.5% additive	-10.6	2134	555.2	190.1	-	7.123	1.999
5.0% additive	-34.0	1717	460.4	162.6	36.51	6.704	1.936
Oil D	-	-^∗∗∗	268.5	118.2	34.73	7.375	2.188
5.0% additive	-	-	-	95.51	29.40	6.627	2.056
]Oil E	-	-	-	1376	247.3	28.56	5.186
5.0% additive	-	-	-	974.2	187.0	23.28	4.6276
Oil F	-	< PP	< PP	-^∗∗∗	198.6	34.61	8.279
5.0% additive	-	-	-	-	165.0	29.44	7.368

- Not measured
-^∗∗∗ Temperature very close to the pour point of the oil. Viscosity of the oil at the relevant temperature not measured.

The above results demonstrate that diphenylether significantly can reduce viscosity, cold temperature viscosity and gassing tendency. Other tests performed have shown that diphenylether has no detectable impact on oxidation stability and very little impact on the flash point of the solution.

Example 3 - bibenzyl (also referred to as 1,2-diphenylethane or dibenzyl)

In this example, using the mixing procedure in example 1, the effect of bibenzyl on viscosity at different temperatures, and gassing tendency, respectively, were tested using Oils A, D, E, and F, respectively.

	Gassing Tendency ASTM D2300 (ml/min)	Visc -40°C ASTM D445 (cSt)	Visc -30°C ASTM D445 (cSt)	Visc -20°C ASTM D445 (cSt)	Visc 0°C ASTM D445 (cSt)	Visc 40°C ASTM D7042 (cSt)	Visc 100°C ASTM D7042 (cSt)
Oil A	33.5	2666	682.3	226.8	46.28	7.623	2.070
2.5% additive	20.0	2127	556.2	191.5	41.05	7.184	2.008
5.0% additive	8.5	1741	460.9	163.7	37.10	6.817	1.956
Oil D	-	-	268.5	118.2	34.73	7.375	2.188
2.5% additive	-	-	-	106.2	31.97	6.954	2.121
Oil E	-	-	-	1376	247.3	28.56	5.186
2.5% additive	-	-	-	-	-	25.61	4.904
Oil F	-	<PP	<PP	-^∗∗∗	198.6	34.61	8.28
2.5% additive	-	-	-	-	178.8	31.45	7.736

The above results demonstrate that bibenzyl significantly can reduce viscosity, cold temperature viscosity and gassing tendency. Other tests performed have shown that bibenzyl has no detectable impact on oxidation stability and very little impact on the flash point of the solution.

Claims

A dielectric liquid selected from the group consisting of naphthenic mineral oil, paraffinic mineral oil, natural ester, synthetic ester, synthetic iso-paraffin, or a mixture of any thereof for a transformer containing 1-10 % by weight of an additive consisting of one or more compounds selected from diphenylether, diphenylethane, methylbiphenyl, dimethylbiphenyl, ethylbiphenyl, trimethylnapthalene, ethylmethylnapthalene, propylnaphthalene, isopropylnapthalene, isopropylmethylnaphthalene and diethylnapthalene.
The dielectric liquid of claim 1, wherein said compound is diphenylether.
The dielectric liquid of claim 1 or 2, wherein the dielectric liquid is a naphthenic mineral oil.