EP2388785A1 - Verfahren zur Herstellung einer auf Pflanzenöl basierenden dielektrischen Flüssigkeitszusammensetzung - Google Patents

Verfahren zur Herstellung einer auf Pflanzenöl basierenden dielektrischen Flüssigkeitszusammensetzung Download PDF

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EP2388785A1
EP2388785A1 EP11174287A EP11174287A EP2388785A1 EP 2388785 A1 EP2388785 A1 EP 2388785A1 EP 11174287 A EP11174287 A EP 11174287A EP 11174287 A EP11174287 A EP 11174287A EP 2388785 A1 EP2388785 A1 EP 2388785A1
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Prior art keywords
dielectric fluid
vegetable oil
pour point
astm
composition
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English (en)
French (fr)
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Kevin James Rapp
Gary Arden Gauger
Charles Patrick Mcshane
Arthur Warren Lemm
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Cooper Industries LLC
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Cooper Industries LLC
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • 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
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • 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
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • C10M2207/4045—Fatty vegetable or animal oils obtained from genetically modified species 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/60—Electro rheological properties
    • 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
    • C10N2030/64—Environmental friendly compositions
    • 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 disclosure relates to dielectric fluids for use in electrical apparatus.
  • Dielectric (or insulating) fluid compositions used in electrical distribution and power equipment act as an electrical insulating medium, i.e., exhibit dielectric strength, and they transport generated heat away from the equipment, i.e., act as a cooling medium.
  • dielectric fluids transport heat from the windings and core of the transformer or connected circuits to cooling surfaces.
  • Liquid filled electrical apparatus used in certain climates may require a dielectric fluid composition that maintains its electrical and physical properties, particularly pourability, for extended periods at low temperatures. This pourability requirement has limited the range of applications for vegetable oil based dielectric fluid compositions, which typically have pour points above about -10 °C.
  • a vegetable oil base fluid may be blended with petroleum based mineral oils or silicones, or formulated with significant amounts of non-biologically based synthetic additives.
  • these additives are expensive, toxic and/or non-biodegradable, and accidental spillage or leakage from the electrical apparatus could damage the surrounding environment.
  • this disclosure is directed to a dielectric fluid composition including at least one refined, bleached and deodorized (RBD) vegetable oil.
  • RBD vegetable oil has a sufficiently low pour point (less than about -20 °C, preferably less than about -25 °C, as measured according to either of ASTM D97 or ASTM D5950) to make the composition well suited for use in electrical apparatus, particularly in cold climates.
  • Such RBD vegetable oils may be used in the compositions, dielectric fluid compositions and methods according to the other aspects of this invention recited herein.
  • the present disclosure is directed to a composition consisting of at least one vegetable oil and at least one antioxidant, wherein the composition has a pour point of less than about -20 °C as measured according to either of ASTM D97 or ASTM D5950.
  • the present disclosure is directed to a composition consisting of at least one vegetable oil, at least one antioxidant, and at least one pour point depressant, wherein the composition has a pour point of less than about -30 °C as measured according to either of ASTM D97 or ASTM D5950.
  • the present disclosure is directed to a dielectric fluid composition including at least one rapeseed oil selected from Brassica Juneca, Brussica Campestris and combinations thereof; and a synthetic ester.
  • the dielectric fluid compositions may be used in an electrical device such as, for example, transformers, switchgear, regulators and reclosers.
  • the present disclosure is directed to a method of making a dielectric fluid, including providing at least one refined, bleached and deodorized rapeseed oil with a pour point of less than about -20 °C as measured by at least one of ASTM D97 and ASTM D5950; treating the rapeseed oil with clay; and filtering the rapeseed oil to produce a processed rapeseed oil.
  • the dielectric fluid compositions described herein have excellent electrical properties, even when formulated with a minimal amount of non-biologically based compounds.
  • the dielectric fluid composition qualifies as at least one of: (I) readily biodegradable as defined by USEPA OPPTS 835.2110; (2) ultimately biodegradable as defined by USEPA OPPTS 835.3100; and (3) biodegradable as measured by method OECD 301.
  • the excellent low temperature performance of the vegetable oil dielectric fluid compositions, as well as their environmentally safe and bio-based nature allows use of the fluids in apparatus and in climatic areas in which vegetable oil based fluids have not been previously employed. Since many components of the vegetable oil dielectric fluid compositions are derived from renewable, seed-based resources, the fluids may be produced easily and at a reasonable cost.
  • FIG. 1 is a cross-sectional view of a transformer including a vegetable oil dielectric fluid composition.
  • FIG. 2 is a plot showing the viscosity of dielectric fluids over time at temperatures of 10 °C and - 20°C.
  • This disclosure is directed to dielectric fluid compositions including at least one refined, bleached and deodorized (RBD) vegetable oil.
  • RBD vegetable oil has a pour point of less than about-20 °C, preferably less than about -25 °C, as measured according to either of ASTM D97 or ASTM D5950. This low pour point makes the dielectric fluid compositions including the RBD vegetable oil well suited for use in electrical apparatus, particularly in cold climates.
  • this disclosure is directed to a dielectric fluid composition that consists of at least one RBD vegetable oil and an antioxidant.
  • the dielectric fluid composition has a pour point less than about -20 °C, preferably less than about -25 °C.
  • RBD vegetable oil refers to crude vegetable oils that have been further processed at a vegetable oil refinery.
  • crude vegetable oil is de-gummed after addition of water followed by alkali refining with a base such as NaOH, bleaching with clay and deodorization using vacuum steam stripping.
  • alkali refining with a base such as NaOH
  • bleaching with clay and deodorization using vacuum steam stripping.
  • Such RBD processing of oils is well known in the art. The processing steps remove contaminants from the crude vegetable oils that would cause poor dielectric performance. Crude vegetable oils also contain more waxy components that would cause less desirable cold temperature performance.
  • the pour point of the dielectric fluid composition may be measured by either of two different methods, ASTM D97 or ASTM D5950 (pour point measurements per the test methods herein may vary as much as ⁇ 3 °C).
  • ASTM D97 a manual technique, is an accepted standard test method for determination of pour point in the electrical equipment industry.
  • automated equipment to measure pour point may in some cases provide improved speed and consistency per ASTM Method D5950.
  • the D5950 method is not yet approved in the electrical industry, although the lubricating fluids industry has converted to and approved the D5950 automated method.
  • the vegetable oil is preferably obtained by processing naturally occurring (non-genetically modified, or non-GMO) seed stocks, but may also be obtained from genetically modified (GMO) or from blends of oils obtained from GMO and non-GMO seeds.
  • One suitable vegetable oil for the dielectric fluid composition may be obtained by processing GMO rapeseed, non-GMO rapeseed, and combinations thereof.
  • Preferred oils are obtained from seeds grown in northern European regions. Oils obtained from non-GMO "winter" rapeseeds grown in northern European climates have particularly low pour points, and are preferred for use in electrical apparatus operated in cold climates. Oils obtained from the seeds of Brassica Juneca and Brassica Campestris plants are particularly preferred, and suitable oils are available from Cargill, Inc., Minneapolis, MN, under the trade designation Agri-Pure 60 Rapeseed Oil.
  • RBD oils obtained from northern European rapeseeds such as, for example. Brassica Juneca and Brassica Campestris seeds, have a fatty acid distribution that results in a pour point of less than about -20 °C, preferably less than about -25 °C, as measured according to either of ASTM D97 or ASTM D5950.
  • Other RBD rapeseed oils such as, for example, those available from North American seed stocks, exhibit a much higher pour point of about -10 to about -16 °c.
  • northern European rapeseed oils derived from Brassica Juneca and Brassica Campestris can provide a significant advantage in low temperature applications.
  • the Brassica Juneca and Brassica Campestris oils used in the dielectric fluid composition may be obtained from a single year's harvest, or oils from various cultivars may be blended to provide a vegetable oil dielectric fluid composition with the desired electrical, chemical and physical properties.
  • dielectric fluid compositions including the preferred RBD Brassica Juneca and Brassica Campestris oils have excellent electrical properties after appropriate processing.
  • the dielectric fluid compositions preferably have a dielectric strength of at least about 55 kv, preferably greater than about 60 kV.
  • the dielectric strength may be measured per ASTM method D1816 using a 0.08 inch (2 mm) gap between VDE electrodes. The determination of dielectric strength is well known in the art and is within the knowledge of the skilled person.
  • the dielectric fluid composition also preferably has a fire point greater than 300 °C, as well as a flash point greater than about 275 °C. Both fire point and flash point may be measured by ASTM D92. The determination of fire point is well known in the art and is within the knowledge of the skilled person.
  • the dielectric fluid composition also preferably has a dissipation factor (DF) at 25°C of less than about 0.1%, and a dissipation factor at 100 °C of less than about 4%.
  • DF dissipation factor
  • the dissipation factors may be measured using ASTM D924. The determination of dissipation factor is well known in the art and is within the knowledge of the skilled person.
  • the vegetable oil used in the composition should preferably have a kinematic viscosity between 2 and 15 cSt at 100°C and less than 110 cSt at 40°C.
  • the fluids used in the dielectric fluid composition have a kinematic viscosity between about 20 and about 50 cSt at 40°C.
  • a common method for measuring the kinematic viscosity at 40/100°C is ASTM D445, however, at cold temperatures of-10°C and -20°C and colder, a different technique may be used.
  • the yield stress and viscosity were measured using a Cannon mini-rotary viscometer (MRV) per ASTM D3829.
  • the MRV operated as a concentric cylinder viscometer in which the yield stress is determined by observing the movement of the cylinder under different applied stress. For example, a 5 gram weight may be used to apply the yield stress and the viscosity may be determined by measuring the time to complete three revolutions.
  • the time is multiplied by a constant, which depends on the cell used for the measurement, and the applied stress, to determine the dynamic viscosity in centipoise (cP).
  • the dynamic viscosity in cP is converted to kinematic viscosity in centistokes (cSt) by dividing the dynamic viscosity by the density of the fluid at the specific temperature of measurement.
  • cSt centistokes
  • the density may be determined using a 250 ml volumetric flask with a 15 ml graduated cylinder for a neck.
  • the internal volume was calibrated with water at a known temperature and mass prior to measuring the fluid.
  • the densities of the fluids at temperature were calculated using the weight of the fluid with the measured volume.
  • the vegetable oil dielectric fluid composition further includes one or more antioxidant compounds.
  • antioxidant compounds include, for example, BHA (butylated hydroxyanisole), BHT (butylated hydroxytoluene), TBHQ (tertiary butylhydroquinone), THBP (tetrahydrobutrophenone), ascorbyl palmitate (rosemary oil), propyl gallate, and alpha-, beta- or delta-tocopherol (vitamin E).
  • the antioxidant compounds may be present in the dielectric fluid composition at less than about 1 wt%, preferably less than about 0.5 wt%, based on the total weight of the composition.
  • any of the dielectric fluid compositions described herein may optionally include other vegetable oils as extenders or to modify its properties, including adjusting the pour point.
  • Any commercially available seed oil may be used, and suitable additional vegetable ails include, for example, soybean, sunflower, crambe, corn, olive, cottonseed, safflower, vernonia, lesquerella and combinations thereof. Of these additional oils, soybean oil and sunflower oil are preferred.
  • the additional vegetable oils may be present or used in any amount, as long as their presence does not substantially degrade the physical, chemical and electrical properties of the composition.
  • the vegetable oil dielectric fluid composition consists of at least one vegetable oil as described above, at least one antioxidant as described above, and at least one pour point depressant.
  • pour point depressants include polyvinyl acetate oligomers and polymers and/or acrylic oligomers and polymers.
  • Suitable pour point depressant compounds include (meth)acrylates such as those available from Rohmax, Philadelphia, PA, under the trade designation Viscoplex. Alkyl methacrylates with a molecular weight of about 200,000, such as Viscoplex 10-310, have been found to be particularly suitable.
  • the pour point depressant may be used alone or may optionally be further diluted with a vegetable oil.
  • Suitable vegetable oil diluted pour point depressant compounds include, for example, the vegetable oil diluted alkyl methacrylates available from Functional Products, Cincinnatiia, OH, under the trade designation PD-551.
  • the pour point depressant is present in the vegetable oil dielectric fluid composition up to about 4 wt%, preferably about 0.2 wt% to about 2 wt%, and more preferably from about 0.4 wt% to 2 wt%.
  • Vegetable oil dielectric fluid compositions include an antioxidant and a pour point depressant typically have a pour point of less than about -30 °C, preferably less than about - 33 °C, as measured by at least one of ASTM D97 and ASTM D5950. Including these additives, the vegetable oil dielectric fluid composition typically has a fire point greater than about 300 °C, preferably greater than about 350 °C, and a flash point of greater than about 275 °C, preferably greater than about 325 °C. Other properties of a typical vegetable oil dielectric fluid composition with additives are shown in Table 5 below.
  • any of the dielectric fluid compositions described herein may optionally include a small amount of one or more additives to inhibit the growth of microorganisms.
  • Any antimicrobial substance that is compatible with the dielectric fluid may be blended into the fluid.
  • compounds that are useful as antioxidants also may be used as antimicrobials. It is known, for example, that phenolic antioxidants such as BHA also exhibit some activity against bacteria, molds, viruses and protozoa, particularly when used with other antimicrobial substances such as potassium sorbate, sorbic acid or monoglycerides. Vitamin E, ascorbyl palmitate and other known compounds also are suitable for use as antimicrobial additives.
  • any of the vegetable oil dielectric fluid compositions described herein may further optionally include a colorant such as a dye or pigment.
  • a colorant such as a dye or pigment. Any known dye or pigment can be used for this purpose, and many are available commercially as food additives. The most useful dyes and pigments are those that are oil Soluble.
  • the colorant is present in the composition in minor amounts, typically less than about 1 ppm.
  • any of the vegetable oil dielectric fluid compositions described herein may optionally include a minor amount of one or more petroleum derived oils, such as, for example, mineral oils and/or polyatphaotefins.
  • Mineral oils from naphthenic and paraffinic sources are typically refined and processed in to transformer fluids that meet the electrical industry standards per ASTM D3687.
  • Suitable mineral oil-based dielectric fluids include, for example, those available from Petro-Canada under the trade designation Luminol TR, those available from Calumet Lubricating Co. under the trade designation Cattran 60-15, and those available from Ergon Refining Inc. under the trade designation Hivolt II.
  • Suitable polvalphaolefins have a viscosity from about 2 cSt to about 14 cSt at 100°C, and are available from Chevron under the trade designation Synfluid PAO, Amoco under the trade designation Durasyn and Ethyl Corp. under the trade designation Ethylflo.
  • Particularly preferred polyalphaolfins have a viscosity from about 4 cSt to about 8 cSt, and originate from dimers, trimers and tetramers of chains of 10 carbons. The most preferred viscosity range for the polyalphaolefins is from about 6 cSt to about 8 cSt.
  • the petroleum derived oils and polyalphaolefins may be incorporated into the composition at less than about 10% by weight, preferably less than about than 5 percent by weight.
  • the present disclosure is directed to a vegetable oil dielectric fluid composition including at least one vegetable oil as described above, and a synthetic ester compound.
  • the vegetable oil dielectric fluid composition preferable further includes an antioxidant as described above and a pour point depressant as described herein.
  • the synthetic ester may be blended with the vegetable oil and other optional components in an amount sufficient to modify the properties of the dielectric fluid composition, particularly to further lower pour point for a particular cold temperature application.
  • synthetic ester refers to esters produced by a reaction between: (1) a bio-based or petroleum-derived polyol; and, (2) a linear or branched organic acid that may be bio-based or petroleum-derived.
  • polyol refers to alcohols with two or more hydroxyl groups.
  • esters may be derived from biologically based compounds, petroleum by-products, or combinations thereof, biologically based esters derived from renewable compounds produced by animals and plants are preferred.
  • bio-based refers to compounds derived from substances produced by either animals and/or naturally occurring or cultivated plants.
  • the plant and animal sources for the bio-based compounds may be GMO, non-GMO and combinations thereof, and non-GMO sources are preferred.
  • the term "bio-based” has the meaning set forth in the USDA FB4P (2002 Farm Bill), e.g. 70 Fed. Reg. 1792 (January 11, 2005) and 71 Fed. Reg. 59862 (October 11,2006) (to be codified at 7 C.F.R. pt. 2902).
  • bio-based synthetic esters include those produced by reacting a polyol and an organic acid with carbon chain lengths of C8-C10 derived from a vegetable oil such as, for example, coconut oil, Suitable synthetic esters are available from Cargill (Brazil) under the trade designation Innovatti, as well as from Hatco Chemical Co., Kearney, NJ.
  • Envirotemp 200 E200
  • Hatco 5005 from Hatco Chemical Co.
  • TMP trimethylolprapane
  • polyols suitable for reacting with organic acids to make synthetic esters include, for example, neopentyl glycol, dipentaerythritol, and 2-ethylhexyl, n-octyl, isooctyl, isononyl, isodecyl and tridecyl alcohols.
  • the synthetic esters may be used in the vegetable oil dielectric fluid composition at up to about 70% by weight, preferably about 30% by weight to about 70% by weight, and even more preferably about 25% by weight to 70% by weight. Generally, larger amounts of the synthetic ester result in a dielectric fluid composition with a lower pour point. For example, some vegetable oil dielectric fluid compositions including up to about 30 wt% synthetic ester have a pour point of less than about -38 °C, while some compositions including up to about 70 wt% synthetic ester have a pour point of less than about -50 °C, according to at least one of ASTM D97 and ASTM D5950.
  • the composition should preferably be biodegradable, nontoxic and formulated with a minimum of non-bio based material.
  • the vegetable oil dielectric fluid composition should preferably include at least 70% bio-based material and more preferably at least about 72.5% bio-based material.
  • bio-based content can be determined by using ASTM Method D 6866, which is based on the amount of bio-based carbon in the material as % of the mass of the total organic carbon in the product.
  • the vegetable oil dielectric fluid compositions described above should also preferably be formulated to includes a minimum amount non-biodegradable material.
  • the amount of synthetic and/or non-biodegradable additives in the vegetable oil dielectric fluid composition should preferably be limited such that the composition qualifies as at least one of: (1) readily biodegradable as defined by USEPA OPPTS 835.3110; (2) ultimately biodegradable as defined by USEPA OPPTS 835.3100; and (3) biodegradable as measured by method OECD 301.
  • Readily biodegradable as defined by USEPA OPPTS 835.3110 is an arbitrary classification of chemicals which have passed certain specified screening tests for ultimate biodegradability. These tests are so stringent that it is assumed that such compounds will rapidly and completely biodegrade in aquatic environments under aerobic conditions.
  • Ultimate biodegradabitity as defined by USEPA OPPTS 835.3100 is the breakdown of an organic compound to CO 2 , water, the oxides or mineral salts of other elements, and/or to products associated with normal metabolic processes of microorganisms.
  • the vegetable oil dielectric fluid compositions described above should preferably be formulated to be essentially free of GMO material, which means that the composition includes no more than about 5% by weight GMO material. Even more preferably, the composition should be substantially free of GMO material (no more than about I wt% GMO), and most preferably completely free of GMO material, which means that no GMO material is present in the composition except for impurities. In the present application, substantially does not exclude completely, e.g. a composition that is substantially free from GMO material may be completely free from GMO material. Where necessary, the world substantially may be omitted from the definition of the invention.
  • the vegetable oil dielectric fluid compositions described above may be made by taking commercially available refined, bleached and deodorized (RBD) vegetable oils and treating the oils to remove impurities and improve electrical properties.
  • RBD oils are typically treated by removing moisture and stirring with an absorber, such as an activated clay, to remove impurities, which can be detrimental to the electrical properties of the oils.
  • the RBD oils may be heated and/or filtered to remove particles, microorganisms and the like.
  • the RBD oils are treated by adding about 10 wt% heated clay (170°C) to the heated oil white stirring. The oil is then filtered to remove the clay particles containing the absorbed contaminants followed by vacuum processing to less than about 10 torr.
  • preferred processed oils contain a maximum of about 200 ppm water, more preferably a maximum of about 100 ppm water.
  • the processed oils may be used alone as dielectric fluids in electrical apparatus. However, prior to use the oils are typically blended with the additives described above, e.g. antioxidants, pour point depressants, colorants and the like. The processed oils may be further blended with additional vegetable oils, synthetic esters, synthetic or petroleum derived oils and the like to tailor their properties for a particular application.
  • the present disclosure is directed at electrical apparatus having therein a dielectric fluid composition including at least one RBD vegetable oil as described above and an antioxidant.
  • the dielectric fluid composition has a pour point of less than about -20 °C. preferably less than about -25 °C, as measured according to either of ASTM D97 or ASTM D5950.
  • the dielectric fluid composition in the electrical apparatus may further include any of the additives described above, including, for example, pour point depressants, additional vegetable oils, synthetic esters, mineral oils, polyalphaolefins, and the like.
  • the vegetable oil dielectric fluid composition may be incorporated into any electrical equipment or apparatus including, but not limited to, transformers, switchgear, regulators and reclosers.
  • a transformer 10 includes a tank body 12 enclosing a transformer core coil assembly and windings 15, The core coil assembly and windings 15 are at least partially immersed in a dielectric fluid 18.
  • the space between a surface of the fluid 18 and the tank body 12, referred to as the headspace 20, may optionally include an oxygen permeable container 24 housing an oxidation reducing composition 22 such as those described in US 2005/0040375 .
  • a pre-packaged oxygen scavenging compound such as is available commercially under the Ageless and Freshmax trade names, may be encased in a pouch constructed of a oxygen permeable polymer film, a polyester felt or a cellulose pressboard.
  • the tank body 12 may also include optional features such as a threaded plug 28 with a view port 30, and a pressure release device 40.
  • the dielectric fluid compositions preferably are introduced into the electrical apparatus in a manner that minimize the exposure of the fluid to atmospheric oxygen, moisture, and other contaminants that could adversely affect their performance.
  • a preferred process includes drying of the tank contents, evacuation and substitution of air with dry nitrogen gas, filling under partial vacuum, and immediate sealing of the tank. If the electrical device requires a headspace between the dielectric fluid and tank cover, after filling and sealing of the tank, the gas in the headspace may be evacuated and substituted with an inert gas, such as dry nitrogen.
  • Electrical transformers and switchgear typically are constructed by immersing the core and windings and other electrical equipment in a dielectric fluid and enclosing the immersed components in a sealed housing or tank.
  • the windings in larger equipment frequently are also wrapped with a cellulose or paper material.
  • the vegetable oil dielectric fluid compositions described herein also may be used to protect and extend the useful service life of the cellulose chains of the paper insulating material. While not wishing to be bound by any theory, presently available evidence indicates that the vegetable oil dielectric fluids absorb water from the paper, which prevents the paper from hydrolytic degradation, and provides long-chain fatty acids that transesterify the cellulose and further reduce paper breakdown, particularly at higher equipment operating temperatures.
  • the vegetable oil dielectric fluids compositions can also be used to retrofill existing electrical equipment that incorporate other, less desirable dielectric fluids. Retrofilling existing equipment can be accomplished using any suitable method known in the art, though because of the increased sensitivity of vegetable oil fluids to moisture, the components of the electrical equipment may optionally be dried prior to the introduction of the vegetable oil based dielectric fluid. This may be particularly Useful if the equipment includes cellulose or paper wrapping, which can absorb moisture over time. Because of the relatively high solubility of water in vegetable oils, a vegetable oil fluid can itself be used to dry out existing electrical equipment.
  • Table 1 Sample Crop Year Pour Point (°C) (ASTM D97) 1 2004 -26 2 2005 -25 3 2006 -26
  • the rapeseed oil was Cargill Agri-Pure 60 from Antwerp, Belgium, and included the preferred genus and species types Brassica Juneca and Brassica Campestris .
  • the RBD soybean oil had a pour point of about -10 to about-16 °C according to ASTM D5950, white the RBD rapeseed oil had a pour point of -26 °C.
  • the processed oils were then blended with additives to enhance their performance as electrical insulating fluids.
  • the processed oils were blended with 0.40% by weight of BHT antioxidant, and 1.0 wt% of a pour point depressant, Viscoplex 10-310, available from Rohmax, Philadelphia, PA.
  • Soybean Oil refers to a soybean oil derived dielectric fluid available from Cooper Power Systems. Waukesha, WI. under the trade designation Envirotemp FR3 Fluid.
  • Table 6 Base Fluid Synthetic Ester E200 Synthetic Ester EXP 1906 Pour Point (°C) (ASTM D 5950) Pour Point (°C) (ASTM D97) Beneficial Aspects Fire Point > 300°C >70% Bio-based & Renewable Example C1 30 % Soybean Oil 0 70% -18 Yes (304°C) Yes
  • Example 3-1 30 % Euro-Rapeseed 0 70% -50 Yes (303°C) Yes
  • Example 3-2 70 % Euro-Rapeseed 0 30% -39 -38 Yes (321°C) Yes
  • Example 3-3 30 % Euro-Rapeseed 70% 0 -51 Yes No
  • Example C2 compared to examples 3-2 and 3-4 show the improved cold temperature performance of the Euro-Rapeseed fluid compared to a soybean oil based fluid.
  • Fig. 2 show that, when introduced into electrical power equipment, the substantially bio-based and biodegradable formulations of the presently described dielectric fluid flow and maintain a relatively constant viscosity for an extended period of time compared to a conventional oil.

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  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Lubricants (AREA)
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JP5209581B2 (ja) * 2009-08-27 2013-06-12 北芝電機株式会社 変圧器
US20110232940A1 (en) * 2010-03-23 2011-09-29 Massachusetts Institute Of Technology Low ionization potential additive to dielectric compositions
KR101984342B1 (ko) * 2011-12-30 2019-05-30 다우 글로벌 테크놀로지스 엘엘씨 파네센 기재 올리고머를 갖는 유전 유체
CN110819428B (zh) * 2019-10-30 2022-08-23 国网湖南省电力有限公司 一种石墨烯改性的植物绝缘油及其制备方法

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