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United States Patent (19) 11) Patent Number: 4,806,276 Maier (45) Date of Patent: Feb

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United States Patent (19) 11) Patent Number: 4,806,276 Maier (45) Date of Patent: Feb United States Patent (19) 11) Patent Number: 4,806,276 Maier (45) Date of Patent: Feb. 21, 1989 (54 ADDITIVE FORTRANSFORMER OILS EPRI Report Project 2028-12, Mar. 1986, pp. S-2-S-4 and 4-1-4-4. (76) Inventor: Bruce R. Maier, 3000 Woodbine, Moore, Fire Protection Handbook, 16th ed., Section 19, Columbia, Mo. 65203 Ch. 2, "Halogenated Agents and Systems'. 21 Appl. No.: 130,014 Primary Examiner-Robert A. Wax 22) Filed: Dec. 8, 1987 Attorney, Agent, or Firm-Kokjer, Kircher, Bradley, 51) Int. Cl. ............................................... HOB 3/24 Wharton, Bowman & Johnson 52 U.S. C. .................................... 252/570; 252/162; 57 ABSTRACT 252/171; 252/172; 252/400.1; 585/6.6 An additive for transformer oils comprising a non-ionic 58) Field of Search ............ 252/162, 171, 172,400.1, fluorosurfactant and a halogenated hydrocarbon where 252/570; 585/6.6 the co-mixture is a liquid at least 70 F. and methods for (56) References Cited preparing and using same. The halogenated hydrocar U.S. PATENT DOCUMENTS bon is preferably chosen from the group comprising C1-C3 alkanes which can be fully halogenated or can 3,772,195 11/1973 Francen ............................. 252/8.05 3,954,882 5/1976 Kalopissis et al. ... 424/70 retain some hydrogen atoms on the structure. The most 4,169,076 9/1979 Kawakami et al. ... ... 252/558 preferred halogenated hydrocarbons being dibromotet 4,207,421 6/1980 Scardera et al. .................... 568/625 rafluoroethane, dibromodifluoromethane or bromo 4,238,373 12/1980 Hardy et al. ........................ 252/546 chloromethane. The most useful surfactants for use in 4,242,516 12/1980 Mueller ............................... 546/248 this invention are those that are capable of dispersing and holding a halogenated hydrocarbon evenly OTHER PUBLICATIONS throughout an oil. This is best accomplished through Anon., "Nonflammable substitute for PCB introduced use of a non-ionic fluoro-surfactant. The additive of this in U.K.," Chem. & Eng. News, vol. 62, No. 13, Mar. 26, invention can be used with any transformer oil to in 1984. crease the useful life of the oil as well as to enhance the Sanders, "The totally non-flammable transformer,' operational parameters of the transformer. Electronics and Power, May, 1986, pp. 361-363. SCS, "Pyrolysis and Combustion of PCB Substitutes,” 36 Claims, No Drawings 4,806,276 1. 2 cals. This sequence of events causes the progressive ADDITIVE FORTRANSFORMER OLS hydrogen removal on the carbon chains of the oil. As a result, the oil which originally was long, organized BACKGROUND OF THE INVENTION carbon chains becomes short carbon chains with a re This invention relates in general to an additive for duced capability for heat transfer and a reduced dielec transformer oils and more particularly to such an addi tric strength. This breakdown is continual and self-per tive comprising a mixture of a surfactant and a haloge petuating in that organic acids, which amplify the nated hydrocarbon that is a liquid at room temperature. breakdown process, are a by-product of the reaction. Transformers are used in electricity and special volt Therefore, it is important that an additive for trans age delivery systems. A transformer can be used to 10 step-up or step-down voltage and change the voltage former oil have characteristics that limit the oxidation through electromagnetic induction. A typical high process and resulting breakdown of the oil. voltage transformer has massive coil windings around a Heretofore, the most widely used transformer oil metal core. The coil winding is typically an insulated additives were polychlorinated biphenyls (PCBs). copper or other low resistivity metal wire and the core 15 PCBs are very effective in improving the longevity of preferably comprises a plurality of thin steel laminations transformers and transformer oils. Typically, a PCB stacked side-by-side. Transformer coil windings of this would be added to the transformer oil to a concentra type are known to breakdown after a period of time by tion of greater than 1000 parts per million (ppm) of oxidation of the coil windings, and by such occurrences transformer oil. as arcing, metal flaking and by the constant heat created Although polychlorinated biphenyls impart ideal by the transformers. This breakdown is greatly reduced characteristics to transformer oils, the use of poly by submersing the coil windings in an enclosed bath of chlorinated biphenyls has been drastically reduced due oil. Most high-voltage transformers are oil-filled sys to its extraordinary environmental hazard. Federal reg temS. ulations now require that transformer oils contain less Transformer oils must, therefore, be able to enhance 25 than 500 parts per million (ppm) polychlorinated biphe the performance of the transformer and prolong the nyls. Such uses of polychlorinated biphenyls in trans useful life of the transformer before breakdown. The formers are prohibited if the equipment poses a risk to extremitus temperature range that transformer oils are food or feed. Federal regulations now also prohibit the subject to is between O' F. and 350 F. The conventional manufacture of polychlorinated biphenyls. operating range is between 60' F. and 190 F. Trans 30 former oils have previously consisted of petroleum Non-polychlorinated biphenyl containing trans based naphthenic oils. It has been forecasted that the former oils are now being used, but these oils are dra supply of such naphthenic oil will be depleted by 1990. matically less effective in that they demonstrate poorer As an alternative, petroleum based paraffinic oils and electrical resistance, greater flammability, and a higher vegetable oils can be used as a suitable transformer oil. 35 tendency to oxidize with the resulting effect of compro Paraffinic oils are generally straight carbon chains. mising the power factor of the transformers. As a result, Vegetable and paraffinic oils are more economical and electric utilities and service organizations incur signifi ubiquitous, but have inconsistent breakdown character cant costs in recycling and exchanging non-poly istics that requires periodic monitoring, while in use in chlorinated biphenyl oils and must also frequently test the transformer, as to its continued effectiveness. the non-polychlorinated biphenyl containing oils to Transformer oils do not have an infinite life span. assure their continued effectiveness in protecting the Most transformer oils undergo auto-oxidation, de transformer. A further consequence of using non-poly creases in pH, and other physical and/or chemical chlorinated biphenyl oils is that more voltage step changes that ultimately permit the transformer to fail down stations are needed where such stations were less due to the inadequacies of the oil. Thus, transformer oil 45 necessary when polychlorinated biphenyl containing additives were developed to improve the longevity and transformers were used. characteristics of transformer oils, and the transformers It is thus evident that a need exists for a transformer themselves. oil additive that protects transformer oils and trans In order for a chemical compound to be an effective formers from frequent breakdown and enhances the transformer oil additive, it must be capable of simulta SO neously raising or stabilizing the resistivity of the final transformers capability and longevity, and that also has mixture, maintaining and stabilizing the dielectric a relatively low level of toxicity. strength of the final mixture, and retarding the rate of A number of different chemicals or compounds have oxidation of the oil. These objects must be met while been tried as substitutes for the polychlorinated biphe also imparting heat stability and fire resistance to the 55 nyl additive for transformer oils. Pyrizolidines, sulphur final mixture. It is also important that the final mixture compounds and other organo-aromatic compounds have a low level of environmental toxicity. have been tried. But while these have been shown to The primary reason for transformer oil breakdown, decrease the oxidation of oil, they also decrease the oil's and subsequent transformer failure, is oxidation of the electrical resistivity thus making them less useful as a oil. When the oil is oxidized, hydrogen atoms are re 60 substitute additive. moved or freed from the oil's molecular chain. This Alkylbenzenes and other petroleum compounds have causes the formation of a "free radical' or a highly been experimented with and used as substitute additives. active intermediate that has a tendency to shear itself These compounds do increase electrical resistance of and other chains into smaller chains. These smaller, the oils, but they also auto-oxidize and are highly com sheared chains have a tendency to associate with avail bustible so as to make the oil flash points dangerously able oxygen molecules or other radicals to form "hype low for safe and effective transformer applications. roxides.' These chains, as hyperoxides, are capable of Additionally, all of the above additives are considered to attacking the remaining chains to create more free radi be relatively toxic. 4,806,276 3 4. former power factor over other non-PCB additives SUMMARY OF THE INVENTION being used. I have discovered that a co-mixture comprising a Other and further objects of the invention, together surfactant and a halogenated hydrocarbon that is a liq with the features of novelty appurtenant thereto, will uid at at least 70 F. performs as an effective additive appear in the course of the following description of the when combined with transformer oils. invention. Dense halogen substituted hydrocarbons have not heretofore been used in oil applications because when in DETAILED DESCRIPTION OF THE the liquid phase they generally have a specific gravity INVENTION greater than 1.8 gm/ml, whereas oil mixtures have a 10 I have discovered that a mixture of a halogenated specific gravity of about 0.9 gm/ml. Thus, liquid halo hydrocarbon that is a liquid at at least 70 F. and a genated hydrocarbons sink to the bottom of an oil mix surfactant is unexpectedly effective as an additive to ture as an immiscible compound.
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