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WO1988000849A1 - Reclassification d'appareils electriques contamines par pcb - Google Patents

Reclassification d'appareils electriques contamines par pcb Download PDF

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Publication number
WO1988000849A1
WO1988000849A1 PCT/US1987/001830 US8701830W WO8800849A1 WO 1988000849 A1 WO1988000849 A1 WO 1988000849A1 US 8701830 W US8701830 W US 8701830W WO 8800849 A1 WO8800849 A1 WO 8800849A1
Authority
WO
WIPO (PCT)
Prior art keywords
transformer
fluid
leaching fluid
leaching
polychlorinated biphenyls
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1987/001830
Other languages
English (en)
Inventor
Michael J. Massey
David R. Hopper
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
R E I TECHNOLOGIES Inc
Rei Technologies Inc
Original Assignee
R E I TECHNOLOGIES Inc
Rei Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by R E I TECHNOLOGIES Inc, Rei Technologies Inc filed Critical R E I TECHNOLOGIES Inc
Priority to BR8707765A priority Critical patent/BR8707765A/pt
Priority to DE19873779646 priority patent/DE3779646T2/de
Priority to AT87905135T priority patent/ATE76766T1/de
Publication of WO1988000849A1 publication Critical patent/WO1988000849A1/fr
Priority to KR1019880700348A priority patent/KR880701574A/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/006—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents of waste oils, e.g. PCB's containing oils
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/20—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by hydropyrolysis or destructive steam gasification, e.g. using water and heat or supercritical water, to effect chemical change
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/08—Cooling; Ventilating
    • H01F27/10—Liquid cooling
    • H01F27/12—Oil cooling
    • H01F27/14—Expansion chambers; Oil conservators; Gas cushions; Arrangements for purifying, drying, or filling

Definitions

  • This invention relates to an apparatus and method for cleaning or reclassifying electrical apparatus, such as transformers and capacitors, designed to use as a liquid dielectric fluid polychlorinated byphenyls, and a porous internal construction.
  • electrical apparatus such as transformers and capacitors
  • Such apparatus is characterized by the adsorption of the liquid into the pores of structural support media, thereby rendering difficult the complete removal of said liquid.
  • PCB polychlorinated byphenyls
  • PCB's polychlorinated byphenyls
  • Dielectric fluids containing such PCB ' s have often been generically called askarels where the PCB is often present as a mixture in a chlorinated benzene solvent.
  • PCB's were hazardous environmental contaminants and their use was discontinued; however, by that time many pieces of electrical apparatus had been built using the PCB's as an insulation media.
  • a primary use of PCB is in electrical transformers and electrical capacitors as a coolant dielectric fluid.
  • This invention relates to cleaning PCB's from such apparatus and eventual reclassification of it as non-PCB equipment. For reclassification it is presently necessary that tests demonstrate a contamination of less than 50 ppm of PCB in the dielectric fluid after three months of operation succeeding the completion of cleaning.
  • Transformers designed for PCB use all have a major similarity in that they contain a cellulosic material as insulation, usually a paper wrap, on the wire comprising the core of the transformer. Included in the transformer may be wooden structures acting as insulators. Because of these two major items, the interior of the transformer acts somewhat like a sponge and PCB's become impregnated into these materials. They are contained in such a manner that simple washing will not remove them, and that, over a period of time, the PCB's will leach out of the cellulosic material and come to an equilibrium level in the transformer even if it had been filled with clean, non-PCB, oil. Transformers which use a mineral oil dielectric are different and the invention does not apply. A similar problem is encountered in the disposal of transformers and capacitors which are impregnated with more than 500 ppm PCB or PCB contaminated liquids which are understood to be liquids containing from 50 to 500 ppm PCB.
  • the present invention relates to apparatus and methods for cleaning and reclassifying liquid filled electric apparatus designed to use PCB dieletric fluid to meet at least the present U. S. government EPA standards as "non-PCB" equipment. Apparatus designed to use mineral oils are not cleaned hereby.
  • the present invention therefore provides a method for cleaning electrical apparatus for reclassification contaminated with polychlorinated biphenyls capable of being practiced while the apparatus, containing a leaching fluid capable of separation by distillation from polychlorinated biphenyls, is energized, comprising the steps of: (a) withdrawing leaching fluid contaminated with polychlorinated biphenyls from the apparatus being cleaned and reclassified, (b) distilling the leaching fluid to produce an overhead stream of leaching fluid substantially free of polychlorinated biphenyls and a bottom stream containing the polychlorinated biphenyls, (c) recycling the leaching fluid to the apparatus, and repeating steps (a) -(c) for a time sufficient to reduce the polychlorinate biphenyls remaining in the electrical apparatus to an amount whereby the apparatus may be reclassified.
  • the present invention is also directed to an apparatus for cleaning for reclassification an electrical apparatus contaminants with polychlorinated biphenyls which comprises means for removing and conducting a leaching fluid contaminated with polychlorinated biphenyls from electrical apparatus, first single stage distillation column configured to form an overhead vapor stream consisting essentially of the leaching fluid and a bottoms stream contaminated with polychlorinated biphenyls, condensing means for condensing the vapor, means for returning the condensed leaching fluid to the electrical apparatus, means for withdrawing and conducting the bottoms stream from the first distillation column, a second single stage distillation column to receive the bottoms stream configured to form an overhead vapor streams consisting essentially of the leaching fluid and a bottoms stream containing polychlorinated biphenyls, condensing means for condensing the vapor, and means for conducting the condensed leaching fluid to the first distillation column.
  • This invention allows cleaning of electrical apparatus designed for PCB use, such as a transformer, while the apparatus is energized and operating on line. Normally only a single discontinuance of service of the electrical apparatus is necessary, and occurs to initially drain a PCB, or PCB contaminated, fluid from the electrical apparatus. Maintenance can then be performed. During this time the apparatus can be modified if necessary and connected to the cleaning apparatus, which includes a distillation unit.
  • the apparatus is filled with a leaching fluid chosen both to leach PCB's from the core, or cellulosic material insulation on the core wiring of a transformer, and to serve as the insulating dielectric fluid coolant for maintaining the electric apparatus on line and energized while the method of reclassification is being performed.
  • Leaching fluid is circulated from the electric apparatus through the distillation unit, where it is separated from PCB's being removed from the electrical apparatus, and recirculated back through the transformer.
  • the concentrated PCB's are accumulated on site for disposal.
  • Fig. 1 is a schematic flow sheet showing the method of this invention as applied to reclassifying a PCB, or PCB- contaminated, transformer.
  • Fig. 2 is a schematic flow sheet of a preferred embodiment of the method of this inventior employing a single stage distillation column.
  • Fig. 3 shows the rate of removal of residual PCB's from transformers in the practice of the invention of this application (Example 1).
  • Fig. 4 shows the leaching rate of removing the residual PCB's from the core material during cleaning of transformer prior to the reclassification of transformers (Example 1).
  • Fig. 5 shows the PCB levels in transformer dielectric fluid for three months monitoring for reclassification after the cleaning process of the instant invention has been completed (Example 1).
  • Fig. 6 is a schematic flow sheet of another preferred embodiment of the method of this invention employing dual, single stage distillation columns. Detailed Description of the Preferred Embodiments
  • the method of the present invention can be understood by its application to one preferred embodiment; i.e., the draining, decontamination and reclassifying of electrical power transformers which have been previously insulated with a PCB coolant fluid. It will be understood that other liquid materials including chlorinated benezene which are often found accompanying PCB's in electrical apparatus like power transformers may be removed by the process of this invention along with the PCB's.
  • the primary advantage of the method of the present invention comes from the onsite, unattended reclassification of electrical apparatus in a manner which is capable of being conducted without substantial periods of interruption of operations of such equipment.
  • This method can be practiced either continuously or in a periodic, batch mode as described herein where operation is not continuous but is positioned in a batch mode and carried out in such a manner that operation of the apparatus could proceed without interruption.
  • the equipment useful in the practice of this invention may also be placed near the electrical apparatus the contaminated fluid may be transported to the equipment.
  • the equipment here a transformer
  • the transformer is then preferably washed with an amount of solvent, or leaching fluid, of from about one to about ten percent of its volume to remove any major gross puddles of
  • the liquid solvent, or leaching fluid is dispersed throughout the case to flush out radiators and other parts of the transformer. This solvent is then either removed from the transformer and stored for further processing at the site or run through the distillation unit as hereinafter described in the practice of the invention to separate it from the PCB's. Maintenance would be preferably performed on the apparatus to change gaskets and the like during this period.
  • PCB's available for contaminating the new fluid amounts to small amounts relative to the total liquid capacity of the transformer.
  • significant amounts of PCB's remain absorbed in the core of the transformer, available to leach out once the transformer is refilled with dielectric fluid and placed back on-line.
  • the transformer may be conveniently fitted with means for removing the fluid, connections and valves and the like, to provide for conducting leaching fluid in and out of the transformer without interrupting on-line, energized cleaning and reclassification in accordance with this invention.
  • the added valves allow the possibility of refilling of the transformer with a dielectric fluid different from the leaching fluid with a minimum of interruption, if any, of the operation of the transformer.
  • a distillation unit as described herein is attached to fittings, hereinafter described, on the transformer which, for purposes of this discussion, is filled with a liquid leaching fluid.
  • the liquid leaching fluid may be any fluid which is a solvent for the PCB and which has a boiling point sufficiently distant from that of the PCB to be easily separated by distillation; i.e., having a boiling point sufficiently below that of the PCB to form a sharp separation.
  • PCB compounds normally used for electrical apparatus are usually a wide range of cogeners which boil within the range of about 250° to about 500°C.
  • Commonly used PCB containing fluids were called askarels which were often mixtures of biphenyls having differing degrees of chlorination in a trichlorobenzene (TCB) solvent; for example, common mixtures contained from about 50% to about 85% mixed PCB's and corresponding from about 15% to about 50% TCB.
  • TCB trichlorobenzene
  • the leaching fluid will also have a boiling point sufficiently high to avoid special equipment requirements for condensation of vapors that are generated.
  • the leaching fluid should have the essential properties of a coolant dielectric fluid and be compatible with the internal core of the transformer such that energized operation of the transformer is possible during the steps of the cleaning and reclassification process.
  • it is important, as is well known to those skilled in the art, to avoid exposure of the core to oxygen and moisture. During operation this is assured by including a siphon leg equipped with a siphon breaking means which controls flow from the transformer to the distillation apparatus which will stop flow of leaching fluid and cause the distillation to stop in the event of danger of the core becoming exposed.
  • a preferred leaching fluid for use in the practice of this invention is perchloroethylene, boiling point about 121°C, either the pure substance having less than about 100 ppm halohydrocarbon contaminants as described in ⁇ . S.
  • Another preferred leaching li lid would be an inhibitor stabilized perchloroethylene containing from 200 ppm to about 500 ppm of trichloroethylene.
  • Any of the leaching fluid containing perchloroethylene as described above may be used alone or in conjunction with a hydrocarbon diluent, preferably from about 1% to about 30% by weight thereof, preferably boiling within about 10°C of the perchloroethylene in order to provide an easy separation by distillation from the PCB's.
  • the hydrocarbon diluent preferably would be selected to preserve the non-flammable nature of the perchloroethylene fluid.
  • a distillation system can be attached on site as hereinafter described, to the transformer and operated either continuously or periodically, circulating the leaching fluid from the transformer through the distillation unit where PCB's are removed from the fluid and cleaned leaching fluid is circulated back to the transformer.
  • a transformer T having core windings W is filled with leaching fluid F which is withdrawn, preferably by gravity, though it may be pumped, from transformer T through nozzle 2, line 4, valve 6 and line 8 to line 10 and discharged into a distillation column D onto, for purposes of illustration, a tray 3.2. Though shown otherwise, flow to distillation column D is preferably by gravity.
  • the leaching fluid in distillation column D is heated in a still 14 through the introduction of heat, shown as coils 16 preferably electric, but. steam or one of the well known heating fluids may be an alternative, to a temperature sufficient to boil the leaching fluid from the PCB's.
  • This temperature will, of course, vary with the selection of leaching fluid but preferably, in the case when using perchloroethylene as the leaching fluid, the temperature will be from about 120°C to about 180°C, and more preferably from about 120°C to about 150°C, to produce an overhead stream 18 which is leaching fluid substantially free of polychlorinated biphenyls, usually less than about 2 ppm by weight PCB's in later stages of operation, with such
  • PCB's being contained form in a bottoms stream 15 collected in the still 14.
  • TCB solvent when the mixture of askarel to perchloroethylene leaching fluid is 50/50, the temperature will be about 135°C; at 90/10, about 190°C. In contrast a pure PCB (no TCB solvent) mixed with leaching fluid would require temperatures of about 140°C and 210°C, respectively.
  • PCB's and still be considered to be substantially free of PCB's while the foregoing limitation of less than about 2ppm is more important at later stages of cleaning prior to reclassification tests.
  • concentration of PCB in overhead stream 18 depends upon concentration of PCB's in bottoms 15, number of stages or trays in column D and the temperature of operation. Further concentration of PCB's can be accomplished as described later.
  • the overhead stream 18 is shown exiting the distillation column D through line 18 as a vapor and proceeding to a condenser C where the vapor is condensed into a liquid through heat exchange, preferably in a finned heat exchanger exposed to atmospheric air for reducing the temperature of the overhead stream 18.
  • line 18 may be packed with a wire mesh such that some condensate is formed which falls back into column D as a limited, but uncontrolled reflux.
  • the overhead stream distillate exits the condenser C through line 20 and valve 22 proceeding through line 24 for return through valve 26 and nozzle 28 to the transformer T.
  • the PCB's collect as bottoms stream 15 in the still 14. Heat is applied through coil 1.6 in the bottoms 15 which contain a portion of the leaching fluid, normally from 50% to about. 75% by weight, preferably 80% to 90% leaching fluid toward the end of the reclassification process of this invention.
  • the concentration of the leaching fluid collected in the still 14 may be decreased by raising the temperature used in the distillation column D and by increasing the number of stages in the column D. Typically, in early stages of cleaning, the concentration of leaching fluid, when perchloroethylene, will be maintained at about 50% to about
  • the leaching fluid concentration in bottoms 15 will preferably be at. least about 80% by weight, preferably about 90% and most preferably, about 95% by weight.
  • level controller 30 serving to operate automatic valve
  • the bottoms stream 3.5 containing PCB's are removed periodically from the column D to purge PCB's from the system and pass through line 34, valve 32 and line 36 to storage for further disposal or further processing.
  • the controller 30 can trigger heat through coil 16 to raise temperature of the still 14 and reduce the volume of the bottoms 15 by increased distillation or to operate valve 6 to regulate flow of leaching fluid to distillation column D.
  • the distillation column D is designed preferably, as mentioned above, to have but a single stage distillation zone for the sake of simplicity of construction and operation as well as simplicity of design for starting, stopping, and restarting the apparatus.
  • the number of distillation stages required may be varied considerably dependent upon the leaching fluid chosen, the degree to which the PCB's are to be separated from the leaching fluid in a single pass and the maximum concentration of PCB's to be permitted in the bottoms stream 15 of the distillation column D.
  • the distillation be sufficiently complete to have a PCB concentration of less than about 100ppm early and later, two parts per million by weight in the overhead stream 18.
  • the parameters stated above require only one stage for distillation when the leaching fluid is perchloroethylene, its concentration in the bottoms 15 is from about 50% to about 75% by weight during the early stages of cleaning, and when in the later stages of cleaning the concentration of the leaching fluid is preferably from about 80% to about 95% by weight.
  • leaching fluid make-up is added, for example, through line 40, valve 42 and line 44 into line 24 and thus to the transformer T through valve 26 and nozzle 28 to maintain the level of the leaching fluid F in the transformer T at a level above the coil windings W so that while the leaching and PCB removal steps are occurring, the transformer can be maintained in an energized, on-line state performing its function.
  • Other means of addition may be used, including initial changing of enough extra fluid at the initial filling of the transformer to allow for the quantities to be removed during cleaning through discharge from the still 14.
  • the rate at which the leaching fluid is recycled to the transformer is preferably chosen to insure that during most of the time required for the cleaning of a transformer
  • PCB's are being removed from the fluid more rapidly than they are being leached from the transformer core into the fluid.
  • Additional make-up fluid is at least added in amounts to assure that, the leaching fluid in the transformer always covers the core of the transformer in order that it may be maintained in an energized state during the practice of the method of this invention.
  • the leaching fluid In order to maintain a capability for the on-line status of the transformer, the leaching fluid must serve as the coolant/ dielectric fluid and cover the core of the transformer being cleaned and reclassified. Otherwise the output of the transformer would be unavailable.
  • the rate of recycle must be substantially equal to the rate at which the contaminated fluid is withdrawn.
  • a preferred means for assuring that the core remains covered, independently of the rate of withdrawal of leaching fluid, is a siphon loop through which the leaching fluid is withdrawn from the transformer which will be described in greater detail later.
  • the process can then be stopped and, if desired, leaching fluid discharged through valve 56 or bottoms valve 32 and an alternative transformer fluid introduced through line 40 and the succeeding elements into the transformer T to replace the leaching fluid F.
  • the substitution will require that the transformer T be taken off line while the leaching fluid is drained and the transformer T is filled. It is possible, though risky, to make the substitution of fluids while the transformer is energized.
  • valve 22 would be closed and valve 50 would be opened to allow the condensed leaching fluid in line 20 to be removed through line 52, valve 50 and line 54 for collection and further use at a later time.
  • line 54 could join into line 10 allowing the column D to remain operable during the substitution.
  • valve 56 (or valve 32) would be opened to allow the drainage of leaching fluid F through nozzle 2, valve 6 and line 8 to divert the fluid through line 58, valve 56, and line 66 into an appropriate collecting vessel (not shown).
  • the alternative dielectric fluid can be introduced as described above. Once the transition to the alternative fluid is complete, then the transformer T can again be energized by closing valves
  • the apparatus of this invention can then be disconnected from the transformer T for movement to practice the process of this invention at another time and another place.
  • a siphon breaker means may be installed at nozzle 68 and valve 70 connected to a siphon loop in line 10 as appropriate.
  • a transformer is connected to a single stage distillation unit substantially as schematically shown in Fig. 2.
  • the transformer T with the core W and preferably a perchloroethylene containing leaching fluid is placed on line.
  • the leaching fluid is withdrawn from transformer T through line 104, valve 106 and thence to line 110 through which it is introduced into the distillation column D having a single stage 112 with a still 114 to retain bottoms 115 containing perchloroethylene and PCB's configured to be heated by an electric coil 116 which may be, though not preferable, connected to level control sensors 130 by which the level of the bottoms 115 in the still 114 may be controlled by increasing or decreasing the temperature of the bottoms 115 through the heating coils 116.
  • Such control is preferably set manually and held substantially constant. The higher temperature, of course, would cause the distillation of larger amounts of perchloroethylene and thus lower the level of the bottoms 115 and increase the concentration of PCB's.
  • level control sensors 130 can be connected to the solenoid valve 106 to admit more leaching fluid when called for.
  • Reboiler heater 116 causes a vapor stream to form in the distillation column D which passes plate 112 where it enters a cooling zone, or condensing means, 117 cooled by the water or air cooled condenser C.
  • the condensate stream collects on tray 112 and is withdrawn as a liquid from the distillation column D through line 118, which is preferrably packed witha wire mesh, where it is thence stored in a polychloroethylene storage and make-up tank 119 before proceeding through pump 120 into line 124 through valve 126 and line 128 back to transformer T.
  • the distillation column D is also fitted with a drain 134 having a valve 132 for removal of PCB bottoms 115 for further processing or disposal. Also included is an overhead vapor line 140 equipped with a valve 142 in order to provide an optional separate removal for the vapors created during the operation of this experiment.
  • a transformer T2 is connected to a combination of two interconnected single stage distillation columns substantially as schematically shown.
  • the transformer T2 with the core W2 is filled with a leaching fluid F such as perchloroethylene.
  • the leaching fluid F is withdrawn from transformer T2 through nozzle 202 at or near the bottom of transformer T, line 204, valve 206 and loop
  • Distillation column D2 preferably has a single stage distillation zone in still 214 and is operated at substantially zero reflux except for such concentration as might occur in exit overhead line 218.
  • the leaching fluid F in first distillation column D2 is heated in still 214 through the introduction of heat, shown as coils 216 preferably electric or with steam or one of any other well known heating fluids as an alternative, to a temperature sufficient to boil the leaching fluid from the PCB's.
  • this temperature will be from about 120°C to about 180°C, more preferably from about 120°C to about 150°C.
  • the overhead stream produced from first distillation column D2 will preferably be substantially free of PCB's at later stages of transformer cleaning, more preferably about 2 ppm by weight PCB's or less.
  • the PCB concentration in the bottoms 215 should be kept below about 20% by weight, preferably below about 10% by weight, still more preferably below 5% by weight.
  • bottoms 215 must be periodically drained or, preferably, discharged to a second distillation column D2a, where the bottoms stream is further distilled, usually at a higher temperature (as detailed below), to remove a substantial portion of the remaining leaching fluid from the PCB's.
  • This leaching fluid is then condensed and recycled back to distillation column D2, while the remaining PCB's axe initially accumulated within the distillation column D2 and eventually discharged to a second distillation column D2a.
  • Level controller 230 may optionally actuate valve 206 to change the rate of flow from transformer T2 or heat coil 216 to raise the temperature of still 214 and reduce the volume of bottoms 215 by increased distillation until the PCB concentration in the bottom of D2 reaches about 20%, preferably about 10% or less, and more preferably about 5% or less. It is preferable to actuate valve 206 for the circulation of additional fluid from the transformer T2 to the first distillation unit D2. Other schemes for accomplishing basic control of D2 will be appreciated by one skilled in the art.
  • bottoms 215 are preferably drained through line 234, valve 232 and line 236 into a second distillation column D2a.
  • Distillation column D2a like distillation column D2, preferably has a single stage distillation zone and is operated as set forth above.
  • the bottoms 215 in distillation column D2a is heated in a still 214a through the introduction of heat, shown as coils 216a preferably electric or with steam or one of any other well known heating fluids as an alternative, to a temperature sufficient to boil a substantial amount of the leaching fluid from the PCB's.
  • this temperature will be from about 120°C to about 210°C, more preferably from about 150°C to about 180°C.
  • the leaching fluid is vaporized from the bottoms stream 215a to produce a PCB concentration of from about 70% to about 95%, more preferably from about 80% to about 95%, in the bottoms 215a. Such concentrations reduces the volume of waste for ultimate disposal to about one forth to one tenth of what it would be with only a single stage.
  • the level of bottoms 215a will be monitored and controlled by a controller (not shown) operating heater 216a or valve 232a.
  • the bottoms 215a rich in PCB's may be either accumulated throughout the cleaning period or removed periodically to purge the PCB's from distillation column D2a through line 234a, valve 232a and line 236a to storage and/or further disposal.
  • bottoms from D2 are fed to D2a through valve 232 and line 236 until the controller 230a signals that D2a is full through its high level switches (HLS).
  • HLS high level switches
  • Valve 232 is then closed and heat is applied to D2a to boil leaching fluid away from PCB's. This proceeds until the level of liquid in the bottom of second column D2a falls enough to trigger the low level switch
  • the controller optionally can open valve 232 to receive more fluid from first column D2 or temporarily turn off the heat source to second column D2a.
  • Second distillation zone D2a can be designed to accommodate up to about 50% PCB's and chlorinated benzenes (i.e., TCB solvent) preferably up to about 80% PCB's and chlorinated benzenes, and more preferably up to about 90%
  • the overhead stream produced by distillation column D2a exits through line 218a as a vapor and proceeds to a condensing means C2a, where the vapor is condensed into liquid through heat exchange, preferably in a finned heat exchanger exposed to atmospheric air for reducing the temperature of the overhead stream.
  • the condensate exits condenser C2a through line 220a and is recycled into the bottom of distillation column D2 wherein it commingles with bottoms 215 and fluid entering from line 210 for further treatment therein.
  • the overhead stream produced by distillation column D2 exits through line 218 as a vapor and proceeds to a condenser C2, where the vapor is condensed into liquid through heat exchange, preferably in a finned heat exchanger exposed to atmospheric air for reducing the temperature of the overhead stream.
  • the condensate exits condenser C2 through line 220 and valve 222 and proceeds through line 224 for return through valve 226 and nozzle 228 to the transformer T2.
  • leaching fluid make-up may be added, for example, through line 240, valve 242 and line 244 into line 224 and thus to transformer T2 as previously described.
  • Leaching fluid can additionally be removed, if desired, from line 220 through line 252, valve 250 and line 254.
  • the leaching fluid can be drained from line 210 through line 258, valve
  • a loop 208 is preferably installed between line 204 and 210, and a siphon breaker 272 is installed above fluid level at nozzle 268 and valve 270 (optional) in loop 208 which operators to open if fluid F drops below the limits of level controller 273.
  • Loop 208 is an arched section between lines 204 and 210, with the apex 209 of the arch being higher in elevation than the top of core W2 and below the surface of fluid F normally present in transformer T2.
  • the entrance of line 210 into first distillation zone D2 is usually below the level of fluid F in transformer T2 to provide gravity feed.
  • leaching fluid level drops in transformer T2 exposing the apex 209 of loop 208 to a liquid free void in transformer T2 a potential siphon is broken. This stops the draining of transformer T2 and protects the core W2.
  • the level of fluid in transformer T2 exceeds the level of the apex 209 the flow of fluid F again starts to the first distillation unit D2. Since transformers often have sediment which invades the leaching fluid F the siphon breaker is a protection against the consequences of valve
  • the second specific embodiment as depicted in Fig. 6 and discussed above provides several operational advantages.
  • the dual distillation zones provide the effectiveness of multistage distillation without the process complications attendant to such.
  • the apparatus of Fig. 6 requires no more than on/off process control, whereas a multistage unit would require substantially more and complex proportional or proportional/integral controls, as well as additional equipment in the form of reflux tanks, reflux pumps, flow monitors and controls. Many situations can arise during the operation of this equipment which would require an automatic pause or temporary shutdown of the equipment. Due to the simplified process control of the system of the preferred embodiment, these interruptions in service are easily handled by the on/off nature of the process control. Achievement of such control with a multistage unit is, as is well known by one skilled in the art, at best costly and complicated. EXAMPLE 1
  • Askarel a PCB containing dielectric fluid.
  • one transformer was treated by condensing perchloroethylene vapors on the core and walls with removal of the condensate to remove residual bulk Askarel.
  • the internals of the second transformer were sprayed with perchloroethylene leaching fluid (vapor) which were condensed and drained.
  • the third was cleaned of the bulk residual Askarel by simple liquid flushing with perchloroethylene.
  • the method of this invention was continued in its intermittent manner until it was determined that leaching rates for residual PCB's in the transformer was sufficiently low to permit reclassification. This required approximately five weeks of operation and the resulting curve of the cleaning the test transformers is shown in Fig. 3.
  • Fig. 4 is a plot of such leaching rate as determined upon the analysis of the leaching fluid and the length of time such fluid remained in the energized transformer. Even though the amount of time required to clean individual trasformers may vary widely, points plotted for other transformers as on Fig. 4 for the test transformers can be used to determine the minimum and maximum servicing times for a particular piece of equipment.
  • the leaching fluid may optimally be replaced with a permanent dielectric fluid and the reclassification test, as shown on Fig. 5 for one of the transformers reclassified in this experiment, performed. Accordingly from the foregoing it can be seen that the intermittent practice of the steps of this invention accomplish the result of reclassification as well as the continuous operation hereinbefore described. The operation described above was continued for six to nine weeks with the transformers energized to reduce the PCB leaching rate to a level acceptable for reclassification.
  • Fig. 3 is a composite of the data of all three tests run showing the approximate rate of removal of the residual
  • Fig. 4 is a plot of the combined data obtained from the practice of the method for the cleaning to the point of reclassification of each transformer showing the leaching rate of the PCB from the core as a function of energized transformer cleaning time.
  • Fig. 5 shows the PCB concentration of one transformer during the 90 day reclassifi cation after practice of the method to be well within the 50 ppm now allowed by the EPA for reclassification of the transformers. Even lower levels may be obtained as shown in Fig. 5 should EPA regulations become even more restrictive.
  • Table 1 shows results comparing a single stage processor (Fig. 1 or 2) without a second distillation zone and a first single stage distillation zone combined with a second bottom distillation zone as depicted in Fig. 6.
  • the combination includes the ability to concentrate PCB's in second bottoms D2a, stream, control PCB concentration in column D2 at desired range and ability to control PCB accumulation at less thand 2ppm in the holding tank for recycle to the first distillation zone.
  • a vessel was filled with perchloroethylene based leaching fluid.
  • an askarel containing 50% trichlorobenzene and 50% mixed PCB's was added in the amounts shown and at the times indicated in Table 1.
  • the first distillation unit D2 was configured to draw fluid from the simulated transformer periodically as fluid boiled, thereby lowering the liquid level in the still 214.
  • the temperature in the still 214 varied with the concentration of PCB's, ranging from about 121oC (minimal PCB content) to about 135 to 140°C (40% to 50% PCB's).
  • Condensed leaching fluid was accumulated in holding tank 119 (see Fig. 2) and recirculated to the transformer. As shown in Table 1, over a period of 10 days, regular increments of askarel were added to D2. Due to the boiling and clean recycle action of D2, the level of PCB's in the still 214 rose rapidly, leveling out when additions of askarel to the transformer were stopped and rising again when additions of askarels resumed.
  • the second single stage distillation unit D2a was connected to first distillation unit D2 and portions of the contents of the first still 214 were periodically fed to second distillation zone D2a where they varied with the concentration of PCB's, ranging from about 125°C (about 10%
  • PCB's PCB's
  • PCB's were accumulated in second distillation zone D2a and boiled fluids were recycled to the boiling chamber of first distillation zone D2. As shown in Table 1, immediately following the startup of second distillation zone D2a, the
  • PCB concentration of the boiling chamber in D2 begins to fall while PCB concentration of the still 214a begins to rise.
  • the decline in PCB concentration in the still 214 occurs despite the steady addition of PCB's to the transformer.
  • the concentration of PCB's in the still 214 falls, the residual PCB content of condensed fluid in the holding tank 119 rapidly falls to less than 2 ppm and remains there.
  • the concentration of PCB's in the still 214a rises rapidly.
  • the concentration of PCB's in the first distillation zone D2 falls to about 0.1% and all of the PCB's collect in the still 214a.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Emergency Management (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Toxicology (AREA)
  • Business, Economics & Management (AREA)
  • Organic Chemistry (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Processing Of Solid Wastes (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Transformer Cooling (AREA)
  • Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
  • Electrotherapy Devices (AREA)

Abstract

Un procédé et un appareil de nettoyage et de reclassification d'appareils électriques conçus pour être utilisés avec des fluides électrolytes au biphényle polychloré (PCB) peuvent être utilisés là où l'équipement à nettoyer est situé et pendant que ledit équipement est sous tension.
PCT/US1987/001830 1986-08-01 1987-07-30 Reclassification d'appareils electriques contamines par pcb Ceased WO1988000849A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR8707765A BR8707765A (pt) 1986-08-01 1987-07-30 Processo e aparelho para purificar aparelhos eletricos e transformadores,para reclassificacao,contaminados com bifenilas policloradas e laco condutor
DE19873779646 DE3779646T2 (de) 1986-08-01 1987-07-30 Wiedereingliederung mit pcb verunreinigter elektrischer apparate.
AT87905135T ATE76766T1 (de) 1986-08-01 1987-07-30 Wiedereingliederung mit pcb verunreinigter elektrischer apparate.
KR1019880700348A KR880701574A (ko) 1986-08-01 1988-04-01 Pcb에 오염된 전기장치의 재분류 방법 및 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US89161286A 1986-08-01 1986-08-01
US891,612 1986-08-01

Publications (1)

Publication Number Publication Date
WO1988000849A1 true WO1988000849A1 (fr) 1988-02-11

Family

ID=25398525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1987/001830 Ceased WO1988000849A1 (fr) 1986-08-01 1987-07-30 Reclassification d'appareils electriques contamines par pcb

Country Status (7)

Country Link
EP (1) EP0321469B1 (fr)
JP (1) JPH02501342A (fr)
KR (1) KR880701574A (fr)
AU (2) AU602347B2 (fr)
BR (1) BR8707765A (fr)
CA (1) CA1332140C (fr)
WO (1) WO1988000849A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9209587U1 (de) * 1992-07-17 1993-11-18 Nukem GmbH, 63755 Alzenau Vorrichtung zum Reinigen von mit PCB kontaminierten elektrischen Geräten
RU2215341C2 (ru) * 2001-04-25 2003-10-27 ОАО "Уралэлектротяжмаш" Трансформатор
RU2216807C2 (ru) * 2001-05-30 2003-11-20 ОАО "Уралэлектротяжмаш" Трансформатор

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4494139B2 (ja) * 2004-09-13 2010-06-30 三菱電機プラントエンジニアリング株式会社 油入電気機器の絶縁油処理方法および絶縁油処理装置
JP6017247B2 (ja) * 2012-09-27 2016-10-26 日本シーガテック株式会社 ポリ塩化ビフェニルに汚染された油が収容された変圧器の浄化方法
JP7082598B2 (ja) * 2019-09-13 2022-06-08 Ｊｆｅ環境テクノロジー株式会社 Ｐｃｂ汚染機器をクリーニングする方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0037280A1 (fr) * 1980-04-02 1981-10-07 Westinghouse Electric Corporation Diélectrique liquide pour transformateurs
US4299704A (en) * 1980-05-19 1981-11-10 General Electric Company Method for removing polychlorinated biphenyls from contaminated transformer dielectric liquid
US4353798A (en) * 1980-05-19 1982-10-12 General Electric Company Apparatus for removing polychlorinated biphenyls from contaminated transformer dielectric liquid
US4425949A (en) * 1981-02-03 1984-01-17 Diamond Shamrock Corporation Process for removing undesirable substances from electrical devices
EP0188698A2 (fr) * 1984-11-27 1986-07-30 Union Carbide Corporation Procédé de remplacement d'un agent réfrigérant contenant du PCB dans un appareil électrique d'induction par un agent réfrigérant essentiellement libre de PCB

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0037280A1 (fr) * 1980-04-02 1981-10-07 Westinghouse Electric Corporation Diélectrique liquide pour transformateurs
US4299704A (en) * 1980-05-19 1981-11-10 General Electric Company Method for removing polychlorinated biphenyls from contaminated transformer dielectric liquid
US4353798A (en) * 1980-05-19 1982-10-12 General Electric Company Apparatus for removing polychlorinated biphenyls from contaminated transformer dielectric liquid
US4425949A (en) * 1981-02-03 1984-01-17 Diamond Shamrock Corporation Process for removing undesirable substances from electrical devices
EP0188698A2 (fr) * 1984-11-27 1986-07-30 Union Carbide Corporation Procédé de remplacement d'un agent réfrigérant contenant du PCB dans un appareil électrique d'induction par un agent réfrigérant essentiellement libre de PCB

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9209587U1 (de) * 1992-07-17 1993-11-18 Nukem GmbH, 63755 Alzenau Vorrichtung zum Reinigen von mit PCB kontaminierten elektrischen Geräten
WO1994002209A1 (fr) * 1992-07-17 1994-02-03 Nukem Gmbh Procede et dispositif de nettoyage d'appareils electriques contamines avec du biphenylene surchlore
RU2215341C2 (ru) * 2001-04-25 2003-10-27 ОАО "Уралэлектротяжмаш" Трансформатор
RU2216807C2 (ru) * 2001-05-30 2003-11-20 ОАО "Уралэлектротяжмаш" Трансформатор

Also Published As

Publication number Publication date
EP0321469B1 (fr) 1992-06-03
AU7784787A (en) 1988-02-24
JPH02501342A (ja) 1990-05-10
BR8707765A (pt) 1989-08-15
EP0321469A1 (fr) 1989-06-28
KR880701574A (ko) 1988-11-03
AU602347B2 (en) 1990-10-11
AU7001591A (en) 1991-05-16
CA1332140C (fr) 1994-09-27

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