JP2008229473A - Method of removing pcb in trace pcb contaminated electric equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of removing PCB in trace PCB contaminated electric equipment capable of performing removal treatment safely and economically while grasping an inner state of the equipment when extracting and removing PCB in the electric equipment into a solvent. <P>SOLUTION: In the method of removing PCB in trace PCB contaminated electric equipment, insulating oil is pulled out from the electric equipment into which the insulating oil containing PCB is filled, thereafter, a hydrocarbon solvent is injected, the PCB remaining in the electric equipment is dissolved into the hydrocarbon solvent and the hydrocarbon solvent in which the PCB is dissolved is discharged, wherein circumstances of removal treatment in the electric equipment is calculated by the calculating formula (initial oil PCB concentration × weight × residual oil rate (oil attachment rate) × cleaning efficiency) and the removal treatment is advanced while confirming the calculation result. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a PCB removal method for removing a PCB by cleaning the inside of the electrical device without disassembling a PCB-contaminated electrical device filled with insulating oil containing PCB.

  In 2001, the “Special Measures Law for Promotion of Proper Treatment of Polychlorinated Biphenyl Waste” was enacted, and PCB contaminants such as transformers and capacitors contaminated by PCB and PCB were made harmless by 2016 It is supposed to be processed.

  At present, wide-area treatment facilities for detoxifying PCBs and PCB contaminants have been constructed or planned in five locations nationwide, and some facilities are already in operation, with the aim of completing the treatment by 2016.

  PCBs and PCB contaminants that are processed at these wide-area treatment facilities were discontinued by 1972 and were prohibited from being manufactured, imported, or used by 1979, and have been stored for a long time since then. The high-concentration PCB, the high-concentration PCB-containing transformer or the capacitor, and the like are the objects.

  In addition, the detoxification treatment technology has been established for PCBs, such as chemical treatment by dechlorination using metallic sodium or alkali, and for PCB contaminants, technology for removing PCBs by the cleaning method or vacuum heating method has been established. It has been adopted as the main detoxification technology in wide-area treatment facilities.

  On the other hand, the Ministry of Economy, Trade and Industry and the Japan Electrical Manufacturers' Association (hereinafter referred to as JEMA) announced in July 2002 that “the possibility of mixing a small amount of PCB into transformers using new oil” There was a press announcement stating that the investigation of the cause and the identification of the equipment were instructed, and it was found that there was an electrical equipment in which a small amount of PCB was mixed for some reason in the insulating oil of oil-filled electrical equipment such as transformer It was.

  According to research by JEMA and others, PCB-contaminated electrical equipment mixed with trace amounts of PCBs in the 0.5 to tens of ppm level is extremely widespread, and one theory includes millions of units including large-capacity transformers. Estimated to be close.

  In response to this problem, the “Low-Concentration PCB Contamination Countermeasures Review Committee” has been established at the national level by experts, and the investigation of the cause and countermeasures have been discussed in this committee. It will be launched.

  However, such PCB-contaminated electrical equipment in which a small amount of PCB is mixed in insulating oil for some reason is processed in a wide-area processing facility for high-concentration PCB and transformers or capacitors containing high-concentration PCB. I do not assume that. For this reason, it is difficult to process PCB contaminated electrical equipment mixed with a small amount of PCB in a wide-area processing facility mainly from the viewpoint of processing capacity or economy, and it is an urgent task to establish processing technology in Japan. Yes.

  A typical example in Canada and the United States regarding the treatment of such a PCB contaminated transformer filled with insulating oil containing PCB will be described below.

  For example, Non-Patent Document 1 describes the MOF decontamination method (Ontario Ministry of Environment) (method of the Ontario Environment Agency). The outline of the method is “No. 2” after removing the insulating oil containing PCB. This is a process in which a cleaning solvent such as “fuel oil” or “trichlorethylene” is filled and allowed to stand for immersion, and then the cleaning solvent is removed, followed by a clean cleaning solvent and decontamination.

  Further, in Non-Patent Document 2, retrofilling (reverse filling) with a cleaning solvent (also serving as insulating oil) is desirable for the treatment of PCB-contaminated transformers, and a combination of flushing of PCB-contaminated transformers and cleaning solvent recovery is combined. An automation system is applied.

  In addition, there is a method in which the transformer is used by flushing the inside of the transformer with a special cleaning solvent (also serving as insulating oil), and finally the replacement with silicone oil. By this retrofill, the PCB concentration in the PCB alternative oil (mainly silicone oil is used) is reclassified to 50 ppm or less (PCB regulation value in the United States: 50 ppm or more).

  In this way, when processing and reusing, the transformer is not disassembled, so that only the liquid sample can be analyzed. Since the transformer is a complicated assembly structure composed of various members, it is difficult to elute PCBs uniformly from all the members, and the variation between the members increases with each elution process.

Immediately after the treatment, the variation between the members is remarkable, so that even if the liquid is analyzed, the PCB is not detected and remains in the member. For this reason, in the United States, a standard is set for values measured after three months have passed since processing.
S. Hugh Hawthorne, “Solvent decontamination of PCB electrical equipment”, Ontario Hydro Research Division, CH1740-0 / 82 / 0000-0074 $ 0.75, Conf. Rec. Ind. Commer. Power Syst. Tech. Conf. 1982, pp 74 -78 Yukio Yasufuku “Viewing the Current State of PCB Processing Technology in the United States”, Technical Journal “OHM” October 1988, pp. 76-80

  Considering the fact that processing in a wide-area processing facility is difficult in Japan, the above-mentioned overseas “cleaning without dismantling on site” basically serves as a guideline for processing technology in Japan.

  The present invention has been made in consideration of the above-mentioned points, and when extracting and removing PCBs in electrical equipment as a solvent, it is possible to proceed with the removal process safely and economically while grasping the internal state of the equipment. An object of the present invention is to provide a PCB removal method for a small amount of PCB-contaminated electrical equipment.

In order to achieve the above object, in the present invention,
After the insulating oil is extracted from the electrical equipment filled with insulating oil containing PCB, a hydrocarbon solvent is injected, and the PCB remaining in the electrical equipment is dissolved and discharged in the hydrocarbon solvent. In the PCB removal method of PCB-contaminated electrical equipment to be performed,
The following calculation formula,
PCB concentration in initial oil × weight × residual oil rate (oil adhesion rate) × cleaning efficiency Here, PCB concentration in initial oil: PCB concentration in untreated oil
Weight: Weight of the entire transformer or components
Oil adhesion rate: Oil adhesion rate determined by each component and situation (impregnated material)
(Amount of oil that permeates into 1 g)
Cleaning efficiency: Calculate the status of the removal process in the electrical equipment based on the dissolution rate of PCB per unit cleaning.
PCB removal method for PCB-contaminated electrical equipment, characterized in that the removal process proceeds while confirming the calculation result,
Is to provide.

  As described above, according to the present invention, PCBs can be efficiently removed by cleaning an electrical device mixed with a trace amount of PCB for some reason while grasping the internal state by a basic process. And since the electric equipment is not disassembled locally, it is excellent in economic efficiency and can be safely washed without special temperature and pressure at the time of washing.

  When the PCB-contaminated electrical equipment mixed with a trace amount of PCB for some reason, which is a processing target of the present invention, is arranged with respect to the transformer, (a) the PCB concentration in the insulating oil injected into the transformer is 0.5 to several tens. It is in ppm level. (b) Many transformers cannot be transported without being dismantled. (c) The number of transformers is estimated to be close to 1 million.

  In the present invention, in consideration of these characteristics and the processing at the above-mentioned wide-area processing facility, it is possible to remove the PCB from the transformer by using a processing device that can be moved at the local installation location or the local storage location. After the insulating oil is removed, the inside of the transformer is washed to remove PCB.

  Here, the state after processing is obtained by calculation using a predetermined calculation formula in consideration of the elution rate depending on the internal configuration of the transformer and processing conditions (solvent temperature, processing time, etc.). Basically, the amount of PCB after processing is obtained by subtracting the amount of PCB eluted by processing from the initial amount of PCB.

  Details of how to find it will be described below, taking a transformer as an example.

  First, the initial amount of PCB before being removed, that is, the amount of PCB can be determined from the amount of oil and the PCB concentration in the liquid. This PCB distribution state can be determined from the weight and impregnation rate of each member constituting the transformer.

When the insulating oil mixed with a small amount of PCB is extracted, the oil remaining in the transformer is
(1) Attached to the surface of a non-impregnated material such as metal,
(2) What is impregnated in an impregnated material such as paper,
(3) What remains in the bottom of the container or structural gaps,
It is divided into three types.

  When the solvent is injected after oil removal, the degree of elution of the residual oil varies depending on the type and configuration of the impregnated (or adhered) material. This elution degree is also related to the conditions of elution treatment, and taking these together, obtain the final value of the treatment by a known value or a measurement value obtained by measurement as necessary, and obtain by calculation using that value. be able to.

  In this way, by combining the removal process and the calculation by a predetermined formula, it is possible to grasp the internal state after the removal process of the transformer without disassembling and separating the transformer. By not disassembling and separating, it is economical because the equipment and work related to them are unnecessary, and if the removal process is performed in the same way as maintenance with the transformer connected to the power transmission and distribution line, Continuous use is also possible.

  When reusing a transformer, it is necessary to inspect the influence of the solvent on the transformer in advance by a standard test performed on the transformer insulating oil, and to inject the insulating oil so that the concentration does not become a problem. This mixing amount can also be obtained in the above calculation.

  The PCB concentration imbalance due to the components and the like caused by the treatment is alleviated with the passage of time when left in a state immersed in the liquid, and is brought into an equilibrium state after a sufficient amount of time has passed.

  The parameters required for this calculation are divided into several types depending on the type of transformer. This is because there is a material composition ratio that varies greatly depending on the type of transformer.

  In addition, some of the parameters used for the calculation vary depending on the capacity of the target transformer. For example, a transformer container whose weight ratio increases as the capacity increases corresponds to this.

  Next, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a process diagram showing a processing process according to the present invention, and FIG. 2 is an explanatory diagram showing an apparatus configuration used in the present invention. Hereinafter, each step of the processing process will be described with reference to FIG. 1, and devices used for each process will be described with reference to FIG. 2.

  As a treatment process, an extraction pipe 14, an extraction pump 6, and an oil storage tank 7 are connected to the oil discharge valve 4 of the PCB contamination transformer 1, and the extraction pump 6 is activated to insulate the PCB from the PCB contamination transformer 1. Oil 2 is extracted (FIG. 1, step S1). The insulating oil 2 including the drained PCB is stored in the oil storage tank 7.

  At this time, in order to improve the removal efficiency of the PCB, it is effective to increase the oil removal rate from the PCB contamination transformer 1. As the method, the oil removal nozzle 9 is removed from the hand hole 5 of the PCB contamination transformer 1 after the oil removal. The remaining oil is inserted and recovered in the waste oil storage tank 11 in the same manner as described above (FIG. 1, step S2). The insulating oil 2 including PCB recovered by the oil removal is separately carried into an oil drainage treatment facility and detoxified.

  Next, the cleaning solvent injection pipe 15, the cleaning solvent storage tank 12, the heating circulation device 11, and the circulation pump 10 are connected to the PCB contamination transformer 1, and the exhaust pipe 17 and the exhaust treatment device 18 are connected to the circulation pump. 10 is started and the cleaning solvent 13 in the solvent storage tank 12 is injected into the transformer 1 contaminated with PCB (FIG. 1, step S3), and the solvent is immersed in the circulation or the pump is stopped (FIG. 1, step S4). The waste oil storage tank 7 and the cleaning solvent storage tank 12 may be configured to be connected to the distillation apparatus 19.

  The exhaust gas released at this time passes through the exhaust treatment device 18 composed of activated carbon or photocatalyst in the exhaust treatment device 18 to decompose and remove PCBs in the exhaust gas to prevent release to the environment. . However, the exhaust pipe 17 and the exhaust treatment device 18 may be omitted.

  Here, the solvent 13 used for cleaning employs a petroleum solvent. Although these cleaning solvents 10 are classified as dangerous materials, it is known that they have low toxicity, excellent solubility and stability, are easy to handle, and have excellent cleaning effects from empirical data. good. And since it can wash | clean at the temperature below flash point and atmospheric pressure state, it is excellent also in safety.

  Next, after completion of the above-described circulation cleaning, the extraction pump 6 is activated to recover the cleaning solvent 13 from the PCB-contaminated transformer 1 to the oil storage tank 7 and store it (FIG. 1, step S5).

  The above-described steps from solvent injection and cleaning to oil removal are repeated several times (FIG. 1, steps S3 to S5), and the cleaning effect of the member 3 in the PCB contaminated transformer 1 can be further enhanced.

  When the transformer 1 is continuously used, humidification circulation / drying, degassing oiling (step S6), insulation oil compatibility verification (step S7), and transformer modification shown in steps S6 to S9 in FIG. The process proceeds to performance verification (step S8) and operation (step S9).

  The basic process for removing PCB and the system configuration can enhance the cleaning effect, and the PCB in the member 3 can be efficiently recovered and removed in the cleaning solvent 13.

  The state in which the PCB is removed as described above is normally grasped by disassembling and analyzing, but in the present invention, this is grasped by calculation. This calculation will be described below.

  FIG. 3 is an explanatory diagram showing changes in the internal state of the transformer accompanying the processing according to the present invention. In the transformer 1 in which a small amount of PCB to be mixed is mixed, the PCB concentration in the oil in the transformer 1 is uniform (state 101) before the removal process. When the oil is extracted and the state 102 is obtained, the trace amount of PCB mixed oil is left in each component.

  Here, when the solvent S is injected as shown in the state 103, the PCB gradually melts to the state 104. When the solvent S containing the dissolved PCB is drained, the state 105 is reached, and the amount of PCB inside the transformer 1 can be reduced by repeating the lubrication-elution-oil removal.

  If the transformer is to be used continuously after the removal process, the upper limit of the concentration of contamination that can satisfy the specified value required for the insulating oil of the transformer for the solvent used in the removal process must be determined in advance by testing. The solvent S is removed until the upper limit is reached. Thereafter, insulating oil is injected into the transformer 1. If a sufficiently long time has passed in this state, the PCB concentration of the oil in the transformer 1 reaches equilibrium again and the PCB is uniformly removed (state 106).

  On the other hand, when removing a transformer, a process is complete | finished in the state which drained.

  FIG. 4 is a detailed view of the inside of the transformer 1 in the state 105 of FIG. Inside the transformer 1 is a member 3 in which an insulator such as paper and a metal such as copper are laminated (for example, a core in which a metal such as a coil 3a and an iron core 3b is laminated, and many other things such as wood and press board) Members), each containing oil at a different rate for each type.

  For this reason, the proportion of PCBs eluted by processing varies depending on the type and structure of the member, and when oil is removed from the oil discharge valve 4 after the processing is repeated, the concentration can be distributed. Therefore, when the residual oil rate relating to the oil 2a remaining at the bottom of the container, the oil adhesion rate relating to the oil 2b adhering to the inner surface of the container, and the cleaning efficiency by the members are introduced and calculated, the state inside the transformer accompanying the processing can be obtained. it can.

That is, the following residual concentration formula:
PCB concentration in initial oil × weight × residual oil rate (oil adhesion rate) × cleaning efficiency Here, PCB concentration in initial oil: PCB concentration in untreated oil
Weight: Weight of the entire transformer or components
Oil adhesion rate: Oil adhesion rate determined by each member and situation (impregnated material 1
amount of oil soaking into g)
Washing efficiency: Calculation is based on the dissolution rate of PCB per simple wash.

  By the calculation based on the residual concentration calculation formula, the concentration of the PCB that finally remains can be obtained. Since it is possible to determine the progress of the process, it can be used as a guide for the process.

  These processes are almost the same as normal oil replacement maintenance for transformers and the like, and by performing this simultaneously with the maintenance, it is possible to reduce the burden on the operating transformer.

(Calculation example)
Next, taking a transformer as an example of specific equipment, the PCB concentration is calculated using the above-described residual concentration calculation formula.

1. Transformer target total weight: 21500kg
Oil amount: 6600L
Contents weight: 10500kg
Initial PCB concentration in oil; 35 mg / kg

2. Processing conditions Cleaning solvent: HC370 (manufactured by Tosoh Corporation)
Washing time: 24 hours (per time)
Cleaning temperature: 60 degrees (during cleaning liquid circulation)

3. Calculation of member composition ratio The member composition ratio is obtained as shown in Table 1 from the measurement results obtained so far.

これを元に上記残留濃度計算式により油中ＰＣＢ濃度を計算すると、残留ＰＣＢ量は表３のようになる。

4). Calculation of the amount of residual PCB after processing The amount of PCB remaining after processing is the same as in 2. above. In the case of the above processing conditions, it is obtained as shown in Table 2.

Based on this, when the PCB concentration in oil is calculated by the above-described residual concentration calculation formula, the amount of residual PCB is as shown in Table 3.

5. Determination of the number of treatments From Table 3, it can be seen that the number of treatments is less than or equal to the target of 0.5.

(Other processing)
As described above, as one of the residual PCBs in the equipment, there is oil remaining on the bottom of the container after the oil is removed, and by reducing this, the remaining amount of PCB can be reduced. The valve for oil removal is often provided at the lower part of the device, but since it is not provided on the bottom surface, there is a little remaining amount. The remaining amount can be reduced by inserting the nozzle and collecting it.

  Through the above treatment, a mixture of insulating oil containing PCB and solvent is recovered. When this mixture is separated by distillation, it can be separated into only a solvent and an insulating oil containing PCB. Insulating oil and PCB are transported to the detoxification facility without separating them. For this reason, the PCB does not become darker than the initial concentration, and since the concentrated PCB is not handled, the safety is increased.

  In order to reuse the transformer after the treatment, the insulating oil used for the transformer is injected after removing the solvent. The effect of the solvent on the transformer is examined by a predetermined test, and the cleaning solvent is removed until a problem-free level is reached. As a method of removing, there is oil removal or co-washing.

  Since the solvent used for the treatment is separated from the PCB and reused, it is necessary that the boiling range does not overlap with the PCB.

  In order to reuse the transformer, it is necessary to keep the temperature rise inside the transformer within the specified value. Further, safety is enhanced by washing at a temperature not exceeding the flash point of the solvent. For this reason, the temperature during cleaning is set to 80 degrees or less.

The flowchart which shows the basic process of PCB removal to which this invention is applied. The figure which shows the structure of the transformer which is the application object of the process shown in FIG. 1, and its related system. The schematic diagram showing the state change inside a transformer accompanying a PCB removal process. The figure which shows the distribution state of PCB inside a transformer immediately after a removal process.

Explanation of symbols

1 ... PCB contaminated transformer 2 ... Insulating oil containing PCB 3 ... Transformer internal components 4 ... Oil drain valve 5 ... Hand hole 6 ... Extraction Pump 7... Oil storage tank 8... Oil or waste solvent 9 .. Oil removal nozzle 10. Circulation pump 11. Solvent 14 ... Extraction piping 15 ... Cleaning solvent injection piping 16 ... Cleaning solvent circulation piping 17 ... Vacuum exhaust piping 18 ... Exhaust treatment device 19 ... Initial state 20 of transformer ... The state in which the initial oil is drained 21 ... the petroleum solvent 22 ... the state in which the solvent is injected 23 ... the solvent in which the PCB is eluted 24 ... the state in which the PCB is eluted in the solvent 25 ... the PCB is eluted The state in which the solvent was removed 26 ... PCB dissolved in each member was eluted and homogenized State 27 ... Haiyuben 28 ... coil 29 ... core 30 ... container resid 31 oil adhered to ... vessel wall

Claims (7)

After the insulating oil is extracted from the electrical equipment filled with insulating oil containing PCB, a hydrocarbon solvent is injected, and the PCB remaining in the electrical equipment is dissolved in the hydrocarbon solvent and discharged. In the PCB removal method of PCB-contaminated electrical equipment to be performed,
The following calculation formula,
PCB concentration in initial oil × weight × residual oil rate (oil adhesion rate) × cleaning efficiency Here, PCB concentration in initial oil: PCB concentration in untreated oil
Weight: Weight of the entire transformer or components
Oil adhesion rate: Oil adhesion rate determined by each member and situation (impregnated material)
(Amount of oil that permeates into 1 g)
Cleaning efficiency: Calculate the status of the removal process in the electrical equipment by the PCB elution rate per unit cleaning.
A PCB removal method for PCB-contaminated electrical equipment, wherein the removal process is performed while checking the calculation result. In the PCB removal method of the PCB contaminated electrical equipment according to claim 1,
In the calculation formula, use the configuration of the electrical equipment and the dissolution rate associated with the processing conditions,
A PCB removal method for PCB-contaminated electrical equipment, wherein the number of cleanings is changed by making a minute change depending on the type and capacity of the electrical equipment. In the PCB removal method of the PCB contaminated electrical equipment according to claim 1,
PCB removal of PCB-contaminated electrical equipment characterized in that, during the removal process, the PCB concentration in the washing liquid after washing is measured every predetermined number of washing times, and compared with the calculation result and fed back to the removal process Method. In the PCB removal method of the PCB contaminated electrical equipment according to claim 1,
The cleaning solvent used in the removal process is separated from the mixture of insulating oil and PCB and reused, and the insulating oil and PCB are not separated during this separation. PCB removal for PCB-contaminated electrical equipment Method. In the PCB removal method of the PCB contamination electric equipment according to claim 1,
When the electrical equipment is to be used continuously after removal treatment, the upper limit value of the mixing concentration that can satisfy the specified value required for the insulating oil of the electrical equipment for the solvent used in the removal treatment is obtained in advance by a test. ,
The cleaning solvent is removed until the upper limit value is reached or less. A PCB removal method for PCB-contaminated electrical equipment. In the PCB removal method of the PCB contaminated electrical equipment according to claim 1,
The method for removing PCBs from PCB-contaminated electrical equipment, wherein the hydrocarbon solvent has a boiling point of 250 degrees or less. In the PCB removal method of the PCB contamination electric equipment according to claim 1,
A PCB removal method for PCB-contaminated electrical equipment, wherein the solvent is heated to 80 ° C. or less and circulated.

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