JP2015202455A - Ending determination method of washing processing of pcb contaminated equipment, completion determination method of pcb detoxification processing by washing and estimation method of pcb concentration of washing liquid after washing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an estimation method of a PCB concentration of washing liquid after washing which can estimate PCB concentration of washing liquid after washing before washing PCB contaminated equipment with washing liquid irrespective of specification and dimensions of the PCB contaminated equipment and has versatility, and to provide a method of determining the completion of washing processing according to the estimation method and determining the completion of PCB detoxification processing by washing.SOLUTION: A method of determining the ending of washing processing and the completion of PCB detoxification processing from PCB concentration of washing liquid when washing PCB contaminated equipment which fills insulation oil containing polychlorobiphenyl (PCB) therein and is contaminated with PCB by means of washing liquid is provided. Further, in relation to a method for estimating PCB concentration of the washing liquid before washing, an estimation method of PCB concentration of the washing liquid after washing for determining PCB estimation concentration of washing liquid after washing according to a prescribed numerical equation from the PCB concentration of the insulation oil before washing the PCB contaminated equipment, a name plate weight of the PCB contaminated equipment and a name plate oil quantity of the PCB contaminated equipment is provided.

Description

  The present invention relates to a method for determining the end of a cleaning process for a PCB-contaminated device, a method for determining the completion of a PCB detoxification process by cleaning, and a method for predicting the PCB concentration of a cleaning liquid after cleaning.

  In July 2002, a small amount of PCB was detected in the insulating oil of heavy electrical equipment such as a transformer that should not use polychlorinated biphenyl (PCB). Although the PCB concentration is very small (ppm order), there are a large number of PCB-contaminated devices suspected of PCB contamination, and it is predicted that there will be an enormous number of about 6 million units. Therefore, realization of safe and economical processing of PCB contaminated equipment is strongly desired.

The national government established the “Low Concentration PCB Contamination Countermeasures Review Committee” in 2003 and began studying to solve the problem. In 2009, the Central Environmental Council, Waste and Recycling Subcommittee. In the “Special Committee on Disposal of Disposal Equipment”, the results of examination of disposal measures for waste electrical equipment mixed with trace amounts of PCB were compiled. As the main point, we will promote the incineration demonstration test at the incineration facility, and the technical examination and processing of the method to remove the PCB by replacing the insulating oil of electrical equipment etc. in the storage place and applying the power for a certain period, etc. It is mentioned. In response to this, the Ministry of the Environment has proceeded with incineration demonstration tests, and the introduction of a detoxification treatment certification system by the Minister of the Environment has begun to install facilities for detoxifying PCB contaminants by incineration.
On the other hand, verification of new PCB removal technology has not yet started as a country. The disposal period for PCB waste, which has been studied by the “Examination Committee for Promotion of Proper Treatment of PCB Waste” since 2011, is the “Special Measures Law Enforcement on Promotion of Proper Treatment of Polychlorinated Biphenyl Waste” The cabinet was decided as a “decree to revise part of the decree”, and the period of disposal of PCB waste by businesses was March 31, 39. Since PCB waste disposal deadlines have become clear, verification of new PCB removal technologies and institutional considerations are urgent issues.

  As a result of intensive studies to solve the above problems, the applicant of the present application has removed PCB contaminated oil and replaced it with PCB-free cleaning oil as an economical and safe detoxification treatment technology for trace PCB contaminated transformers. Subsequently, the forced forced circulation cleaning for cleaning the trace PCB-contaminated transformer with PCB-free cleaning oil and the self-charging natural circulation cleaning have already been proposed (see Patent Documents 1 and 2).

In the heating forced circulation cleaning, the elution of PCB from the internal member to the cleaning oil is promoted by the heating circulation of the cleaning oil from the tests using the small transformer and the medium transformer so far. The principle of being able to clean the parts until they meet the PCB detoxification criteria has been demonstrated.
In the electric charging natural circulation cleaning, the elution of PCB from the internal member to the cleaning oil is promoted by the electric power from the tests using the small transformer and the medium size transformer so far. The principle of cleaning until the detoxification treatment standard is satisfied has been proven.
Regarding these cleaning technologies, it is possible to clean even a relatively high PCB concentration of contaminated equipment by repeating the cycle of cleaning for a certain period of time following replacement of the contaminated oil with cleaning oil, as a trace PCB contaminated equipment. It is shown.

  In addition, the heat forced circulation cleaning and the electricity-charging natural circulation cleaning were demonstrated for a large amount of PCB-mixed large transformer at the actual storage or installation (use) location. As a result, in addition to draining insulating oil contaminated with PCB from PCB-contaminated equipment, injecting cleaning liquid, heating forced circulation cleaning with a mobile cleaning device for a certain period of time, or charging natural circulation cleaning by commercial operation, draining of cleaning liquid Demonstrating that it is possible to remove PCBs until they are less than the contamination standard in the corresponding PCB detoxification process for containers and internal components that constitute PCB contamination equipment without affecting the surrounding environment by operating the liquid. It was done.

On the other hand, in practical use of the heating forced circulation cleaning and the electrical charging natural circulation cleaning, it is appropriate and efficient that containers and internal members constituting the PCB-contaminated equipment satisfy the corresponding PCB detoxification treatment standards after cleaning. It is important to develop a means of confirmation.
At present, after the cleaning, a verification analysis of components such as metal, paper, and wood constituting the PCB-contaminated equipment is performed to confirm that the PCB detoxification processing standard is satisfied. However, it is not feasible to collect internal members for each device and perform a verification analysis for a small amount of PCB-contaminated devices that are expected to handle a huge number of units of about 6 million units. Not only will efficiency and economy be reduced, but the processing period will be lengthened. Therefore, means for efficiently determining that the standard for PCB detoxification processing is satisfied is indispensable for solving the problem.

  For this purpose, the end of the cleaning process of the PCB contaminated equipment and the completion of the PCB detoxification process of the PCB contaminated equipment after the cleaning are simply and practically performed according to some index in the cleaning process of the PCB contaminated equipment contaminated with the PCB. A method of judging is needed. Therefore, in the present invention, attention is paid to the PCB concentration of the cleaning liquid as a determination index. That is, when the PCB concentration of the cleaning solution after cleaning is predicted before cleaning, and the predicted concentration does not exceed the set control concentration, the PCB contamination device after cleaning is rendered harmless at the same time as the cleaning processing of the PCB contamination device is completed. It was found that the completion of the treatment can be determined. Therefore, regardless of the specifications and size of the PCB contaminated equipment, it is possible to predict the PCB concentration of the cleaning liquid after cleaning before cleaning, and that the PCB contaminated equipment after cleaning satisfies the PCB detoxification standard. It is necessary to show in

On the other hand, in the cleaning of PCB contaminated equipment, a calculation method for estimating the amount of PCB remaining inside the PCB contaminated equipment after cleaning has been studied. For example, in Patent Document 3, a PCB-contaminated transformer is obtained by calculating a state after processing by a calculation using a predetermined calculation formula in consideration of an elution rate depending on a configuration inside the transformer and processing conditions, and an initial PCB amount. A method has been proposed in which the amount of PCB after processing is determined by subtracting the amount of PCB eluted from the processing. This proposed method can be used to estimate the degree of PCB removal in the cleaning process. However, since the relative relationship between the degree of PCB removal as a whole of the PCB-contaminated equipment and the PCB concentration of the cleaning liquid is unclear as a matter of fact, after cleaning the PCB-contaminated equipment with the cleaning liquid, The PCB concentration of the cleaning liquid is not known as an index for “determining the end”. Similarly, since the relative relationship between the degree of PCB removal as a whole of the PCB-contaminated equipment, the degree of PCB removal of the containers and internal members of the PCB-contaminated equipment, and the PCB concentration of the cleaning liquid is unclear, “PCB by Cleaning The PCB concentration of the cleaning liquid is not known as an indicator of “determination of detoxification treatment”.
Therefore, the proposed method is merely a method for removing the PCB by calculating the amount of PCB after cleaning, and the PCB concentration of the cleaning solution after general cleaning that does not depend on the specification or size of the PCB-contaminated transformer. It is not something to be predicted. “After the PCB-contaminated equipment is cleaned with the cleaning liquid, the end of the cleaning process is determined from the PCB concentration of the cleaning liquid” and “the determination of the PCB detoxification process by the cleaning” cannot be achieved. It is.

Japanese Patent No. 4889557 Japanese Patent No. 5436889 Japanese Patent No. 4898507

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is versatile enough to determine the completion of the PCB detoxification process by cleaning at the same time as the completion of the cleaning process of the PCB contaminated apparatus, regardless of the specification and size of the PCB contaminated apparatus contaminated with PCB. It is an object of the present invention to provide a versatile method capable of predicting the PCB concentration of the cleaning liquid after cleaning before cleaning the PCB-contaminated equipment with the cleaning liquid in order to support and realize the method. To do.

Means for solving the above-described problems are as follows. That is,
In the first embodiment, the method for determining the completion of the cleaning process for PCB-contaminated equipment according to the present invention, after washing the PCB-contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with the cleaning liquid, The end of the cleaning process is determined from the PCB concentration of the cleaning liquid.

  In the first embodiment, the method for determining the completion of PCB detoxification treatment by washing according to the present invention, after washing PCB contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with washing liquid, Completion of the PCB detoxification process is determined from the PCB concentration of the cleaning liquid.

The method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention is that the PCB of the cleaning liquid after cleaning is cleaned before the PCB-contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB is cleaned with the cleaning liquid. A method for predicting concentration,
From the PCB concentration of the insulating oil before cleaning the PCB-contaminated equipment, the nameplate weight of the PCB-contaminated equipment, and the amount of nameplate oil of the PCB-contaminated equipment, the predicted PCB concentration of the cleaning liquid after cleaning is obtained by the following Equation 3. And
[Formula 3]
PCB predicted concentration of cleaning solution after cleaning =
[(Internal member coefficient x Name plate weight x Internal member oil content coefficient x PCB concentration of insulating oil before cleaning) + (Name plate oil amount ^2/3 x Container residual oil coefficient x PCB concentration of insulating oil before washing)] / (Name plate (Oil quantity x Insulating oil specific gravity)
However, in said Numerical formula 3, the said nameplate weight represents the total weight of the PCB contamination apparatus containing the insulating oil described in the nameplate of the said PCB contamination apparatus. The amount of the nameplate oil is the total amount of oil described on the nameplate of the PCB-contaminated equipment, and is set to 2/3 power in consideration of the contact area of the oil for calculating the amount of adhesion to the container wall surface and the container bottom surface. The internal member oil impregnation coefficient represents a coefficient for obtaining the oil content in the internal member of the PCB-contaminated equipment. The internal member coefficient represents a coefficient for obtaining the internal member weight from the nameplate weight. The container residual oil coefficient represents a coefficient for calculating the amount of insulating oil remaining on the container wall surface and the container bottom surface of the PCB-contaminated equipment after the insulating oil is extracted from the PCB-contaminated equipment.

  In the second embodiment, the method for determining the completion of the cleaning process for the PCB-contaminated equipment according to the present invention is based on the predicted PCB concentration of the cleaning liquid after the cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after the cleaning according to the present invention. Determine the end of.

  In the second embodiment, the method for determining the completion of PCB detoxification by cleaning according to the present invention is the PCB harmless from the predicted PCB concentration of the cleaning liquid after cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention. The completion of the conversion process is determined.

  According to the present invention, the above-described problems can be solved and the object can be achieved, and before the PCB-contaminated equipment is cleaned with a cleaning liquid, regardless of the specification and size of the PCB-contaminated equipment contaminated with PCB. The PCB concentration of the cleaning liquid after the cleaning that can predict the PCB concentration of the cleaning liquid after cleaning at the same time, and the PCB decontamination by the cleaning simultaneously with the completion of the cleaning process of the PCB contaminated equipment by the prediction method A method for determining completion of processing can be provided.

FIG. 1 is a schematic diagram showing an example of the concept of the method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention. FIG. 2 is a graph showing the relationship between the actually measured PCB concentration of the cleaning oil and the predicted PCB predicted concentration of the cleaning oil. FIG. 3A is a graph showing the relationship between the actually measured PCB concentration of the insulating oil before cleaning (base oil PCB concentration) and the predicted predicted predicted PCB concentration of the cleaning oil. FIG. 3B is a partially enlarged view of FIG. 3A. FIG. 4 is a drawing showing an example of the structure of an outer iron core having a wound iron core and the structure of a copper coil. FIG. 5 is a drawing showing an example of the structure of an inner iron core having a wound iron core and the structure of a copper coil.

(Prediction method of PCB concentration of cleaning liquid after cleaning)
The method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention is that the PCB of the cleaning liquid after cleaning is cleaned before the PCB-contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB is cleaned with the cleaning liquid. A method for predicting concentration,
From the PCB concentration of the insulating oil before cleaning the PCB-contaminated equipment, the nameplate weight of the PCB-contaminated equipment, and the amount of nameplate oil of the PCB-contaminated equipment, the predicted PCB concentration of the cleaning liquid after cleaning is obtained by the following Equation 3. .
[Formula 3]
PCB predicted concentration of cleaning solution after cleaning =
[(Internal member coefficient x Name plate weight x Internal member oil content coefficient x PCB concentration of insulating oil before cleaning) + (Name plate oil amount ^2/3 x Container residual oil coefficient x PCB concentration of insulating oil before washing)] / (Name plate (Oil quantity x Insulating oil specific gravity)
However, in said Numerical formula 3, the said nameplate weight represents the total weight of the PCB contamination apparatus containing the insulating oil described in the nameplate of the said PCB contamination apparatus. The amount of the nameplate oil is the total amount of oil described on the nameplate of the PCB-contaminated equipment, and is set to 2/3 power in consideration of the contact area of the oil for calculating the amount of adhesion to the container wall surface and the container bottom surface. The internal member oil impregnation coefficient represents a coefficient for obtaining the oil content in the internal member of the PCB-contaminated equipment. The internal member coefficient represents a coefficient for obtaining the internal member weight from the nameplate weight. The container residual oil coefficient represents a coefficient for calculating the amount of insulating oil remaining on the container wall surface and the container bottom surface of the PCB-contaminated equipment after the insulating oil is extracted from the PCB-contaminated equipment.

In order to solve the above-mentioned problems, the present inventors have conducted extensive studies at the development and demonstration stage of heating forced circulation cleaning and electric charging natural circulation cleaning, satisfying the cleaning conditions such as temperature and period, and after cleaning. When the PCB concentration of the cleaning liquid falls within the specified range, the corresponding verification analysis is performed on the container and internal parts of the PCB contaminated equipment after cleaning, and it is confirmed that the PCB decontamination processing standards are satisfied. It was found that the completion of the PCB detoxification process of the device after cleaning can be determined simultaneously with the end of the cleaning process. Moreover, it discovered that the method of estimating the PCB density | concentration of the washing | cleaning liquid after washing | cleaning a PCB contaminated apparatus before washing | cleaning is required.
And, as a result of further diligent investigation by the present inventors from the above knowledge, from the PCB concentration of the insulating oil before cleaning the PCB-contaminated equipment, the nameplate weight of the PCB-contaminated equipment, and the nameplate oil amount of the PCB-contaminated equipment, No. 3 found a method for obtaining the predicted PCB concentration of the cleaning liquid after cleaning, and the present invention was made.
The method for predicting the PCB concentration of the cleaning liquid after the cleaning according to the present invention is not only scientific knowledge showing the accuracy of the determination of the detoxification treatment of the PCB-contaminated equipment by the predicted PCB concentration of the cleaning liquid after the cleaning, but also before the cleaning. Since the cleaning result can be predicted, the cleaning process such as efficient cleaning order according to the PCB contamination concentration, preparation of the cleaning liquid, and saving of the cleaning liquid is extremely useful in practical use.

  Hereinafter, a method for obtaining the predicted PCB concentration of the cleaning liquid after cleaning from the PCB concentration of the insulating oil before cleaning the PCB-contaminated equipment, the nameplate weight of the PCB-contaminated equipment, and the amount of nameplate oil of the PCB-contaminated equipment will be described. .

First, the amount of PCB contained in the insulating oil before cleaning impregnating the internal member of the PCB contaminated device can be obtained from the following formula 1.
[Formula 1]
PCB amount in internal member (mg) = nameplate weight × PCB concentration of insulating oil before cleaning × internal member coefficient × internal member oil impregnation coefficient In the formula 1, the nameplate weight is described on the nameplate of the PCB contaminated device. Represents the total weight of PCB contaminated equipment containing insulating oil. The internal member coefficient represents a coefficient for obtaining the internal member weight from the nameplate weight. The internal member oil impregnation coefficient represents a coefficient for obtaining the oil content in the internal member of the PCB-contaminated equipment.

  The internal member is not particularly limited as long as it contains and adheres to PCB, and can be appropriately selected according to the purpose. For example, if the PCB-contaminated equipment is a transformer, an iron core, coil (winding) Wire), insulating material, cooling structural material (radiator), conservator, elephant and the like.

The PCB concentration of the insulating oil before washing can be measured by, for example, a high resolution mass spectrometer (HRGC-HRMS).
The amount of PCB in the internal member is calculated by deriving the amount of oil contained in the internal member from the weight of the nameplate of the PCB contaminated device, and multiplying the amount of oil contained in the internal member by the PCB concentration of the insulating oil before cleaning. Can be calculated.

Next, the amount of PCB contained in the insulating oil before cleaning remaining on the container wall surface and the container bottom surface of the PCB contaminated device can be obtained from the following Equation 2.
[Formula 2]
PCB amount (mg) remaining on container wall surface and bottom surface of container = nameplate oil amount ^2/3 × PCB concentration of insulating oil before washing × container residual oil coefficient However, in equation 2, the nameplate oil amount is the amount of PCB contamination. This is the total amount of oil described on the nameplate of the device, and was set to the 2/3 power in consideration of the contact area of the oil in order to calculate the amount of adhesion to the container wall surface and the container bottom surface. The container residual oil coefficient represents a coefficient for calculating the amount of oil remaining on the container wall surface and the container bottom surface after the insulating oil before washing is drained.

Next, the PCB amount that is the sum of Equation 1 and Equation 2 is divided by the amount of cleaning oil obtained from the amount of nameplate oil and the specific gravity of the insulating oil, which serves as a guide for the amount of cleaning fluid at the time of cleaning. The predicted concentration can be obtained from Equation 3 below. The specific gravity of the insulating oil is 0.87.
[Formula 3]
PCB predicted concentration of cleaning solution after cleaning =
[(Internal member coefficient x Name plate weight x Internal member oil content coefficient x PCB concentration of insulating oil before cleaning) + (Name plate oil amount ^2/3 x Container residual oil coefficient x PCB concentration of insulating oil before washing)] / (Name plate (Oil quantity x Insulating oil specific gravity)

  Regarding the “internal member coefficient”, the “internal member residual oil coefficient”, and the “container residual oil coefficient” in the mathematical formula 3, a plurality of various transformers are actually disassembled, and locations (coils, iron cores, containers) It can be determined by actually measuring the weight, oil content, PCB content and adhesion amount for each member (paper, copper wire, wood).

  Therefore, according to the method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention, the PCB concentration of the insulating oil before cleaning, the nameplate weight of the PCB contaminated device, and From the amount of nameplate oil of the PCB-contaminated equipment, the predicted PCB concentration of the cleaning liquid after cleaning can be easily and reliably obtained by the equation 3.

The method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention can be suitably applied to the method for determining the end of the cleaning process for the PCB-contaminated equipment and the method for determining the completion of the PCB detoxification process by the cleaning described below.
In the cleaning plan, for example, setting of the order of PCB-contaminated equipment to be cleaned using the PCB concentration of the insulating oil before cleaning as an index, estimation of the required amount of cleaning liquid, and the like can be mentioned.
Further, at the time of cleaning, it is useful for management of the cleaning process and prediction of the cleaning end time together with the actually measured PCB concentration.
In practical use, care must be taken because the cleaning conditions and the homogeneity of oil removal are the fluctuation factors of the predicted value. Once the fluctuation factors can be grasped, they should be widely applied regardless of the size and specifications of the PCB contaminated equipment. Can do.

(Method for determining completion of cleaning process for PCB contaminated equipment and method for determining completion of PCB detoxification process by cleaning)
In the first embodiment, the method for determining the completion of the cleaning process for PCB-contaminated equipment according to the present invention, after washing the PCB-contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with the cleaning liquid, The end of the cleaning process is determined from the PCB concentration of the cleaning liquid.

  In the second embodiment, the method for determining the completion of the cleaning process for the PCB-contaminated equipment according to the present invention is based on the predicted PCB concentration of the cleaning liquid after the cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after the cleaning according to the present invention. Determine the end of.

  In the first embodiment, the method for determining the completion of PCB detoxification treatment by washing according to the present invention, after washing PCB contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with washing liquid, Completion of the PCB detoxification process is determined from the PCB concentration of the cleaning liquid.

  In the second embodiment, the method for determining the completion of PCB detoxification by cleaning according to the present invention is the PCB harmless from the predicted PCB concentration of the cleaning liquid after cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention. The completion of the conversion process is determined.

  The PCB concentration of the cleaning liquid after the PCB-contaminated equipment is cleaned with the cleaning liquid in the method for determining the completion of the cleaning processing of the PCB-contaminated equipment of the first form and the method for determining the completion of the PCB detoxification process by the cleaning of the first form May be an actually measured value or a predicted value. In the case of the predicted value, it is preferable that the predicted PCB concentration of the cleaning liquid after cleaning is obtained by the method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention.

In the method for determining the completion of the cleaning process for the PCB-contaminated equipment according to the first aspect and the method for determining the completion of the PCB detoxification process by the cleaning according to the first aspect, the insulating oil is extracted from the PCB-contaminated equipment and the cleaning liquid is injected. If the PCB concentration in the cleaning liquid after cleaning the PCB-contaminated equipment with the cleaning liquid in the subsequent cleaning cycle is 0.5 ppm or less, the PCB decontamination processing by the cleaning is completed at the same time as the cleaning processing of the PCB-contaminated equipment is completed. Can be determined.
The fact that the containers and internal components of the PCB-contaminated equipment after washing meet the PCB detoxification criteria is “the method for verifying the standards for specially controlled general waste and specially controlled industrial waste” (Notification by the Ministry of Health, Labor and Welfare in 1992) No. 192) By satisfying both the third (wiping test) judgment standard of the third table, the third (member sampling test) judgment standard of the third table, and the fourth judgment standard of the same table Can be confirmed.

In the method for determining the end of the cleaning process for the PCB-contaminated equipment according to the second mode and the method for determining the completion of the PCB detoxification process by the cleaning according to the second mode, the removal of the insulating oil from the PCB-contaminated equipment and the injection of the cleaning liquid If the PCB predicted concentration of the cleaning liquid after cleaning is 0.5 ppm or less in the cleaning cycle subsequent to the cleaning, it is determined that the PCB detoxification processing by cleaning is completed at the same time as the cleaning processing of the PCB contaminated equipment is completed. be able to.
In this case, the PCB concentration of the insulating oil before cleaning, which is derived from the predicted PCB concentration of the cleaning liquid after cleaning of 0.5 ppm, is 20.9 ppm. In the case of one cleaning cycle, 20.9 ppm applies the judgment. This is the upper limit of the PCB concentration of the cleaning liquid before cleaning.
The fact that the containers and internal components of the PCB-contaminated equipment after washing meet the PCB detoxification criteria is “the method for verifying the standards for specially controlled general waste and specially controlled industrial waste” (Notification by the Ministry of Health, Labor and Welfare in 1992) No. 192) By satisfying both the third (wiping test) judgment standard of the third table, the third (member sampling test) judgment standard of the third table, and the fourth judgment standard of the same table Can be confirmed.

<PCB contamination equipment>
There is no restriction | limiting in particular as said PCB contamination apparatus, According to the objective, it can select suitably, For example, a small transformer, a medium-sized transformer, a large-sized transformer, a super-large transformer, a sealing device (large-sized bushing, OF Cable), and the like. Among these, a small transformer, a medium transformer, a large transformer, and a super large transformer are preferable.
The small transformer means that the nameplate weight is less than 1.0 t.
The medium-sized transformer means that the nameplate weight is 1.0 t or more and less than 10.0 t.
The large transformer means one having a nameplate weight of 10.0 t or more and less than 200 t.
The ultra-large transformer means one having a nameplate weight of 200 t or more.

<< Transformer >>
As the structure of the transformer, for example, (1) iron core (core) related, (2) winding (coil) related, (3) insulation related, (4) tap switching device, (5) tank / painting related, (6) Accessory related.

Examples of (1) iron core-related include iron core materials, wound iron cores, stacked iron cores, and iron core structures.
Examples of the iron core material include a cold rolled silicon steel strip, a directional silicon steel strip, a magnetic domain control silicon steel strip, and an amorphous iron core material.
Examples of the wound core include an uncut core (NC), a step joint core (1TC), a double step lap joint core (DSL), and the like.
Examples of the iron core include a strip-shaped iron core, a frame-shaped iron core, and a V-notch type iron core.
Examples of the iron core structure include an inner iron type and an outer iron type.
The inner iron type is an iron core type having an independent closed magnetic circuit for each phase winding, and has an appearance that the iron core is inside the winding.
The outer iron type is an iron core type having two independent closed magnetic paths for each phase winding, and has an appearance that the iron core is outside the winding.

Examples of (2) windings include winding materials and winding structures.
Examples of the winding material include formal copper wire (or formal aluminum wire), formal rectangular copper wire, paper-wrapped rectangular copper wire, electrodeposition-coated rectangular copper wire, dislocation conductor, copper strip (aluminum strip), and the like.
Examples of the structure of the winding include cylindrical winding, plate winding, interleave winding, concentric arrangement, and alternate arrangement.

Examples of the (3) insulation related include an insulating material and insulating oil.
Examples of the insulating material include coil insulating paper, press board, and adhesive insulating paper.
As said insulating oil, 1 type (mineral oil) No. 2 of insulating oil A prescribed | regulated to JIS C2320-1999 (electrical insulating oil) can be used, for example. The specific gravity of the insulating oil is 0.87.

Examples of the (4) tap switching device include a tap plate, a non-voltage tap switching device, and a load tap switching device.
The tap means a lead wire drawn out from the middle of the winding so that the number of turns suitable for the voltage can be selected when the voltage received by the transformer fluctuates.

Examples of (5) tank / painting related include tanks (containers), radiators, and painting.
Examples of the container include a cylindrical shape, an oval shape, and a square shape.
Examples of the radiator include a rib (fin) type radiator, a panel type radiator, and a corrugated type radiator.
Examples of the coating include baking coating, natural drying coating, ordinary coating, and salt-resistant coating.

(6) Examples of accessories include bushings, high-pressure insulation caps, foundation bolts, ground terminals, oil drain plugs, oil drain valves, oil level gauges, thermometers, anti-vibration rubber, anti-vibration anti-vibration stands, wheels There is a respiratory organ.
The bushing is a device that has a passage through which a conductor passes through a partition wall (transformer cover, case, etc.), insulates the conductor from the partition wall, and supports and fixes the seal function. The bushing includes a primary bushing and a secondary bushing.

Here, an example of the transformer will be described. The transformer includes an outer can container and an internal member housed in the outer can container, and further includes other members as necessary.
The internal member is roughly classified into an outer iron core shown in FIG. 4 and an inner iron core shown in FIG.

  For example, as shown in FIG. 4, the outer iron core is composed of one iron core and two copper coils. The iron core is a wound iron core wound with a thin silicon steel plate, the inner side of the copper coil is secondary copper wire and papers, and the outer side of the copper coil is primary copper wire and papers.

  For example, as shown in FIG. 5, the inner iron core includes two iron cores and one copper coil. Here, the iron core is a wound iron core wound with a thin silicon steel plate, the outer side and the inner side of the copper coil are secondary copper wire and papers, and the central part of the copper coil is primary copper wire and papers is there.

The method for determining the end of the cleaning process for the PCB-contaminated equipment according to the present invention, the method for determining the completion of the PCB detoxification process by the cleaning according to the present invention, and the method for predicting the PCB concentration of the cleaning liquid after the cleaning according to the present invention are all used. It is preferably used for cleaning at least one of contaminated equipment and used PCB contaminated equipment.
The in-use PCB-contaminated device means a device that is currently used, and includes cases where the device is not used after cleaning and continues to be used.

The method for determining the completion of the cleaning process for the PCB-contaminated equipment according to the present invention, the method for determining the completion of the PCB detoxification process by the cleaning according to the present invention, and the method for predicting the PCB concentration of the cleaning liquid after the cleaning according to the present invention are all heated forced circulation cleaning. In addition, it is preferably used for at least one of the electric charge natural circulation cleaning.
Among these, it is particularly preferable to use it for the self-charging natural circulation cleaning of the PCB contaminated equipment during use. This is because, in the electricity-recycling natural circulation cleaning of in-use PCB-contaminated equipment contaminated with PCB, there is a remaining life of the equipment even after the PCB is removed, and it is desired to continue use from the viewpoint of resource recycling. Therefore, it is not practical to collect the internal member by disassembling the PCB-contaminated equipment after cleaning and perform the assay analysis. Therefore, in particular, in the practical application of the electric charging natural circulation cleaning, the PCB concentration in the cleaning liquid after cleaning is predicted before cleaning, and the end of the cleaning process of the PCB contaminated equipment is determined from the predicted result, After ensuring that it does not become a PCB contaminant again even if it continues, it is possible to determine whether or not the containers and internal members constituting the PCB contaminated equipment can satisfy the applicable PCB detoxification criteria after cleaning. Is needed.

<Heating forced circulation cleaning>
In the forced heating circulation cleaning, the insulating oil containing PCB is drained from the PCB contaminated equipment, and the cleaning liquid after replacement with the cleaning liquid is heated and forcedly circulated in the PCB contaminated equipment, so that the container of the PCB contaminated equipment is obtained. This is a technique for washing out PCBs adhering to the inner wall, the bottom of the container, and the inner member.
The heated forced circulation cleaning includes an oil removal process, an injection process, and a heating process, and further includes other processes as necessary. In addition, the said oil removal process, the said injection | pouring process, and the said heating process can be performed in arbitrary orders.

<< Oil removal process >>
The oil removal step is a step of removing the insulating oil containing PCB from the PCB contaminated equipment.
In the oil removal step, first, the outer can container and the inner member are separated. Next, the insulating oil (base oil) contaminated with PCB in the outer can container is transferred to a metal tank using a pump.
As described above, the oil removal is not limited to using the pump to extract the insulating oil contaminated with the PCB in the outer can container. For example, the oil removal is provided at the lower part of the PCB-contaminated equipment. The insulating oil contaminated with PCB may be drained from the mouth.

<< Injection process >>
The injection step is a step of injecting a cleaning liquid into the PCB contaminated device.
In the injection step, first, an internal member is installed in an outer can container. The cleaning liquid is then injected into the PCB contaminated equipment.
There is no restriction | limiting in particular as said washing | cleaning liquid, Although it can select suitably according to the objective, It should be at least 1 sort (s) selected from the oil which does not contain PCB substantially, and the organic solvent which can melt | dissolve PCB. preferable.
The oil substantially free of PCB means an oil having a PCB content concentration within a regulation (standard) range, and the PCB content concentration is 0.5 mg-PCB / kg-oil (0.5 ppm) or less. Of oil.
Examples of the oil substantially free of PCB include natural oils used in fuel oils, lubricating oils, edible oils, mineral oils including electrical insulating oils, and synthetic oils. The oil may be waste oil, recycled oil, oil obtained by decomposing PCB by chemical treatment, or oil from which PCB has been removed by physical treatment.

  Examples of the organic solvent capable of dissolving PCB include hydrocarbon-based cleaning agents selected from the second petroleums and the third petroleums.

<< Heating process >>
The heating step is a step of heating the cleaning solution by circulation cleaning so that the temperature of the cleaning solution injected in the injection step is 40 ° C. to 90 ° C.
In the whole period of the circulation cleaning, the liquid feeding speed (circulation flow rate) of the circulated oil is preferably a speed at which at least the oil in the transformer is replaced at least once per hour.
The temperature of the cleaning liquid is preferably 40 ° C to 90 ° C, more preferably 50 ° C to 90 ° C, and still more preferably 50 ° C to 70 ° C.
The heating rate of oil in the heating step is preferably 6 ° C / hr to 8 ° C / hr.

<< Other processes >>
As the other steps, for example, a temperature adjustment step for adjusting the temperature of the cleaning liquid to 30 ° C. to 40 ° C., the cleaning liquid is naturally cooled by heating so that the temperature of the cleaning liquid becomes 40 ° C. to 90 ° C., and then again, The second heating step for heating the cleaning liquid so that the temperature of the cleaning liquid is 40 ° C. to 90 ° C., the oil that is not contaminated with PCB in the PCB-contaminated equipment, or the PCB content concentration is within the regulation (standard) range. An oil purification step for sufficiently removing dust, moisture, dissolved gas, and the like in the oil by filtration and vacuum degassing when the oil is injected.

<Electricity natural circulation cleaning>
The above-mentioned electric charge natural circulation cleaning removes the insulating oil containing PCB from the PCB contaminated equipment, promotes heat generation of the internal members by applying the PCB contaminated equipment after replacement with the cleaning liquid, and naturally causes the cleaning liquid to move inside the PCB contaminated equipment. This is a technique for washing out the PCB adhering to the inner wall of the container, the bottom surface of the container, and the inner member of the PCB contaminated equipment.
The electrical charging natural circulation cleaning includes an oil removal process, an injection process, and an electrical charging process, and further includes other processes as necessary. In addition, the said oil extraction process, the said injection | pouring process, and the said electrical charging process can be performed in arbitrary orders.

<< Oil removal process >>
The oil removal step is the same as the oil removal step of the forced heating circulation cleaning.

<< Injection process >>
The injection process is the same as the injection process of the heating forced circulation cleaning.

<< Electricity transmission process >>
The power application step is a step of applying power to the PCB-contaminated equipment.
In the power application step, the inside of the PCB contaminated device is caused to generate heat, and the temperature of the cleaning liquid in the PCB contaminated device is changed by heating.
The temperature of the cleaning liquid is preferably from outside air temperature to 100 ° C, more preferably from 30 ° C to 80 ° C. Thus, by controlling the temperature of the cleaning liquid, ignition during cleaning can be suppressed.
By applying the electric power in the electric charging process, not only the temperature of the cleaning liquid in the PCB-contaminated equipment is changed by heating, but also the effects such as circulation of the cleaning liquid in the PCB-contaminated equipment by heating and vibration of internal members by electromagnetic induction are expected. Is done.
In the case where the PCB-contaminated equipment is a transformer, the electrical power applied to the PCB-contaminated equipment in the power application process is determined by the type of insulation when the transformer is operated at a rated load. It is performed by a transformer temperature test method (for example, return load method, equivalent load method, actual load method) used for the purpose of verifying that it is within a certain limit, or by connection to an electric system.
Connection to the electric system is performed without connecting a transformer to the actual electric system and artificially controlling the current value and the oil temperature.

<< Other processes >>
As the other steps, for example, a second oil removal step for removing the injected cleaning liquid from the PCB-contaminated equipment after the electric power application step, and when injecting oil that does not substantially contain PCB, An oil purification process that sufficiently removes dust, moisture, dissolved gas, and the like by filtration and vacuum degassing. In addition, in the oil removal step, an oil draining step by external heating or heat retention, in the electric power application step, external heating, external cooling, heat retention, strength of the applied voltage, strength of the applied voltage, intermittent implementation of the applied power, and The process etc. which perform at least any one of natural cooling are also mentioned.

  The method for determining the completion of the cleaning process for the PCB-contaminated equipment according to the present invention and the method for determining the completion of the PCB detoxification process by cleaning include the PCB concentration of the cleaning liquid after cleaning the PCB-contaminated equipment with the cleaning liquid, or the cleaning liquid after the cleaning according to the present invention. The completion of the PCB detoxification process of the PCB contaminated equipment after cleaning can be determined simultaneously with the completion of the cleaning process of the PCB contaminated equipment from the predicted PCB concentration of the cleaning liquid after the cleaning obtained by the method for predicting the PCB concentration.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the examples shown below, “small transformer”, “medium transformer”, and “large transformer” were used as PCB contaminated devices to be cleaned. The “insulating oil before cleaning” filled in the transformer is called “source oil”. The “cleaning liquid” was referred to as “cleaning oil”.

<Results of Transformer Testing and Transformer Information Used to Establish Judgment Method and Prediction Method for Completion of PCB Detoxification Processing of Cleaned Device Simultaneously with Completion of Cleaning Processing of PCB Contaminated Device>
Testing of PCB detoxification treatment criteria used for the construction and verification of methods for determining the completion of PCB detoxification processing for devices after cleaning and PCB concentration prediction of cleaning liquid after cleaning at the same time as cleaning of PCB contaminated devices The method is summarized in Table 1.

  As shown in the following Table 2-1 and Table 2-2, these transformers were cleaned by heating forced circulation cleaning or electricity-charging natural circulation cleaning, but in the construction of a method for predicting the PCB concentration of the cleaning liquid after cleaning. The difference in cleaning method and cleaning cycle was not used separately.

<Insulating oil and component analysis method>
As shown in Table 1, the collected insulating oil and internal components are mainly the methods described in the Standard Examination Method for Specially Controlled General Waste and Specially Controlled Industrial Waste (Heisei 1992 No. 192) Pretreatment and measurement were performed according to
Specifically, base oil and cleaning oil are shown in Appendix 2 (PCB analysis method in oil), container inner wall and iron core are shown in Appendix Table 3 (second wipe method), and primary and secondary copper wires are shown in Appendix 3 The third (member sampling test method), wood and paper were analyzed in accordance with Appendix 4 (eluate test method). In addition, wood and paper were separately analyzed according to the content test method 15.

<Concept of the end judgment method of cleaning processing of PCB contaminated equipment and the end judgment method of PCB detoxification processing by cleaning>
In the method for determining the end of the cleaning process for the PCB-contaminated equipment and the method for determining the completion of the PCB detoxification process by the cleaning, in order to determine the completion of the PCB detoxification process for the apparatus after the cleaning simultaneously with the end of the cleaning process for the PCB-contaminated equipment, Some indication is needed in the cleaning process of contaminated equipment contaminated with PCB. Therefore, attention was paid to the PCB concentration of the cleaning liquid as an index for determining the completion of the PCB detoxification process. That is, when the PCB concentration of the cleaning liquid after cleaning is predicted before cleaning, and the actual PCB concentration of the cleaning liquid does not exceed the predicted concentration and is equal to or lower than the PCB concentration of the cleaning liquid set as the management concentration of the cleaning process, The completion of the PCB detoxification process for the apparatus after cleaning is determined simultaneously with the end of the cleaning process for the PCB contaminated apparatus. This is because the predicted concentration is calculated on the assumption that most of the PCB contained in the PCB-contaminated equipment is dissolved in the cleaning liquid, and the predicted concentration is actually measured as the control concentration in the actual cleaning process. This is because it is designed as a method for obtaining matching between the predicted concentration and the actually measured concentration. For this purpose, the PCB concentration of the cleaning liquid after cleaning can be predicted before cleaning regardless of the specifications and size of the PCB contamination equipment shown below, and the PCB contamination equipment after cleaning should satisfy the PCB detoxification standard. It is necessary to show general and universal.

<Concept of method for predicting PCB concentration of washed oil after washing>
The PCB concentration of the cleaning oil after cleaning is determined by the fact that PCB contained in the oil remaining in the transformer after the base oil is extracted in the transformer to be cleaned dissolves in the cleaning oil poured after the cleaning.
Since the amount of lubrication is controlled by the cleaning process and can be measured with relatively high accuracy, the PCB concentration after cleaning is simply estimated from the amount of base oil remaining in the transformer after oil removal prior to cleaning. It can be determined by dividing the amount by the amount of lubrication.
In practice, however, it is extremely difficult to predict the amount of PCB from the amount of raw oil remaining in the transformer after oil removal. This is because there is no means for accurately calculating the amount of raw oil remaining in the transformer. In the first place, since the insulating oil used in the transformer is reduced or added as appropriate through operation and repair, it is extremely difficult to accurately grasp the actual amount of oil used in practice.
As an indication of the actual oil amount, the nameplate oil amount, which is the oil amount at the time of designing the transformer, can be mentioned, but in large transformers, the oil amount is often adjusted with an oil meter during operation. The amount of oil on the nameplate does not always match.
Therefore, even if the amount of oil extracted during cleaning is subtracted from the amount of nameplate oil, the amount of base oil remaining in the transformer cannot be obtained accurately. Furthermore, it is easily assumed that a storage transformer that has been drained and the amount of draining is unknown is to be cleaned. In such a case, it is impossible to obtain the oil amount remaining in the transformer from the oil removal amount. For these reasons, it is not practical to calculate the amount of oil remaining in the transformer from the amount of oil withdrawal and convert it to the amount of PCB.

As described above, in order to predict the PCB concentration of the cleaning oil after cleaning before the cleaning, it is necessary to fundamentally change the concept, but in reality, the PCB concentration of the cleaning oil after cleaning is predicted before the cleaning. The only information to be provided is the nameplate oil amount, nameplate weight, and base oil PCB concentration.
Therefore, a method for predicting the PCB concentration of the cleaning oil after cleaning was examined from these information. Basically, the PCB concentration of the cleaning oil after cleaning is determined by the fact that the PCB contained in the base oil remaining in the transformer after the base oil is extracted is dissolved in the cleaning oil. For this reason, as shown in FIG. 1, the amount of oil remaining inside the transformer after the base oil is extracted is roughly divided into the base oil impregnated in the internal members and the base oil remaining on the container wall surface and the container bottom surface of the transformer. Predicted.
If the oil amount can be predicted, the PCB amount can be calculated by multiplying the base oil PCB concentration.

First, the amount of PCB contained in the base oil impregnated in the internal member of the PCB contaminated device was determined from the following formula 1a.
[Formula 1a]
PCB amount in internal member (mg) = nameplate weight × source oil PCB concentration × internal member coefficient × internal member oil impregnation coefficient In the formula 1a, the nameplate weight is the insulation described on the nameplate of the PCB contaminated equipment. Represents the total weight of PCB contaminated equipment containing oil. The internal member coefficient represents a coefficient for obtaining the internal member weight from the nameplate weight. The internal member oil impregnation coefficient represents a coefficient for obtaining the oil content in the internal member of the PCB-contaminated equipment.
From these coefficients, the amount of oil contained in the internal member was derived from the weight of the nameplate of the transformer, and the amount of PCB contained in the internal member was calculated by multiplying the amount of oil contained in the internal member by the base oil PCB concentration.

Next, the amount of PCB contained in the base oil remaining on the container wall surface and the container bottom surface of the transformer was determined from the following formula 2a.
[Formula 2a]
PCB amount (mg) remaining on the container wall surface and the bottom surface of the container = nameplate oil amount ^2/3 × source oil PCB concentration × container residual oil coefficient However, in the formula 2a, the nameplate oil amount is on the nameplate of the PCB-contaminated equipment. It is the total oil amount described, and was set to 2/3 power in consideration of the contact area of the oil for calculating the amount of adhesion to the container wall surface and the container bottom surface. The container residual oil coefficient represents a coefficient for calculating the amount of oil remaining on the container wall surface and the container bottom surface after the base oil is extracted.
The amount of PCB remaining on the container wall surface and the bottom surface of the transformer was calculated by multiplying the obtained oil amount by the base oil PCB concentration.

The amount of PCB that is the sum of Equation 1 and Equation 2 is divided by the amount of washing oil obtained from the specific gravity of the nameplate oil amount and the insulating oil, which is a measure of the amount of washing oil at the time of washing. The predicted concentration was determined from Equation 3a below.
[Formula 3a]
PCB predicted concentration of cleaning solution after cleaning =
[(Internal member coefficient x Name plate weight x Internal member oil impregnation coefficient x Base oil PCB concentration) + (Name plate oil amount ^2/3 x Container residual oil coefficient x Base oil PCB concentration)] / (Name plate oil amount x Insulating oil specific gravity)

<Results of cleaning test used for construction and verification of prediction method for PCB concentration of cleaning oil>
As a cleaning method, heating forced circulation cleaning or electric charge natural circulation cleaning is used.
The heating forced circulation cleaning was performed by a self-made cleaning device.
The electrical charging natural circulation cleaning was performed by connecting to temporary and commercial electric circuits.
As the cleaning oil, an electrical insulating oil conforming to Japanese Industrial Standard was used.
The cleaning cycle is a case where the main oil is removed from the transformer and the cleaning oil is added once, and then the cleaning is performed again after the cleaning oil is extracted and the cleaning oil is reapplied. Was made twice.
The PCB concentration of the cleaning oil was the concentration at the completion of cleaning in the first cleaning cycle. In the case of the second washing cycle, the sum of the concentrations at the completion of the first and second washings was described as the washing oil PCB concentration.

<Determination of internal member coefficient and internal member residual oil coefficient>
The “internal member coefficient” and “internal member residual oil coefficient” in Equation 3a were determined as follows.
First, the nameplate weights and internal member weights of the small and medium-sized transformers (transformer numbers 4 to 34) and large transformers (transformer numbers 35 to 43) that were used in the cleaning tests performed so far were arranged. In addition, the transformer number was made common in Table 2-1 and Table 2-2.
The internal member weight was obtained by manually disassembling, disassembling, and separating the constituent members and measuring the total weight for each member or measuring a part thereof, and determining the total weight for each member from the ratio.
In the case of the large transformer, the weight of each member used at the time of manufacture was obtained from the manufacturer.
From the above results, a positive linear relationship was recognized between the internal member weight and the nameplate weight for a total of 21 small and medium transformers and a large transformer. From this relational expression, the weight of the internal member was determined from the weight of the nameplate, and the “internal member coefficient” of the mathematical formula 3a was determined.
The amount of oil contained in the internal member was measured, and the total amount of oil contained in these members was defined as the internal member oil content coefficient.

<Determination of container residual oil coefficient>
The “container residual oil coefficient” in Equation 3a was determined as follows.
Measured base oil PCB concentration, name plate oil amount and name plate weight corresponding to Table 2-1 and Table 2-2 for a total of 21 small and medium size transformers and large transformers shown in Table 2-1 and Table 2-2 Got. Substituting it into the formula 3a, the PCB predicted concentration of the washed oil after washing was obtained. The predicted PCB PCB concentrations of these cleaning oils were compared with the actually measured cleaning oil PCB concentrations after cleaning shown in Table 2-1. From the obtained positive linear relationship, the container residual oil coefficient, which is an unknown coefficient of the mathematical formula 3a, was obtained.
As described above, the predicted PCB concentration of the cleaning oil after the cleaning can be obtained from the formula 3a.

<Comparison of measured value and predicted value in cleaning oil PCB concentration>
In order to verify the method for predicting the PCB concentration of the cleaning oil after the cleaning, the predicted PCB concentration of the cleaning oil after the cleaning was obtained from the formula 3a and compared with the actual measured value of the cleaning oil or base oil PCB concentration. The predicted PCB concentration was calculated for a total of 43 small and large transformers shown in Tables 2-1 and 2-2. In the calculation, the nameplate weight, oil amount, and base oil PCB concentration described in Table 2-1 were substituted into Equation 3a. The results are shown in FIG.
From the result of FIG. 2, a positive linear relationship with a slope of 0.9908 is obtained between the measured value of the PCB concentration of the cleaning oil and the predicted PCB concentration of the cleaning oil after cleaning, and the coefficient of determination is 0.7278. Met.
Similarly, the relationship between the predicted PCB concentration of the cleaning oil after cleaning and the actual PCB measurement value of the base oil PCB concentration was examined. The results are shown in FIG. 3A and FIG. 3B, which is a partially enlarged view thereof. From the results of FIG. 3A and FIG. 3B, a positive linear relationship was recognized between the two, and the determination coefficient was 0.9337.

<Verification of PCB detoxification standards after cleaning>
Transformer containers and internal components cleaned by forced forced circulation cleaning and electricity-charging natural circulation cleaning shown in Table 2-1 and Table 2-2 are specially controlled general waste and specified controlled industrial waste shown in Table 3 below. Tested according to the standard test method for goods (Heisei 1992 No. 192) 13.

* Measurements were made using the standard verification method for specially controlled municipal solid waste and specially controlled industrial waste shown in Table 1 (Heisei 1992 No. 192).

  From Table 3, the containers and internal members after cleaning in all transformers satisfied the corresponding PCB detoxification treatment standards. In the case of two washing cycles, the test is the result at the end of the second cycle.

As described above, a method for predicting the PCB concentration of the cleaning oil after cleaning was obtained from the base oil PCB concentration, the nameplate weight, and the oil amount. The method for predicting the PCB concentration of the cleaning oil after cleaning is practically useful for predicting the cleaning result before cleaning and for preparing and saving the cleaning oil. Further, the prediction method is extremely useful because it shows the certainty in the determination of the detoxification process based on the PCB concentration in the cleaning oil.
Therefore, from the prediction method, the end of the cleaning process of the PCB-contaminated equipment and the determination of the completion of the PCB detoxification process by cleaning were examined.

<Verification of completion of cleaning process of PCB contaminated equipment by PCB predicted concentration of cleaning oil and verification of completion of PCB detoxification process by cleaning>
The completion determination of the cleaning process means that it is determined from the PCB concentration of the cleaning oil after the cleaning that the container and the internal member constituting the transformer satisfy the corresponding PCB detoxification processing standard after the cleaning. It also means that the cleaning process is completed at the same time.
In order to establish the end of the cleaning process, the following points were mainly verified when the PCB concentration of the cleaning oil did not change in the forced heating circulation cleaning or the charged natural circulation cleaning under certain cleaning conditions.
(1) Setting of PCB predicted concentration of cleaning oil after cleaning to be determined (2) Confirmation of PCB detoxification processing standard of determined member (3) Setting of base oil PCB concentration range to which determination can be applied

In the test shown in Table 3, (1) was set to 0.5 mg-PCB / kg-oil (0.5 ppm) except for some trial tests. That is, when a certain cleaning time has passed under a predetermined cleaning condition, the cleaning processing is performed when the PCB concentration of the cleaning oil falls within the predicted concentration range and is 0.5 mg-PCB / kg-oil (0.5 ppm) or less. Judged the end of.
As a basis for the concentration setting, 0.5 mg-PCB / kg-oil (0.5 ppm) which is a standard when the oil is subjected to PCB detoxification treatment can be mentioned. Therefore, according to the present invention, since a method for predicting the PCB concentration of the cleaning oil has been proposed, the grounds for setting become clearer and versatile.

3A and 3B, among the 43 transformers, the number of actually measured cleaning oil PCB concentrations exceeding 0.5 mg-PCB / kg-oil (0.5 ppm) is 18 units, It was predicted that the PCB concentration of the washing oil exceeded 0.5 mg-PCB / kg-oil (0.5 ppm) in both the tables.
On the other hand, there are 25 units in which the PCB concentration of the measured cleaning oil is 0.5 mg-PCB / kg-oil (0.5 ppm) or less, but 24 units have a PCB concentration of 0.5 mg-PCB in the cleaning oil. / Kg-oil (less than 0.5 ppm) could be predicted.
The actual measured cleaning oil PCB concentration is 0.5 mg-PCB / kg-oil (0.5 ppm), but only one unit has a cleaning oil PCB concentration of 0.5 mg-PCB / kg-oil (0.5 ppm). Concentration above was predicted. The fact that these measured values and predicted values are in good agreement in the concentration classification is verification of the end of the cleaning process of the PCB-contaminated equipment and the determination of the completion of the PCB detoxification process by cleaning, as well as the accuracy of the prediction method. It is also verification.

  At the same time, in setting the cleaning oil PCB concentration in the cleaning completion determination, it is a basis for explaining versatility applied to transformers of various specifications and sizes. In other words, the PCB concentration of the cleaning oil that satisfies the PCB detoxification processing standard corresponding to the container and the internal member constituting the transformer after cleaning is determined by setting the PCB concentration being measured with respect to the PCB detoxification processing standard of the oil. The main oil PCB concentration of the transformer used for the test was 117 mg-PCB / kg-oil (117 ppm) as the upper limit, and up to two cleaning cycles, the transformer after cleaning from the PCB concentration in the cleaning oil within the range of cleaning conditions performed It can be determined that the container and the internal member constituting the above satisfy the corresponding PCB detoxification treatment standard.

Further, in the case where the cleaning cycle for performing the cleaning after the draining of the base oil and the injection of the cleaning oil is one time, the grounds of the above (1) to (3) related to the detoxification treatment determination based on the cleaning oil PCB concentration are provided.
In the above (1), the determination based on the PCB concentration of the cleaning oil is performed with 0.5 mg-PCB / kg-oil (0.5 ppm), and the basis for setting the concentration is the PCB concentration of the cleaning liquid after cleaning according to the present invention. This is shown from the verification of the prediction method.
The above (2) is the PCB detoxification treatment standard applicable to all members constituting the equipment, regardless of the size and specifications of the transformer, as in the case of one cleaning cycle shown in Table 2-1. It has been confirmed that the PCB has been removed until satisfaction.
It is extremely important that the base oil PCB concentration range to which the determination of (3) can be applied is predicted in the case of one cleaning cycle. 3A and 3B, the base oil PCB concentration when the PCB concentration of the cleaning oil is 0.5 mg-PCB / kg-oil (0.5 ppm) based on the prediction method is 20.9 mg-PCB / kg-oil (20. 9 ppm), and when the cleaning cycle is one, the same concentration is the upper limit of the base oil PCB concentration to which the determination can be applied.

As described above, when the cleaning cycle is one time, at least a base oil PCB concentration of about 20.9 mg-PCB / kg-oil (20.9 ppm), which is explained from the method for predicting the PCB concentration of the cleaning liquid after cleaning according to the present invention. For the transformers up to and including the PCB prediction of the cleaning oil after cleaning that the container and the internal members constituting the transformer satisfy the applicable PCB detoxification processing standards after cleaning at the same time as the cleaning processing of the PCB contaminated equipment is completed It was found that it could be judged from the concentration.
Among these, the upper limit PCB concentration of the base oil supported from the PCB balance evaluated as the safe side is extremely important in the electric charging natural circulation cleaning. This is because the in-use device in which the PCB is mixed has a remaining life of the device, and it is desired to continue using it after removing the PCB from the viewpoint of resource recycling. In order to continue the use, it is not possible to collect the internal members by disassembling the transformer after the electricity-charging natural circulation cleaning, and to perform the assay analysis of the PCB detoxification process.
Therefore, it is necessary to determine the standard of detoxification treatment from the PCB concentration of the cleaning oil after cleaning, and it is significant that the application upper limit PCB concentration was explained in one cleaning cycle. In addition, since the application upper limit PCB concentration also considers the case where the PCB is completely washed out with the cleaning oil, it is considered that the PCB contamination transformer will not be re-established when the use is continued.

Thus, a method for predicting the PCB concentration of the cleaning oil after cleaning was obtained from the base oil PCB concentration, the nameplate weight, and the nameplate oil amount.
There are various practical methods for determining the completion of the cleaning process for the PCB-contaminated equipment according to the present invention, the method for determining the completion of the PCB detoxification process by the cleaning according to the present invention, and the method for predicting the PCB concentration of the cleaning liquid after the cleaning according to the present invention. Very useful in cleaning operations.
Further, in the cleaning plan, for example, setting of the order of transformers to be cleaned using the base oil PCB concentration as an index, estimation of a required amount of cleaning oil, and the like can be mentioned.
Further, at the time of cleaning, it is useful for management of the cleaning process and prediction of the cleaning end time together with the actually measured PCB concentration.
Also, in practical use, care must be taken because the cleaning conditions and the uniformity of oil removal are factors that fluctuate the predicted value, but once the factors are known, it should be widely applied regardless of the size and specifications of the transformer. Can do.

As an aspect of this invention, it is as follows, for example.
<1> After cleaning a PCB-contaminated device filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with a cleaning solution, the end of the cleaning process is determined from the PCB concentration of the cleaning solution. This is a method for determining the end of a cleaning process for a PCB-contaminated device.
<2> The method for determining completion of cleaning processing of a PCB-contaminated device according to <1>, which is used for cleaning at least one of a PCB-contaminated device in use and a used PCB-contaminated device.
<3> The method for determining the end of the cleaning process for a PCB-contaminated device according to any one of <1> to <2>, which is used for at least one of heating forced circulation cleaning and electric charge natural circulation cleaning.
<4> The PCB contamination apparatus according to any one of <1> to <3>, wherein the cleaning liquid is at least one selected from an oil substantially free of PCB and an organic solvent capable of dissolving PCB. This is a method for determining the end of a cleaning process.
<5> The PCB contamination according to any one of <1> to <4>, wherein the PCB contaminated device is at least one selected from a small transformer, a medium transformer, a large transformer, and a super large transformer. This is a method for determining the end of the cleaning process of the device.
<6> After the PCB-contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB is cleaned with the cleaning solution, the completion of PCB detoxification treatment is judged from the PCB concentration of the cleaning solution This is a method for determining the completion of the PCB detoxification process by cleaning.
<7> The method for determining completion of PCB detoxification processing by cleaning according to <6>, which is used for cleaning at least one of in-use PCB-contaminated equipment and used PCB-contaminated equipment.
<8> A method for determining the completion of PCB detoxification treatment by cleaning according to any one of <6> to <7>, which is used in at least one of heating forced circulation cleaning and electrical charging natural circulation cleaning.
<9> The PCB harmless by the cleaning according to any one of <6> to <8>, wherein the cleaning liquid is at least one selected from an oil substantially free of PCB and an organic solvent capable of dissolving PCB This is a method for determining whether to complete the process.
<10> By the cleaning according to any one of <6> to <9>, wherein the PCB-contaminated equipment is at least one selected from a small transformer, a medium transformer, a large transformer, and a super-large transformer. This is a method for determining completion of PCB detoxification processing.
<11> A method for predicting the PCB concentration of the cleaning liquid after cleaning before cleaning the PCB contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with the cleaning liquid,
From the PCB concentration of the insulating oil before cleaning the PCB-contaminated equipment, the nameplate weight of the PCB-contaminated equipment, and the amount of nameplate oil of the PCB-contaminated equipment, the predicted PCB concentration of the cleaning liquid after cleaning is obtained by the following Equation 3. This is a method for predicting the PCB concentration of the cleaning liquid after cleaning.
[Formula 3]
PCB predicted concentration of cleaning solution after cleaning =
[(Internal member coefficient x Name plate weight x Internal member oil content coefficient x PCB concentration of insulating oil before cleaning) + (Name plate oil amount ^2/3 x Container residual oil coefficient x PCB concentration of insulating oil before washing)] / (Name plate (Oil quantity x Insulating oil specific gravity)
However, in said Numerical formula 3, the said nameplate weight represents the total weight of the PCB contamination apparatus containing the insulating oil described in the nameplate of the said PCB contamination apparatus. The amount of the nameplate oil is the total amount of oil described on the nameplate of the PCB-contaminated equipment, and is set to 2/3 power in consideration of the contact area of the oil for calculating the amount of adhesion to the container wall surface and the container bottom surface. The internal member oil impregnation coefficient represents a coefficient for obtaining the oil content in the internal member of the PCB-contaminated equipment. The internal member coefficient represents a coefficient for obtaining the internal member weight from the nameplate weight. The container residual oil coefficient represents a coefficient for calculating the amount of insulating oil remaining on the container wall surface and the container bottom surface of the PCB-contaminated equipment after the insulating oil is extracted from the PCB-contaminated equipment.
<12> The method for predicting a PCB concentration of a cleaning liquid after cleaning according to <11>, which is used for cleaning at least one of in-use PCB contaminated equipment and used PCB contaminated equipment.
<13> The method for predicting the PCB concentration of the cleaning liquid after cleaning according to any one of <11> to <12>, which is used for at least one of heating forced circulation cleaning and electric charging natural circulation cleaning.
<14> The cleaning liquid after cleaning according to any one of <11> to <13>, wherein the cleaning liquid is at least one selected from an oil substantially free of PCB and an organic solvent capable of dissolving PCB This is a method for predicting the PCB concentration.
<15> After cleaning according to any one of <11> to <14>, wherein the PCB contaminated device is at least one selected from a small transformer, a medium transformer, a large transformer, and a super large transformer. This is a method for predicting the PCB concentration of the cleaning liquid.
<16> The end of the cleaning process is determined from the predicted PCB concentration of the cleaning liquid after cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after cleaning according to any one of <11> to <15>. This is a method for determining the end of the cleaning process for the PCB-contaminated equipment.
<17> In one cleaning cycle in which the insulating oil is drained from the PCB-contaminated equipment and the cleaning liquid is injected, if the predicted PCB concentration of the cleaning liquid after cleaning is 0.5 ppm or less, the PCB-contaminated equipment after cleaning This is a method for determining the end of the cleaning process for PCB-contaminated equipment according to <16>, in which the container and the internal member satisfy the PCB detoxification standard.
<18> Containers and internal components of PCB-contaminated equipment after cleaning are listed in “Approval Method for Standards Related to Specially Managed General Waste and Specially Controlled Industrial Waste” (Ministry of Health, Welfare Notification No. 192). Any one of <16> to <17> satisfying all of the second (wiping test) judgment standard, the third third (member sampling test) judgment standard, and the fourth judgment standard of the same table This is a method for determining the end of the cleaning process for PCB contaminated equipment.
<19> Determining the completion of the PCB detoxification process from the predicted PCB concentration of the cleaning liquid after cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after cleaning according to any one of <11> to <15> This is a method for determining completion of PCB detoxification processing by cleaning.
<20> In a single cleaning cycle in which the insulating oil is drained from the PCB contaminated equipment and the cleaning liquid is injected, if the predicted PCB concentration of the cleaning liquid after cleaning is 0.5 ppm or less, the PCB contaminated equipment after cleaning This is a method for determining the completion of PCB detoxification treatment by cleaning according to <19>, wherein the container and the internal member satisfy the PCB detoxification criteria.
<21> Containers and internal components of PCB-contaminated equipment after cleaning are listed in “Approval Method for Standards Concerning Special Management General Waste and Special Management Industrial Waste” (Ministry of Health, Welfare Notification No. 192) Any one of <19> to <20> satisfying all of the second (wiping test) judgment standard, the third third (part sampling test) judgment standard, and the fourth judgment standard of the same table This is a method for determining the completion of the PCB detoxification process by cleaning.

Claims (21)

  A PCB-contaminated device characterized in that after cleaning a PCB-contaminated device filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with a cleaning solution, the end of the cleaning process is determined from the PCB concentration of the cleaning solution. Method for determining the end of the cleaning process.   The method for determining the end of a cleaning process for a PCB-contaminated device according to claim 1, which is used for cleaning at least one of a PCB-contaminated device in use and a used PCB-contaminated device.   The method for determining the end of a cleaning process for a PCB-contaminated device according to any one of claims 1 to 2, wherein the method is used for at least one of heating forced circulation cleaning and electrical charging natural circulation cleaning.   The method for determining the end of the cleaning process for PCB-contaminated equipment according to any one of claims 1 to 3, wherein the cleaning liquid is at least one selected from an oil substantially free of PCB and an organic solvent capable of dissolving PCB. .   The PCB contaminated equipment cleaning process according to any one of claims 1 to 4, wherein the PCB contaminated equipment is at least one selected from a small transformer, a medium transformer, a large transformer, and an extra large transformer. Judgment method.   Cleaning after cleaning PCB contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with cleaning liquid, and determining completion of PCB detoxification process from PCB concentration of cleaning liquid Method for determining the completion of PCB detoxification processing by a computer.   The method for determining completion of PCB detoxification processing by cleaning according to claim 6, which is used for cleaning at least one of in-use PCB-contaminated equipment and used PCB-contaminated equipment.   The method for determining completion of PCB detoxification processing by cleaning according to any one of claims 6 to 7, wherein the method is used for at least one of heating forced circulation cleaning and electric charging natural circulation cleaning.   The method for determining completion of PCB detoxification treatment by cleaning according to any one of claims 6 to 8, wherein the cleaning liquid is at least one selected from an oil substantially free of PCB and an organic solvent capable of dissolving PCB. .   The PCB detoxification process by cleaning according to any one of claims 6 to 9, wherein the PCB contaminated device is at least one selected from a small transformer, a medium transformer, a large transformer, and a super-large transformer. Judgment method. A method for predicting the PCB concentration of a cleaning liquid after cleaning before cleaning the PCB contaminated equipment filled with insulating oil containing polychlorinated biphenyl (PCB) and contaminated with PCB with the cleaning liquid,
From the PCB concentration of the insulating oil before cleaning the PCB-contaminated equipment, the nameplate weight of the PCB-contaminated equipment, and the amount of nameplate oil of the PCB-contaminated equipment, the predicted PCB concentration of the cleaning liquid after cleaning is obtained by the following Equation 3. A method for predicting the PCB concentration of the cleaning liquid after cleaning.
[Formula 3]
PCB predicted concentration of cleaning solution after cleaning =
[(Internal member coefficient x Name plate weight x Internal member oil content coefficient x PCB concentration of insulating oil before cleaning) + (Name plate oil amount ^2/3 x Container residual oil coefficient x PCB concentration of insulating oil before washing)] / (Name plate (Oil quantity x Insulating oil specific gravity)
However, in said Numerical formula 3, the said nameplate weight represents the total weight of the PCB contamination apparatus containing the insulating oil described in the nameplate of the said PCB contamination apparatus. The amount of the nameplate oil is the total amount of oil described on the nameplate of the PCB-contaminated equipment, and is set to 2/3 power in consideration of the contact area of the oil for calculating the amount of adhesion to the container wall surface and the container bottom surface. The internal member oil impregnation coefficient represents a coefficient for obtaining the oil content in the internal member of the PCB-contaminated equipment. The internal member coefficient represents a coefficient for obtaining the internal member weight from the nameplate weight. The container residual oil coefficient represents a coefficient for calculating the amount of insulating oil remaining on the container wall surface and the container bottom surface of the PCB-contaminated equipment after the insulating oil is extracted from the PCB-contaminated equipment.   The method for predicting the PCB concentration of the cleaning liquid after cleaning according to claim 11, which is used for cleaning at least one of in-use PCB-contaminated equipment and used PCB-contaminated equipment.   The method for predicting the PCB concentration of a cleaning liquid after cleaning according to any one of claims 11 to 12, wherein the method is used for at least one of heating forced circulation cleaning and electrical charging natural circulation cleaning.   The method for predicting the PCB concentration of a cleaning liquid after cleaning according to any one of claims 11 to 13, wherein the cleaning liquid is at least one selected from an oil substantially free of PCB and an organic solvent capable of dissolving PCB. .   The PCB concentration of the cleaning liquid after cleaning according to any one of claims 11 to 14, wherein the PCB contaminated device is at least one selected from a small transformer, a medium transformer, a large transformer, and a super large transformer. Prediction method.   An end of the cleaning process is determined from the predicted PCB concentration of the cleaning liquid after cleaning obtained by the method for predicting the PCB concentration of the cleaning liquid after cleaning according to any one of claims 11 to 15. Method for determining the end of the cleaning process.   In a single cleaning cycle in which the insulating oil is drained from the PCB-contaminated equipment and the cleaning liquid is injected, if the predicted PCB concentration of the cleaning liquid after cleaning is 0.5 ppm or less, the container of the PCB-contaminated equipment after cleaning and The method for determining the end of a cleaning process for a PCB-contaminated device according to claim 16, wherein the internal member satisfies a PCB detoxification standard.   The container and internal parts of the PCB-contaminated equipment after washing are “test method for standards pertaining to specially managed general waste and specially controlled industrial waste” (Notification No. 192 of the Ministry of Health, Welfare 1992). 18. The cleaning of PCB-contaminated equipment according to any one of claims 16 to 17, which satisfies all of the determination criteria of Test (3), the determination criteria of Third (Parts Extraction Test) of Attached Table 3, and the determination criteria of Attached Table 4 Processing end determination method.   The completion of the PCB detoxification process is determined from the predicted PCB concentration of the washed liquid obtained by the method for predicting the PCB concentration of the washed liquid after washing according to any one of claims 11 to 15. Completion judgment method of PCB detoxification process.   In a single cleaning cycle in which the insulating oil is drained from the PCB-contaminated equipment and the cleaning liquid is injected, if the predicted PCB concentration of the cleaning liquid after cleaning is 0.5 ppm or less, the container of the PCB-contaminated equipment after cleaning and 20. The method for determining completion of PCB detoxification processing by cleaning according to claim 19, wherein the internal member satisfies the PCB detoxification criteria.   The container and internal parts of the PCB-contaminated equipment after washing are “test method for standards pertaining to specially managed general waste and specially controlled industrial waste” (Notification No. 192 of the Ministry of Health, Welfare 1992). 21. The PCB detoxification by cleaning according to any one of claims 19 to 20, which satisfies all of the test criteria of the test (3), the third criteria of the third table (part sampling test), and the fourth criteria of the same table Processing completion judgment method.