JP2011165851A - Estimating method of amount of copper sulfide generated in oil-filled electric equipment, diagnostic method of failure occurrence, estimating method of initial concentration of dibenzyl disulfide in insulating oil, and diagnostic method of possibility of failure occurrence - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of predicting possibility of failure (sulfidation corrosion) in oil-filled electrical apparatus with high precision, by analyzing a component in an insulating oil to precisely estimate a generation amount of copper sulfide even if 2, 6-di-t-butyl-4-methyl phenol is added to the insulating oil in the oil-filled electric equipment. <P>SOLUTION: The method of estimating the amount of copper sulfide generated in oil-filled electrical apparatuses includes (1) a first step which measures an amount of a particular product of one or more kinds which is contained in the insulating oil collected from the oil-filled electrical apparatus, and (2) a second step for estimating the generation amount of the copper sulfide, based on the amount of the particular product; and here, the particular product includes a reactive product between the radicals generated from the 2, 6-di-t-butyl-4-methyl phenol and that generated from dibenzyl disulfide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for estimating the amount of copper sulfide produced in an oil-filled electrical device such as a transformer, a method for diagnosing abnormality, a method for estimating an initial concentration of dibenzyl disulfide (hereinafter abbreviated as “DBDS”) in insulating oil, The present invention also relates to a method for diagnosing the possibility of occurrence of an abnormality. More specifically, the present invention relates to a technique for diagnosing sulfidation corrosion of oil-filled electrical equipment based on the concentration in the insulating oil of a reaction product of a sulfur compound and copper that causes sulfidation corrosion.

  In oil-filled electrical equipment such as oil-filled transformers, insulation paper is wound around coil copper, which is a current-carrying medium, and a structure is generally adopted in which coil copper does not short-circuit between adjacent turns. . In the oil-filled electrical device, the coil copper and the insulating paper are installed in insulating oil that plays a role of a cooling medium or the like.

  On the other hand, some insulating oils used in oil-filled electrical equipment contain sulfur components. In this case, the sulfur component in the insulating oil reacts with the copper component, so that conductive copper sulfide is deposited on the surface of the insulating paper, and a conductive path is formed between the adjacent turns to cause a galvanic corrosion that causes dielectric breakdown. It is known that it may occur (for example, Non-Patent Document 1).

  From this point of view, the selection of insulating oil that hardly generates copper sulfide and the development of copper sulfide suppression technology are attracting attention. However, since the amount of insulating oil used for oil-filled electrical equipment is generally large and has a long service life, it is not easy to replace it. For this reason, in each oil-filled electrical device using an insulating oil containing a sulfur component, there is a demand for a method capable of predicting the possibility of occurrence of an abnormality such as a dielectric breakdown caused by the precipitation of copper sulfide. This is because it is possible to take appropriate measures according to the state of each oil-filled electrical device by predicting the possibility of occurrence of an abnormality.

  DBDS is known as a causative substance in insulating oil for depositing copper sulfide (for example, Non-Patent Document 2).

The mechanism by which copper sulfide is generated from DBDS will be described with reference to FIG. As shown in FIG. 8, it has been found in previous studies that copper sulfide is produced by the following three-stage reaction (Non-Patent Document 3).
(First stage) Reaction in which DBDS is coordinated (adsorbed) to a copper plate.
(Second stage) A reaction in which DBDS reacts with copper to form a DBDS-Cu complex.
(Third stage) A reaction in which the DBDS-Cu complex is decomposed into copper sulfide, benzyl radical and benzylsulfenyl radical by thermal decomposition or the like.

  Therefore, the production of copper sulfide consumes DBDS in the insulating oil and produces benzyl radicals and benzylsulfenyl radicals. The benzyl radical and benzylsulfenyl radical generate bibenzyl and dibenzyl sulfide as by-products by a reaction that occurs between the same radicals or between two radicals. Therefore, it is thought that the information regarding the production amount of copper sulfide can be obtained by measuring the production amount (concentration) of these by-products.

  However, when 2,6-di-tert-butyl-4-methylphenol (hereinafter abbreviated as “DBPC”), which is an antioxidant, is added to the insulating oil, the amount of the by-product is as follows. Therefore, there is a problem that accurate information on the amount of copper sulfide produced cannot be obtained.

CIGRE TF A2.31, “Copper sulphide in transformer insulation,” ELECTRA, No. 224, pp. 20-23, 2006 F. Scatiggio, V. Tumiatti, R. Maina, M. Tumiatti M. Pompilli and R. Bartnikas, “Corrosive Sulfur in Insulating Oils: Its Detection and Correlated Power Apparatus Failures”, IEEE Trans. Power Del., Vol. 23, pp. 508-509, 2008 S.Toyama, J.Tanimura, N.Yamada, E.Nagao, T.Amimoto, "Highly Sensitive Detection Method of Dibenzyl Disulfide and Elucidation of Mechanism of Copper Sulfide Generation in Insulating Oil", IEEE TDEI, Vol.16, No. 2, pp509-515, 2009

  Even when DBPC is added to insulating oil in oil-filled electrical equipment, the present invention can estimate the amount of copper sulfide generated with high accuracy by analyzing the components in the insulating oil. It is an object of the present invention to provide a method capable of predicting the possibility of occurrence of abnormality (sulfide corrosion) in equipment with high accuracy.

  DBPC is added in order to generate radicals as shown in FIG. 1 and to prevent oxidative degradation of oil by suppressing radical chain. It has been found that the radicals generated from the reaction. Therefore, the amount of copper sulfide in the insulating oil to which DBPC is added can be calculated more accurately by analyzing the reaction product of the radical generated from DBPC and the radical generated from DBDS.

That is, the present invention is a method for estimating the amount of copper sulfide produced in oil-filled electrical equipment,
(1) a first step of measuring an amount of one or more specific products contained in insulating oil collected from the oil-filled electrical device; and
(2) including a second step of estimating the production amount of the copper sulfide based on the amount of the specific product,
The specific product is a method for estimating a copper sulfide production amount including a reaction product of a radical generated from DBPC and a radical generated from DBDS.

  The oil-filled electrical device is preferably an oil-filled electrical device using an insulating oil containing DBPC.

  The insulating oil collected from the oil-filled electrical equipment is analyzed by a gas chromatograph mass spectrometer, and the peak area value of the fragment ion peak of M / Z = 310 or the fragment ion peak of M / Z = 219, Or it is preferable to obtain | require the quantity of the reaction product of the radical produced | generated from the said DBPC, and the radical produced | generated from DBDS using the total value of these peak area values.

  The one or more specific products preferably further include at least one compound selected from the group consisting of benzyl alcohol, benzaldehyde, benzoic acid, dibenzyl sulfoxide, toluene, bibenzyl and dibenzyl sulfide.

The second step includes
Converting each concentration of the one or more specific products into a molar concentration of the benzene ring, and calculating a total molar concentration summing them, 2-1 step; and
It is preferable to include the 2-2nd step of estimating the production amount of the copper sulfide based on the total molar concentration.

  The present invention also relates to an abnormality occurrence diagnosis method for diagnosing occurrence of an abnormality in an oil-filled electrical device based on the amount of copper sulfide produced estimated using the above method.

Further, the present invention is a method for estimating the initial concentration of dibenzyl disulfide in insulating oil in oil-filled electrical equipment,
(1) a first step of measuring the concentration of one or more specific products contained in the insulating oil collected from the oil-filled electrical device; and
(2) including a second step of estimating an initial concentration of the dibenzyl disulfide based on the concentration of the one or more specific products.
The one or more specific products include a reaction product of a radical generated from 2,6-di-t-butyl-4-methylphenol and a radical generated from dibenzyl disulfide, and benzyl alcohol. At least one compound selected from the group consisting of benzaldehyde, benzoic acid, dibenzyl sulfoxide, toluene, bibenzyl and dibenzyl sulfide,
The second step includes
Step 2-1 for converting each concentration of the one or more specific products into a molar concentration of benzene rings and calculating a total molar concentration of the total concentrations.
From the total molar concentration, step 2-2 for calculating the amount of decrease in DBDS using a calibration curve prepared in advance, and
The present invention also relates to a method for estimating the initial concentration of DBDS in insulating oil, including a second to third step of calculating the initial concentration of DBDS from the concentration of DBDS and the decrease amount of DBDS.

  Furthermore, the present invention also relates to a diagnostic method for the possibility of occurrence of abnormality, which diagnoses the occurrence of abnormality in an oil-filled electrical device based on the initial concentration of DBDS estimated using the above method.

  In the present invention, even when DBPC is added to the insulating oil in the oil-filled electrical device by measuring the amount of the reaction product of the radical generated from DBPC and the radical generated from DBDS in the insulating oil, The amount of copper sulfide produced can be estimated with high accuracy, and the occurrence of abnormalities (sulfur corrosion) in oil-filled electrical equipment can be diagnosed with high accuracy.

  In the present invention, in addition to the amount of the reaction product of the radical generated from DBPC and the radical generated from DBDS, benzyl alcohol, benzaldehyde, benzoic acid, dibenzyl sulfoxide, toluene, bibenzyl and dibenzyl sulfide By measuring the amount of a specific product containing at least one compound selected from the group consisting of: an insulating oil in an oxygen-containing atmosphere and an oxygen-free atmosphere regardless of the type of oil-filled electrical equipment In any of the cases below, the amount of copper sulfide produced can be estimated with high accuracy, and the occurrence of abnormality (sulfidation corrosion) in oil-filled electrical equipment can be diagnosed with high accuracy.

  In addition, the initial concentration of DBDS can be estimated with high accuracy by estimating the initial concentration of DBDS based on the amount of radicals generated from DBPC and reaction products of radicals generated from DBDS in the insulating oil. .

(A), (b) is a figure which shows the structural formula of two types of radicals produced | generated from DBPC. It is a figure which shows the structural formula of the reaction product of the radical (FIG.1 (b)) produced | generated from DBPC, and a benzyl radical. 3 is a graph showing the amount of bibenzyl produced in an insulating oil to which DBPC is added and the relationship between the amount of compound produced in FIG. 2 and the amount of copper sulfide. It is a graph which shows the relationship between the amount of bibenzyl production | generation in the insulating oil to which DBPC is not added, and the amount of copper sulfide. It is a graph which shows the relationship between the compound production amount of FIG. 2 in air and nitrogen, and the amount of copper sulfide. It is a graph which shows the relationship between the total amount of a by-product in air and nitrogen, and the amount of copper sulfide. It is a graph which shows the relationship between the total amount of the by-product in air and nitrogen, and the amount of reduction | decrease of DBDS. It is a schematic diagram which shows the mechanism in which copper sulfide produces | generates from DBDS.

(Embodiment 1)
In this embodiment,
As one or more specific products contained in insulating oil collected from oil-filled electrical equipment, the concentration of only the reaction products of radicals generated from DBPC and radicals generated from DBDS is measured,
Based on the amount of this specific product, the amount of copper sulfide produced in the oil-filled electrical device is estimated.

(1) Measurement of specific products The amount (concentration) of specific products (reaction products of radicals generated from DBPC and radicals generated from DBDS) contained in the insulating oil is determined using various known methods. For example, it can be measured using a gas chromatograph / mass spectrometer (GC / MS).

  Specifically, the insulating oil is analyzed by GC / MS and, for example, the peak of a fragment ion peak with M / Z (mass to charge ratio) = 310 or a fragment ion peak with M / Z = 219. The amount of reaction products of radicals generated from DBPC and radicals generated from DBDS can be measured using the area value or the sum of these peak area values.

  As a result of estimation by the fragment ion peak of GC / MS, the fragment ion peak of M / Z = 310 is 4-benzyl-2,6, which is a reaction product of a radical generated from DBPC and a benzyl radical. It is considered to be a peak due to -di-t-butyl-4-methyl-2,5-cyclohexadienone (the structural formula is shown in FIG. 2, hereinafter abbreviated as “compound of FIG. 2”). The fragment ion peak of M / Z = 219 is also considered to be a peak due to the same compound.

(2) Estimating the amount of copper sulfide produced As a method for estimating the amount of copper sulfide produced in oil-filled electrical equipment based on the amount (concentration) of the reaction product of radicals produced from DBPC and radicals produced from DBDS The method of preparing the calibration curve which shows the correlation with the density | concentration of the said reaction product and the amount of copper sulfide production beforehand is mentioned. Such a calibration curve is obtained by, for example, filling an oil-filled electrical equipment model with an insulating oil having a known initial concentration of the reaction product and copper sulfide, and increasing the concentration of the specific product and the sulfide under predetermined conditions. It can be created by measuring the increasing concentration of copper.

  There is a good correlation between the amount of reaction products (for example, the compound of FIG. 2) of radicals generated from DBPC and benzyl radicals and the amount of copper sulfide produced. By measuring the reaction product of a radical generated from DBPC and a benzyl radical, the amount of copper sulfide produced at that temperature can be determined with higher accuracy.

  4-Benzyl-2,6-di-t-butyl-4-methyl-2,5-cyclohexadienone (compound of FIG. 2) is generated from the radical of FIG. 1 (b) generated from DBPC and DBDS. It is a reactive organism with the benzyl radical. Even when the amount of reaction products of radicals generated from other DBPCs (radicals in FIGS. 1A and 1B) and radicals generated from DBDS (benzyl radicals, benzylsulfenyl radicals) is measured, the same applies. Thus, the amount of copper sulfide produced can be determined. Moreover, multiple types of the above reaction products may be measured, and the amount of copper sulfide produced may be estimated based on the total amount thereof.

(Embodiment 2)
In this embodiment,
As one or more specific products contained in insulating oil collected from oil-filled electrical equipment, in addition to the reaction products of radicals generated from DBPC and radicals generated from DBDS, benzyl alcohol, benzaldehyde, The amount of at least one compound selected from the group consisting of benzoic acid, dibenzyl sulfoxide, toluene, bibenzyl and dibenzyl sulfide is measured;
Based on the amount of this specific product, the amount of copper sulfide produced in the oil-filled electrical device is estimated.

  When the insulating oil of oil-filled electrical equipment is in an air atmosphere (under an oxygen-containing atmosphere), such as an open-type transformer, the toluene, bibenzyl, dibenzyl sulfide and DBDS may hardly be generated. In such a case, the amount of toluene, bibenzyl, dibenzyl sulfide and DBDS produced is not correlated with the amount of copper sulfide produced in the conventional manner, and the amount of these by-products produced may be measured. In some cases, accurate information regarding the amount of copper sulfide produced cannot be obtained.

  It is known that this is because the benzyl radical changes to a benzyl peroxide radical under the influence of oxygen and further changes to benzyl alcohol or benzaldehyde or benzoic acid in an environment with a high oxygen concentration. Similarly, benzylsulfenyl radicals have been found to be converted to dibenzyl sulfoxide.

  Therefore, in the present embodiment, in addition to the reaction product of the radical generated from DBPC and the radical generated from DBDS, benzyl alcohol, benzaldehyde, benzoic acid, dibenzyl sulfoxide, toluene, bibenzyl and dibenzyl sulfide. It is preferred to measure the amount of all compounds. By estimating the copper sulfide production amount based on the amounts of all these compounds, it is possible to estimate the copper sulfide production amount with higher accuracy without being affected by the change in the oxygen concentration in the insulating oil. However, it is good also as not measuring about a product whose quantity is remarkably smaller than another product. Thereby, a measuring object can be reduced.

(1) Concentration measurement of specific product Each concentration of one or more specific products contained in insulating oil can be measured using various known methods, for example, gas chromatograph / mass spectrometer It can be measured using (GC / MS).

(2) Estimation of copper sulfide production amount In this embodiment, the specific product contained in the insulating oil is measured, the concentration of each component is converted into the molar concentration of the benzene ring, and the total mol of these components is summed. Based on the concentration (N), the amount of copper sulfide produced is estimated.

  As a method for estimating the production amount of copper sulfide in oil-filled electrical equipment based on the total molar concentration (N), a calibration curve showing the correlation between the total molar concentration (N) and the copper sulfide production amount in advance. The method of making is mentioned. Such a calibration curve is obtained by, for example, filling an oil-filled electrical equipment model with an insulating oil whose initial concentration of the specific product and copper sulfide is known, and increasing the concentration of the specific product under each predetermined condition. It can be created by measuring the increasing concentration of copper sulfide.

(3) Diagnosis of Abnormality Further, the amount of copper sulfide estimated in the present embodiment is compared with a specific reference value (threshold value) in the same manner as in the first embodiment. The occurrence can be diagnosed.

  As in the first embodiment, attention can be urged to preferentially take necessary measures for a transformer diagnosed as having an abnormality.

(Embodiment 3)
In this embodiment,
As one or more specific products contained in the insulating oil collected from the oil-filled electrical device, the concentration of the specific product similar to that of Embodiment 2 is measured, and the concentration of DBDS is further measured.
Based on each concentration of this specific product and the concentration of DBDS, the initial concentration of DBDS in the insulating oil in the oil-filled electrical device is estimated.

The initial concentration of DBDS is important as an index for diagnosing the possibility of occurrence of abnormality.
(1) Concentration measurement of specific product and DBDS The concentration of the specific product contained in the insulating oil can be measured using various known methods, for example, a gas chromatograph / mass spectrometer (GC / MS).

  In addition, as a method for measuring the (residual) concentration of DBDS in the collected insulating oil, various known methods can be used, for example, a method of analyzing by gas chromatography (for example, S. Toyama, J. Tanimura, N. Yamada, E. Nagao and T. Amimoto, “High sensitive detection method of dibenzyl disulfide and the elucidation of the mechanism of copper sulfide generation in insulating oil”, Doble Client Conf., Boston, MA, USA, (See Paper IM-8A, 2008).

(2) Estimation of DBDS initial concentration The method of estimating the DBDS initial concentration in the insulating oil in the present embodiment is as follows.
A step of converting each concentration of the specific product into a molar concentration of the benzene ring and calculating a total molar concentration (N) of the total concentration (step 2-1),
From the total molar concentration (N), a step of calculating a reduction amount of DBDS using a calibration curve prepared in advance (step 2-2), and
A step (second step 3) of calculating an initial concentration of DBDS from the concentration of DBDS and the decrease amount of DBDS is included.

  Therefore, in the present embodiment, a calibration curve indicating the correlation between the total molar concentration (N) of the specific product and the amount of decrease in DBDS is created in advance. Such a calibration curve is obtained by, for example, filling an oil-filled electrical equipment model with an insulating oil whose DBDS initial concentration is known, and calculating the total molar concentration (N) of the specific product and the DBDS reduction amount under certain conditions. Can be created by asking.

  In the same manner as in Embodiment 2, the total molar concentration (N) of the molar concentration of the benzene ring is calculated from the concentration of the specific product, and DBDS is calculated from the calculated total molar concentration (N) using the calibration curve. The amount of decrease is calculated.

The initial concentration of DBDS is expressed by the following formula (1):

“DBDS initial concentration” = “DBDS concentration” + “DBDS decrease amount” (1)

Is calculated from

  DBDS, which is a copper sulfide causative substance, decreases in amount due to the formation of copper sulfide. Therefore, just because DBDS is not included in insulating oil collected from oil-filled electrical equipment that has been operating for years, it cannot be said that the transformer is safe against defects caused by copper sulfide. Moreover, it can be said that the amount of copper sulfide produced in the transformer depends on the concentration of DBDS. Therefore, when estimating the risk for copper sulfide, it is important to estimate the initial concentration of DBDS at the start of operation of the oil-filled electrical device.

(3) Diagnosis of possibility of occurrence of abnormality Diagnosing the possibility of occurrence of abnormality in oil-filled electrical equipment by comparing the initial concentration of DBDS estimated as described above with a specific reference value (threshold). be able to.

  Here, the threshold value of the initial concentration of DBDS includes, for example, a method of determining the threshold value in a test widely used as a test for corrosive sulfur of insulating oil. As this type of test, for example, JIS C 2101 17 (corrosive sulfur test) is often used in Japan, and ASTM D 1275B is often used overseas. Here, ASTM is an abbreviation for “American Society for Testing and Materials”.

  For example, the threshold value can be determined by the following procedure using 17 of JIS C 2101. First, an insulating oil that does not exhibit corrosiveness according to 17 of JIS C 2101 is prepared. As such an insulating oil, for example, a synthetic oil containing no sulfur such as alkylbenzene and α-olefin is preferably used. A predetermined amount (for example, 50, 100, 150, 200 ppm) of DBDS is dissolved in this insulating oil to obtain a sample oil. Using the sample oil thus prepared, the test is performed by the method described in 17.2 to 17.5 of JIS C 2101, and the corrosivity is determined by the method described in 17.6. As a result, for example, when sample oils with DBDS concentrations of 50 and 100 ppm show non-corrosive properties, and sample oils with 150 and 200 ppm show corrosive properties, the upper limit of 100 ppm indicating non-corrosive properties is taken as the threshold value. be able to.

  When the initial concentration of DBDS is equal to or higher than such a specific reference value (threshold value), it is diagnosed that the oil-filled electrical device may have a malfunction (abnormality) due to copper sulfide deposition. . For transformers diagnosed as having the possibility of occurrence of abnormalities, attention can be given to taking necessary measures with priority, and countermeasures can be taken systematically.

  In the present embodiment, since the abnormality occurrence is diagnosed based on the initial concentration of DBDS, not the copper sulfide production amount, it is easy to set the threshold value. The amount of copper sulfide generated calculated according to the present invention indicates the total amount of copper sulfide generated in the oil-filled electrical device, and it is not easy to specify the location where the generated copper sulfide adheres. This is because the initial concentration of DBDS is proportional to the copper sulfide production rate, and it is easier to set the threshold based on the initial concentration of DBDS.

Example 1
First, an insulating oil to which 4000 ppm of DBPC that has been confirmed to contain no sulfur in ASTM D 1275B was prepared. Next, DBDS was added to this insulating oil to a concentration of 300 ppm. After 4 grams of this insulating oil and a copper plate are sealed in a bottle with an internal volume of 10 cc, the gas inside is replaced with nitrogen and a rubber stopper is applied, then at 150 ° C. for a predetermined time (1, 2, 3, 5, 7, 9 hours).

  The insulating oil after heating for a predetermined time is analyzed by GC / MS, and the reaction value of the radical generated from DBPC and the radical generated from DBDS is obtained using the area value of the fragment ion peak of M / Z = 310. The concentration of the product (compound of FIG. 2) was measured. Separately, the amount of copper sulfide produced on the copper plate was measured by the change in weight of the copper plate. The concentration of bibenzyl in the insulating oil was also measured by GC / MS.

  FIG. 3 shows the relationship between the concentration of the compound in FIG. 2 and the amount of copper sulfide produced. In addition, the relationship between the amount of bibenzyl and the amount of copper sulfide produced is also shown in FIG.

  As shown in FIG. 3, there is a good correlation between the amount of the compound of FIG. 2 and the amount of copper sulfide produced. From this, it can be seen that the amount of copper sulfide produced at that temperature can be determined by measuring the amount of the compound in FIG.

  On the other hand, even if the amount of copper sulfide produced increases, the amount of bibenzyl produced hardly increases, indicating that there is no correlation between the amount of bibenzyl produced and the amount of copper sulfide produced.

  For comparison, an experiment similar to the above was performed except that DBPC was not added to the insulating oil. As a result, the relationship between the amount of bibenzyl obtained and the amount of copper sulfide produced is shown in FIG. In contrast to FIG. 3, there is a good correlation between the amount of bibenzyl and the amount of copper sulfide produced in FIG. From this, it can be seen that the method of the present invention is particularly useful for insulating oil to which DBPC is added.

  From the above, by measuring the amount of reaction products of radicals generated from DBPC and radicals generated from DBDS, the amount of copper sulfide generated can be made more accurate even in insulating oil to which DBPC is added. It can be seen that it can be obtained.

(Example 2)
<In nitrogen>
The same experiment as in Example 1 was performed, and in addition to the compound of FIG. 2, benzyl alcohol, benzaldehyde, benzoic acid, dibenzyl sulfoxide, bibenzyl, and dibenzyl sulfide contained in the insulating oil were measured as gas chromatographs. / Analyzed with a mass spectrometer (GC / MS) to determine the concentration of these compounds. Then, each concentration of the product was converted into the molar concentration of the benzene ring, and the total molar concentration (N) obtained by adding them was determined.

<In the air>
Further, an experiment similar to that in Example 1 was conducted except that a stainless steel pipe having an inner diameter of several millimeters was passed through the rubber plug so that the insulating oil could freely come into contact with air. The total molar concentration (N) of the ring was determined.

  FIG. 5 shows the relationship between the amount of compound produced in FIG. 2 and the amount of copper sulfide produced in the above-described experiment in air and nitrogen. As shown in FIG. 5, there is a good correlation between the amount of compound produced in FIG. 2 and the amount of copper sulfide in nitrogen, and the amount of copper sulfide at that temperature can be determined by determining the amount of compound produced in FIG. Can be sought. However, it can be seen that in air, the amount of compound produced in FIG. 2 decreases, and the amount of copper sulfide produced cannot be determined from the amount of compound produced in FIG.

  Next, FIG. 6 shows the relationship between N and the amount of copper sulfide produced for the above experiments in air and nitrogen. As shown in FIG. 6, there is a good correlation between N and the amount of copper sulfide, and by obtaining N, the amount of copper sulfide at that temperature can be obtained.

  Further, as is apparent from FIG. 6, substantially the same linear relationship is shown in air and nitrogen. From this result, N is used (in addition to the compound of FIG. 2, at least one compound selected from the group consisting of benzyl alcohol, benzaldehyde, benzoic acid, dibenzyl sulfoxide, toluene, bibenzyl and dibenzyl sulfide is used. Sulfidation without being influenced by the oxygen concentration in the insulating oil) by measuring and measuring each measured concentration based on the total molar concentration (N) converted into the molar concentration of the benzene ring (estimating the amount of copper sulfide produced) It can be seen that the amount of copper produced can be determined. That is, the amount of copper sulfide produced can be accurately estimated regardless of the type of transformer (for example, an open type transformer or a sealed transformer).

(Example 3)
The same experiment as in Example 2 was performed to determine N, and the residual concentration of DBDS in the insulating oil was measured by GC / MS to determine the amount of DBDS decrease (initial concentration-residual concentration). FIG. 7 shows the relationship between the obtained N and the DBDS reduction amount.

  As shown in FIG. 7, N and the amount of DBDS decrease show a good correlation. From this, it can be seen that by analyzing the insulating oil collected from the aged transformer and obtaining N, the amount of decrease in DBDS can be obtained, and the initial concentration of DBDS can be obtained from the above equation (1).

  Further, as is apparent from FIG. 7, the same linear relationship is shown in air and nitrogen. Therefore, it can be seen that by using N, the initial concentration of DBDS can be determined regardless of the oxygen concentration in the insulating oil. That is, the initial concentration of DBDS can be accurately estimated regardless of the type of transformer (for example, an open type transformer or a sealed transformer).

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Claims (8)

A method for estimating the amount of copper sulfide produced in oil-filled electrical equipment,
(1) a first step of measuring an amount of one or more specific products contained in insulating oil collected from the oil-filled electrical device; and
(2) including a second step of estimating the production amount of the copper sulfide based on the amount of the specific product,
The specific product includes a reaction product of a radical generated from 2,6-di-t-butyl-4-methylphenol and a radical generated from dibenzyl disulfide.   The said oil-filled electrical equipment is an oil-filled electrical equipment in which the insulating oil containing 2, 6-di-t-butyl-4-methylphenol was used, The estimation method of the copper sulfide production amount of Claim 1 .   The insulating oil collected from the oil-filled electrical equipment is analyzed by a gas chromatograph mass spectrometer, and the peak area value of the fragment ion peak of M / Z = 310 or the fragment ion peak of M / Z = 219, Alternatively, using the sum of these peak area values, the reaction product of the radical generated from 2,6-di-t-butyl-4-methylphenol and the radical generated from dibenzyl disulfide The estimation method of the copper sulfide production amount of Claim 1 or 2 which calculates | requires quantity.   The one or more specific products further comprise at least one compound selected from the group consisting of benzyl alcohol, benzaldehyde, benzoic acid, dibenzyl sulfoxide, bibenzyl and dibenzyl sulfide. The estimation method of the copper sulfide production amount in any one of. The second step includes
Converting each concentration of the one or more specific products into a molar concentration of the benzene ring, and calculating a total molar concentration summing them, 2-1 step; and
The estimation method of the copper sulfide production amount in any one of Claims 1-4 including the 2nd-2 process of estimating the production amount of the said copper sulfide based on the said total molar concentration.   An abnormality occurrence diagnosis method for diagnosing occurrence of an abnormality in an oil-filled electrical device based on the production amount of the copper sulfide estimated using the method according to claim 1. A method for estimating the initial concentration of dibenzyl disulfide in insulating oil in oil-filled electrical equipment,
(1) a first step of measuring the concentration of one or more specific products contained in the insulating oil collected from the oil-filled electrical device; and
(2) including a second step of estimating an initial concentration of the dibenzyl disulfide based on the concentration of the one or more specific products.
The one or more specific products include a reaction product of a radical generated from 2,6-di-t-butyl-4-methylphenol and a radical generated from dibenzyl disulfide, and benzyl alcohol. At least one compound selected from the group consisting of benzaldehyde, benzoic acid, dibenzyl sulfoxide, bibenzyl and dibenzyl sulfide,
The second step includes
Step 2-1 for converting each concentration of the one or more specific products into a molar concentration of benzene rings and calculating a total molar concentration of the total concentrations.
From the total molar concentration, step 2-2 for calculating the amount of dibenzyl disulfide decrease using a calibration curve prepared in advance, and
A method for estimating an initial concentration of dibenzyl disulfide in insulating oil, comprising a second to third step of calculating an initial concentration of the dibenzyl disulfide from the concentration of the dibenzyl disulfide and the amount of decrease in the dibenzyl disulfide.   A diagnostic method for the possibility of occurrence of an abnormality, wherein an abnormality occurrence of an oil-filled electrical device is diagnosed based on the initial concentration of dibenzyl disulfide estimated using the method according to claim 7.

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