JP2010008175A - Method and device for analyzing gas in-oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To precisely and quickly analyzing a trace amount of gas component dissolved in an insulation oil. <P>SOLUTION: An analyzing device of a gas in-oil includes: an extracting means for extracting the gas dissolved in a specimen oil; a gas storage means for temporarily storing the extracted dissolved gas; an exhausting means for exhausting the air remaining in the extracting means and the gas storage means; a gas analyzing means analyzing the extracted dissolved gas; a data processing means operating and processing the detection signal outputted from the gas analyzing means; and a flow passage switching means switching the gas storage means to the state which allows communication with the gas extracting means or the gas analyzing means. The gas storage means includes a gas storage pipe where the dissolved gas is stored and a pressure detecting means for detecting the pressure inside of the gas storage pipe. When the pressure of the inside of the gas storage pipe reaches the predetermined pressure, the flow passage switching means is switched so that the total amount of the stored dissolves gas is injected into the inside of the gas analyzing means. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an analysis method and an analysis apparatus for gas components dissolved in insulating oil used in oil-filled equipment such as a transformer.

  When abnormal phenomena such as local overheating and discharge occur inside oil-filled equipment such as transformers, gases such as carbon monoxide, carbon dioxide, hydrogen, methane, ethane, ethylene, and acetylene are generated and dissolved in insulating oil. . Various gases dissolved in the insulating oil are used as indicators when performing abnormality diagnosis and deterioration diagnosis of oil-filled equipment by qualitative and quantitative analysis using a gas analyzer such as a gas chromatograph. Yes. Among the various gas components, most of acetylene is generated due to a discharge phenomenon, and therefore it is desirable that the acetylene can be detected at an early stage (a small amount of stage) from the viewpoint of preventive maintenance.

  As a technique for analyzing a very small amount of gas components dissolved in the insulating oil with high accuracy, for example, a technique described in Patent Document 1 can be cited. In Patent Document 1, a small amount of dissolved gas in oil (hereinafter referred to as dissolved gas) bubbled and extracted using an inert gas is cooled and condensed and accumulated, and the accumulated dissolved gas is heated and vaporized for trapping. The sample is collected in a collection container, and then the high concentration dissolved gas collected in the collection container is analyzed by a gas chromatograph.

Japanese Patent Laid-Open No. 5-288654

  However, in the technique described in Patent Document 1, means for cooling and condensing the dissolved gas and means for heating and vaporizing the accumulated dissolved gas are required, so that the configuration of the apparatus is complicated. In addition, there is a problem that the maintenance management of each means becomes complicated. Moreover, the dissolved gas is once cooled and condensed and accumulated, and the accumulated dissolved gas is heated and vaporized again, so that there is a problem that it takes time and effort to collect the dissolved gas. .

  Moreover, when extracting the dissolved gas in sample oil by bubbling like the technique of patent document 1, it is connected to the connection pipe | tube through which dissolved gas distribute | circulates, the trap pipe | tube with which dissolved gas is condensed, etc. by capillary phenomenon etc. The sample oil often invaded. In this state, if the dissolved gas in the sample oil is continuously extracted, contamination may occur and hinder accurate gas analysis. Therefore, in general, every time dissolved gas is extracted, the contamination gas is contaminated. It was necessary to check for the existence of a nation, which was very troublesome.

  In view of the above-mentioned various problems, the present invention enables high-sensitivity and quick analysis of trace gas components dissolved in insulating oil without using a special apparatus, and further, contamination is not caused. An object of the present invention is to provide an analysis method and an analysis apparatus for gas in oil capable of preventing generation.

  According to the first aspect of the present invention, the step of exhausting the remaining air in the sample oil injection container, the gas storage pipe and the gas flow pipe by the exhaust means, and the sample oil in the sample oil injection container having a predetermined degree of vacuum by the exhaust. Injecting an inert gas into the sample oil to extract a gas component dissolved in the sample oil; and extracting the extracted gas component into the gas storage pipe; The step of storing until a predetermined pressure is reached, and the extraction of the gas component is stopped when the inside of the gas storage pipe reaches the predetermined pressure, and the gas component stored in the gas storage pipe is completely gasified by the carrier gas. The method comprises a step of injecting into the analyzing means and a step of analyzing the gas component injected into the gas analyzing means.

  According to the second aspect of the present invention, there is provided a step of exhausting the remaining air in the sample oil injection container, the gas storage pipe and the gas circulation pipe by the exhaust means, and the sample oil in the sample oil injection container having a predetermined degree of vacuum by the exhaust. A step of injecting an inert gas into the sample oil to extract a gas component dissolved in the sample oil; and a column capacity of the gas analysis means for extracting the extracted gas component into a gas storage pipe A step of storing until a predetermined volume exceeding the predetermined amount, and stopping the extraction of the gas component when a predetermined volume of the gas component is stored in the gas storage pipe, and the gas component stored in the gas storage pipe The method is characterized by comprising a step of injecting the whole amount into the gas analysis means by a carrier gas and a step of analyzing the gas component injected into the gas analysis means.

  According to the third aspect of the present invention, the step of exhausting the remaining air in the sample oil injection container, the gas storage pipe and the gas flow pipe by the exhaust means, and the sample oil in the sample oil injection container having a predetermined degree of vacuum by the exhaust. Injecting an inert gas into the sample oil to extract a gas component dissolved in the sample oil; and extracting the extracted gas component into the gas storage pipe; The step of storing until a predetermined pressure is reached, and the extraction of the gas component is stopped when the inside of the gas storage pipe reaches the predetermined pressure, and the gas component stored in the gas storage pipe is completely gasified by the carrier gas. A step of injecting into the analysis means, a step of analyzing the gas component injected into the gas analysis means, and after analyzing the gas component, the backwash gas is circulated from the gas storage pipe side to the sample oil injection container side, Ingredient extraction The gas reserve tube and the sample oil and penetrated into the gas distribution tube, characterized in that it consists of a step of discharging the oil sample remaining in the sample oil injection vessel to the outside by the capillary phenomenon or the like.

  The invention described in claim 4 includes a step of exhausting the remaining air in the sample oil injection container, the gas storage pipe and the gas circulation pipe by the exhaust means, and the sample oil is put into the sample oil injection container having a predetermined degree of vacuum by the exhaust. A step of injecting an inert gas into the sample oil to extract a gas component dissolved in the sample oil; and a column capacity of the gas analysis means for extracting the extracted gas component into a gas storage pipe A step of storing until a predetermined volume exceeding the predetermined amount, and stopping the extraction of the gas component when a predetermined volume of the gas component is stored in the gas storage pipe, and the gas component stored in the gas storage pipe A step of injecting the total amount of gas into the gas analysis means by the carrier gas; a step of analyzing the gas component injected into the gas analysis means; It comprises a step of circulating and discharging the sample oil that has entered the gas storage pipe and the gas flow pipe due to capillarity or the like during extraction of the gas component, or the sample oil remaining in the sample oil injection container to the outside. And

  The invention according to claim 5 remains in the extraction means for extracting the dissolved gas in the sample oil, the gas storage means for temporarily storing the extracted dissolved gas, and the extraction means and the gas storage means. An exhaust means for exhausting air; a gas analysis means for analyzing the extracted dissolved gas; a data processing means for computing a detection signal output from the gas analysis means; and a gas storage means for extracting means, or In the oil-in-gas analyzer comprising a flow path switching means for switching to a state communicating with the gas analysis means, the gas storage means includes a gas storage pipe for storing dissolved gas, and a pressure in the gas storage pipe. Pressure detecting means for detecting, and switching the flow path switching means when the inside of the gas storage pipe reaches a predetermined pressure so as to inject the entire amount of the stored dissolved gas into the gas analyzing means. Characterized in that it was.

  The invention according to claim 6 remains in the extraction means for extracting the dissolved gas in the sample oil, the gas storage means for temporarily storing the extracted dissolved gas, and the extraction means and the gas storage means. An exhaust means for exhausting air; a gas analysis means for analyzing the extracted dissolved gas; a data processing means for computing a detection signal output from the gas analysis means; and a gas storage means for extracting means, or And an in-oil gas analyzer having a flow path switching means for switching to a state communicating with the gas analysis means, wherein the gas storage means is a gas storage capable of storing a dissolved gas having a capacity exceeding the column capacity of the gas analysis means. And when the predetermined volume of dissolved gas exceeding the column capacity of the gas analysis means is stored in the gas storage pipe, the flow path switching means is switched to remove the stored dissolved gas from the gas analyzer. Characterized by being configured to the total amount injected into the inner.

  According to a seventh aspect of the invention, in the gas-in-oil analyzer according to the fifth or sixth aspect of the invention, the backwashing means for circulating the backwashing gas from the gas storage means side to the extraction means side is provided. After the analysis of the dissolved gas is completed, the flow path switching means is switched, and the sample oil that has entered the gas storage means due to capillary action or the like during extraction of the dissolved gas or the sample oil remaining in the extraction means is externally removed by backwashing gas. It is characterized by being configured to discharge to

  According to the first aspect of the present invention, extraction of gas components is continued until the inside of the gas storage pipe reaches a predetermined pressure, and the gas storage pipe is stored in the gas storage pipe when the inside of the gas storage pipe reaches the predetermined pressure. Since the entire amount of the gas component is injected into the gas analysis means, it is possible to inject a large amount of gas component into the gas analysis means by a simple method of controlling the pressure in the gas storage pipe. Even if a small amount of acetylene is dissolved in the sample oil, the acetylene can be detected with high sensitivity and used as an index for abnormality diagnosis and deterioration diagnosis of oil-filled equipment. In addition, since the gas component stored in the gas storage pipe is always injected into the gas analysis means when the pressure becomes constant, the injection amount into the gas analysis means is always constant, and the reproducibility of gas analysis is constant. Can be improved.

  According to the second aspect of the present invention, extraction of the gas component is continued until a predetermined volume of the gas component exceeding the column capacity of the gas analyzing means is stored in the gas storage pipe, and a predetermined volume of the gas storage pipe is stored in the gas storage pipe. Since the gas component stored in the gas storage pipe is completely injected into the gas analysis means when the gas component is stored, the capacity of the gas component stored in the gas storage pipe is controlled simply. By this method, it becomes possible to inject a large amount of gas components into the gas analyzing means. As a result, even if a small amount of acetylene is dissolved in the sample oil, the acetylene is detected with high sensitivity, and It can serve as an index for abnormality diagnosis and deterioration diagnosis of input devices. In addition, since the gas component extracted from the sample oil is always injected into the gas analysis means when it is stored in a certain amount in the gas storage pipe, the injection amount into the gas analysis means is always constant, Repeatability can be improved.

  According to the third aspect of the invention, in addition to the effect of the first aspect of the invention, after the gas analysis is completed, the carrier gas is circulated from the gas storage pipe side to the sample oil injection container side to extract the gas component. The sample oil that has entered the gas storage pipe and gas distribution pipe due to capillary action and the sample oil remaining in the sample oil injection container are discharged to the outside, so contamination is possible even when performing continuous gas analysis. This is very convenient because it is possible to prevent the occurrence of occurrence and perform an accurate analysis and it is not necessary to check the presence or absence of contamination each time a gas analysis is performed. Further, by allowing the carrier gas to flow from the gas storage pipe side to the sample oil injection container side, it is possible to satisfactorily prevent the sample oil from diffusing and entering the gas analysis means side.

  According to the invention described in claim 4, in addition to the effect of the invention described in claim 2, after the gas analysis is completed, the carrier gas is circulated from the gas storage pipe side to the sample oil injection container side to extract the gas component. The sample oil that has entered the gas storage pipe and gas distribution pipe due to capillary action and the sample oil remaining in the sample oil injection container are discharged to the outside, so contamination is possible even when performing continuous gas analysis. This is very convenient because it is possible to prevent the occurrence of occurrence and perform an accurate analysis and it is not necessary to check the presence or absence of contamination each time a gas analysis is performed. Further, by allowing the carrier gas to flow from the gas storage pipe side to the sample oil injection container side, it is possible to satisfactorily prevent the sample oil from diffusing and entering the gas analysis means side.

  According to the fifth aspect of the present invention, the pressure in the gas storage pipe is monitored by the pressure detection means, and when the pressure in the gas storage pipe reaches a predetermined pressure, the flow path switching means is switched and stored in the gas storage pipe. Therefore, it is possible to easily inject a large amount of dissolved gas into the gas analysis means without using a special device. Even if a small amount of acetylene is dissolved therein, the acetylene can be detected with high sensitivity and used as an index for abnormality diagnosis and deterioration diagnosis of oil-filled equipment. In addition, since the dissolved gas stored in the gas storage pipe is always injected into the gas analysis means at a constant pressure, the amount of injection into the gas analysis means is always constant, and the gas analysis is repeatedly reproduced. Can be improved.

  According to the sixth aspect of the present invention, a gas storage pipe capable of storing a dissolved gas having a capacity exceeding the column capacity of the gas analysis means is provided, and a predetermined volume of dissolved gas exceeding the column capacity of the gas analysis means is provided in the gas storage pipe. When the gas is stored, the flow path switching means is switched to inject the entire amount of dissolved gas stored in the gas storage pipe into the gas analysis means, so that the gas analysis means can be used without using a special device. As a result, even if a small amount of acetylene is dissolved in the sample oil, the acetylene can be detected with high sensitivity to diagnose abnormalities in oil-filled equipment. It can be used as an index for diagnosis of deterioration. In addition, since the gas component extracted from the sample oil is always injected into the gas analysis means when it is stored in a certain amount in the gas storage pipe, the injection amount into the gas analysis means is always constant, Repeatability can be improved.

  According to the seventh aspect of the present invention, after the analysis of the dissolved gas by the gas analyzing means is completed, the backwashing gas is circulated from the gas storage means side to the extracting means side by the backwashing means, and the capillaries are extracted when the dissolved gas is extracted. Since the sample oil that has entered the gas storage means due to a phenomenon or the like and the sample oil remaining in the extraction means are discharged to the outside, it is possible to prevent contamination even when performing continuous gas analysis. This is very convenient because it can prevent and perform an accurate analysis and does not need to check the presence or absence of contamination each time a gas analysis is performed. Further, by allowing the backwash gas to flow from the gas storage means side to the extraction means side, it is possible to satisfactorily prevent the sample oil from diffusing and entering the gas analysis means side.

  Hereinafter, the best mode for carrying out the present invention will be described with reference to FIGS. 1 and 2, reference numeral 1 denotes an oil-in-gas analyzer according to the present invention, and the gas analyzer 1 is dissolved in sample oil collected from oil-filled equipment such as a transformer as shown in FIGS. Extraction means 2 for extracting gas components (hereinafter referred to as dissolved gas), gas storage means 11 for temporarily storing the extracted dissolved gas, and exhausting air remaining in the extraction means 2 and the gas storage means 11 Exhaust means 15, gas analysis means 19 for analyzing the dissolved gas stored in the gas storage means 11, data processing means 25 for calculating the detection signal output from the gas analysis means 19, and the gas A flow path switching means 26 for switching the storage means 11 to a state communicating with the extraction means 2 or the gas analysis means 19 is schematically configured. The configuration of each means 2, 11, 15, 19, 25, 26 will be described below with reference to FIGS.

  First, the configuration of the extraction unit 2 will be described. In FIGS. 1 and 2, 3 is a sample oil injection container (hereinafter referred to as an injection container) into which sample oil 4 collected from an oil-filled device (not shown) such as a transformer is injected, and 5 is a sample in the injection container 3. It is a sample oil injection tube for injecting oil 4. Reference numeral 6 denotes a discharge pipe for discharging the sample oil 4 from the injection container 3, and 7 denotes a first on-off valve provided in the middle of the discharge pipe 6. 8 is for bubbling an inert gas for bubbling (for example, a gas having the same component (helium, argon, etc.) as a carrier gas supplied to the gas analyzing means 19 described later) into the sample oil 4 injected into the injection container 3. The first gas supply pipe 9 is a second on-off valve provided in the middle of the first gas supply pipe 8. Reference numeral 10 denotes a first gas circulation pipe that connects the injection container 3 and a flow path switching means 26 described later. The first gas circulation pipe 10 is extracted from the sample oil 4 in the injection container 3. Dissolved gas circulates.

  Next, the configuration of the gas storage unit 11 will be described. 1 and 2, 12 is a gas storage pipe in which the dissolved gas extracted by the extraction means 2 is temporarily stored, and 13 is a pressure detection means for detecting the pressure in the gas storage pipe 12. 14a is a second gas flow pipe that connects one end of the gas storage pipe 12 and a flow path switching means 26, which will be described later, and 14b is a connection between the other end of the gas storage pipe 12 and a flow path switching means 26, which will be described later. It is the 3rd gas distribution pipe to do.

  Next, the configuration of the exhaust means 15 will be described. 1 and 2, 16 is an exhaust pipe having one end connected to a flow path switching means 26 described later, and 17 is an on-off valve provided in the middle of the exhaust pipe 16. 18 is connected to the other end of the exhaust pipe 16, and the air remaining in the injection container 3, the first gas circulation pipe 10, the gas storage pipe 12, the second and third gas circulation pipes 14a and 14b. It is a vacuum pump for exhausting.

  Next, the configuration of the gas analysis means 19 will be described. 1 and 2, 20 is a separation column for separating dissolved gas into single components, 21 is an inlet provided on the inlet side of the separation column 20, 22 is provided on the outlet side of the separation column 20, and the separation A detector for detecting a gas component separated by the column 20, a fourth gas flow pipe for connecting the inlet 21 and a flow path switching means 26 described later, and a constant temperature for storing the separation column 20. It is a tank. In the present invention, as the separation column 20, for example, a wide bore capillary column having an inner diameter of about 0.5 mm to 1.0 mm capable of high sensitivity and analysis in a short time was used. The inlet 21 is a splitless inlet that can inject the entire amount of dissolved gas transferred from the gas storage pipe 12 by the carrier gas into the separation column 20. Further, the detector 22 is, for example, a flame ionization detector (FID) capable of detecting acetylene.

  Next, the data processing means 25 performs arithmetic processing on the detection signal output from the detector 22 corresponding to the amount of each gas component detected by the detector 22 of the gas analyzing means 19, and the result is chromatogram. Are displayed and output, and stored as data used for deterioration diagnosis and abnormality determination.

  Subsequently, the flow path switching means 26 comprises, for example, a six-way valve, and is connected to the first to fourth gas flow pipes 10, 14a, 14b, 23, the exhaust pipe 16, and a carrier gas supply source (not shown). The second gas supply pipes 27 are respectively connected to predetermined positions. Then, by the switching operation of the flow path switching means 26, the gas storage pipe 12 communicates with the extraction means 2 and the exhaust means 15 (see FIG. 1), or the gas storage pipe 12 is connected to the second gas supply pipe 27 and the gas analysis. It is configured to communicate with the means 19 (see FIG. 2).

  The first and second gas supply pipes 8 and 27 are connected to the same gas supply source (not shown).

  Next, the operation of the present invention will be described. First, as shown in FIG. 1, the flow path switching means 26 communicates with the second gas supply pipe 27 and the gas analysis means 19, and the gas storage means 11 communicates with the extraction means 2 and the exhaust means 15. It has been switched to the state. In this state, a carrier gas (helium, argon, etc.) from a carrier gas supply source (not shown) flows into the gas analysis means 19 through the second gas supply pipe 27 → the flow path switching means 26 → the gas flow pipe 23. ing. On the other hand, the first on-off valve 7 provided in the middle of the discharge pipe 6, the second on-off valve 9 provided in the middle of the first gas supply pipe 8, and the sample oil injection pipe 5 are closed, and the exhaust pipe 16 The vacuum pump 18 is started in a state where the third on-off valve 17 provided in the middle is opened, and remains in the injection container 3, the first to third gas flow pipes 10, 14 a, 14 b and the gas storage pipe 12. Exhaust air. When the inside of the injection container 3, the first to third gas flow pipes 10, 14 a, 14 b and the gas storage pipe 12 reaches a predetermined degree of vacuum, a third on-off valve 17 provided in the middle of the exhaust pipe 16. Close.

  Subsequently, sample oil 4 collected from an oil-filled device such as a transformer (not shown) using a syringe or the like is injected into the injection container 3 through the sample oil injection pipe 5 (see FIG. 1). At this time, it goes without saying that the first on-off valve 7 provided in the middle of the discharge pipe 6 is closed. Thereafter, the second on-off valve 9 provided in the middle of the first gas supply pipe 8 is opened, and an inert gas (the same component as the carrier gas) is injected into the injection container 3 from a gas supply source (not shown). The first oil supply pipe 8 immersed in the sample oil 4 is jetted into the sample oil 4 from the tip. Thereby, the dissolved gas such as acetylene dissolved in the sample oil 4 is extracted from the sample oil 4. Then, the dissolved gas extracted from the sample oil 4 is passed through the first gas flow pipe 10 → the flow path switching means 26 → the second gas flow pipe 14 a from the injection container 3 by the inert gas, and the gas storage pipe 12. And is stored in the gas storage pipe 12. When extracting the dissolved gas by the so-called bubbling method as described above, as shown in FIG. 3, the extraction amount of the dissolved gas is large at the beginning of extraction and decreases with time. Almost all of the dissolved gas is stored.

  Here, an object of the present invention is to detect a trace amount of acetylene dissolved in the sample oil 4. In the present invention, a wide bore capillary column is used as the separation column 20 in the gas analysis means 19 so that the dissolved gas extracted from the sample oil 4 can be analyzed with high sensitivity and in a short time. If a capillary column is used, dissolved gas can be analyzed with high sensitivity and in a short time as described above. However, the capillary column is a packed column (also referred to as a packed column) used for general gas analysis. Since the diameter dimension is small compared to the above, there is a disadvantage that the amount of gas that can be injected is small. If the amount of dissolved gas that can be injected is small, it is difficult to detect a small amount of acetylene in the dissolved gas. Therefore, in the present invention, a small amount of acetylene is obtained by injecting the dissolved gas at the injection limit amount of the separation column 20. I try to detect it.

  That is, in the present invention, the pressure detection means 13 for detecting the pressure in the gas storage pipe 12 is provided, and the extraction of the dissolved gas is continued until the inside of the gas storage pipe 12 reaches a predetermined pressure. As described above, by increasing the pressure in the gas storage pipe 12, a large amount of dissolved gas can be injected into the separation column 20. The predetermined pressure is a pressure larger than the column inlet pressure, for example, a pressure at which the peak shape of acetylene is not significantly collapsed in the chromatogram (as confirmed by the present inventors through experiments, For example, when the column inlet pressure is 100 kPa, the limit is about 400 kPa, which is four times that pressure.

  When the gas storage pipe 12 reaches a predetermined pressure, the second on-off valve 9 provided in the middle of the first gas supply pipe 8 is closed to stop the supply of the inert gas (that is, dissolved). Gas extraction is stopped), and the flow path switching means 26 is switched to a state where the gas storage pipe 12 communicates with the second gas supply pipe 27 and the gas analysis means 19 as shown in FIG. As a result, the dissolved gas stored in the gas storage pipe 12 is transferred to the third gas flow pipe 14b → the channel switching means 26 → the fourth by the carrier gas supplied via the second gas supply pipe 27. The gas is transferred through the gas flow pipe 23, and the whole amount is injected into the separation column 20 through the injection port 21. The dissolved gas injected into the separation column 20 is sent to the detector 22 in a state of being separated for each single component, and each gas component is detected by the detector 22. Information of each gas component detected by the detector 22 is output to the data processing means 25 as an electrical signal (detection signal), and arithmetic processing is performed in the data processing means 25. The result of the arithmetic processing is, for example, Is output as a chromatogram.

  In the present invention, since the dissolved gas is injected into the separation column 20 at a pressure larger than the inlet pressure of the separation column 20, a shock peak appears in the chromatogram due to the impact during the injection. The shock peak does not reach the position where the peak of acetylene to be detected in the invention appears. In the chromatogram, although the peak shape of acetylene does not become sensitive, the injection pressure is controlled so that the peak shape does not collapse significantly, so that acetylene can be quantified well from the peak area.

  When the analysis by the gas analyzing means 19 is completed, the sample oil 4 in the injection container 3 is discharged by opening the first on-off valve 7 provided in the middle of the discharge pipe 6, and when the discharge is completed, The first on-off valve 7 is closed again. Further, the flow path switching means 26 is switched from the state shown in FIG. 2 to the state shown in FIG. 1 to prepare for the next gas analysis. Thereafter, when the gas analysis is performed, the above operation may be repeated.

  As described above, in the present invention, the extraction of the dissolved gas is continued until the inside of the gas storage pipe 12 reaches a predetermined pressure, and the flow path switching means 26 is obtained when the inside of the gas storage pipe 12 reaches the predetermined pressure. Since the dissolved gas stored in the gas storage pipe 12 is injected into the separation column 20 of the total gas analysis means 19, a large amount of dissolved gas can be injected into the separation column 20. In combination with the use of a capillary column as the separation column 20, a small amount of acetylene dissolved in the sample oil 4 can be detected quickly and with high sensitivity, and abnormality diagnosis or deterioration diagnosis of the oil-filled equipment is performed. It can be used as an indicator. In addition, since the dissolved gas stored in the gas storage pipe 12 is always injected into the separation column 20 of the gas analyzing means 19 at a constant pressure, the injection amount into the separation column 20 is always constant. Thus, the reproducibility of gas analysis can be improved.

  Next, a second embodiment of the present invention will be described with reference to FIGS. The difference between the first embodiment and the second embodiment is that after performing the gas analysis, the backwash gas is supplied from the gas storage pipe 12 side to the injection container 3 side (that is, the direction opposite to the flow direction of the dissolved gas). The sample oil 4 that has entered the gas storage pipe 12 and the first to third gas circulation pipes 10, 14a, 14b by capillary action or the like during extraction of the dissolved gas or remains in the injection container 3 The backwashing means 30 for discharging the sample oil 4 to the outside is provided. Hereinafter, the configuration of the backwashing means 30 will be described with reference to FIGS. 4 to 6, the same members as those in the first embodiment will be described using the same reference numerals, and detailed description thereof will be omitted.

  As shown in FIGS. 4 to 6, the backwashing means 30 includes, for example, a three-way valve 31 provided in the middle of the exhaust pipe 16, one end connected to the three-way valve 31, and the other end not shown. A third gas supply pipe 32 connected to a supply source of the working gas, and a fourth on-off valve 33 provided in the middle of the third gas supply pipe 32. The third gas supply pipe 32 may be connected to the same gas supply source (not shown) as the first and second gas supply pipes 8 and 27, or a carrier gas (such as nitrogen or air). You may make it connect with the supply source (not shown) of the gas for backwashing cheaper than inert gas, such as helium and argon.

  Subsequently, the operation of the second embodiment will be described. First, as shown in FIG. 4, in the flow path switching means 26, the gas analysis means 19 and the second gas supply pipe 27 communicate with each other, and the gas storage pipe 12 communicates with the extraction means 2 and the exhaust means 15. The three-way valve 31 of the backwashing means 30 is switched to a state where the flow path switching means 26 and the exhaust means 15 are communicated with each other. In this state, a carrier gas (helium, argon, etc.) from a carrier gas supply source (not shown) passes through the second gas supply pipe 27 → the flow path switching means 26 → the fourth gas circulation pipe 23 and the gas analysis means 19. Is flowing in. On the other hand, the first on-off valve 7 provided in the middle of the discharge pipe 6, the second on-off valve 9 provided in the middle of the first gas supply pipe 8, and the sample oil injection pipe 5 are closed, and the exhaust pipe 16 The vacuum pump 18 is started in a state where the third on-off valve 17 provided in the middle is opened, and remains in the injection container 3, the first to third gas flow pipes 10, 14 a, 14 b and the gas storage pipe 12. Exhaust air. At this time, the three-way valve 31 provided in the middle of the exhaust pipe 16 is in a state where the flow path switching means 26 and the vacuum pump 18 are in communication with each other as shown in FIG. The air remaining in the third gas circulation pipes 10, 14a, 14b and the gas storage pipe 12 can be exhausted satisfactorily. When the inside of the injection container 3, the first to third gas flow pipes 10, 14 a, 14 b and the gas storage pipe 12 reaches a predetermined degree of vacuum, a third on-off valve 17 provided in the middle of the exhaust pipe 16. Close.

  Next, the sample oil 4 collected by using a syringe or the like from an oil-filled device such as a transformer (not shown) is injected into the injection container 3 through the sample oil injection pipe 5 (see FIG. 4). At this time, it goes without saying that the first on-off valve 7 provided in the middle of the discharge pipe 6 is closed. Thereafter, the on-off valve 9 provided in the middle of the first gas supply pipe 8 is opened, and the sample oil 4 in which an inert gas (the same component as the carrier gas) is injected into the injection container 3 from a gas supply source (not shown). The sample oil 4 is ejected from the tip of the first gas supply pipe 8 immersed therein. Thereby, the dissolved gas such as acetylene dissolved in the sample oil 4 is extracted from the sample oil 4. Then, the dissolved gas extracted from the sample oil 4 is passed through the first gas flow pipe 10 → the flow path switching means 26 → the second gas flow pipe 14 a from the injection container 3 by the inert gas, and the gas storage pipe 12. Until the inside of the gas storage pipe 12 reaches a predetermined pressure (a pressure higher than the inlet pressure of the separation column 20, for example, a pressure at which the peak of acetylene does not significantly collapse in the chromatogram). Stored. When extracting the dissolved gas by the so-called bubbling method as described above, as shown in FIG. 3, the extraction amount of the dissolved gas is large at the beginning of extraction and decreases with time. Almost all of the dissolved gas is stored.

  When the gas storage pipe 12 reaches a predetermined pressure, the second on-off valve 9 provided in the middle of the first gas supply pipe 8 is closed to stop the supply of the inert gas (that is, dissolved). Gas extraction is stopped), and the flow path switching means 26 is switched to a state in which the gas storage pipe 12 communicates with the second gas supply pipe 27 and the gas analysis means 19 as shown in FIG. As a result, the dissolved gas stored in the gas storage pipe 12 is transferred to the third gas flow pipe 14b → the channel switching means 26 → the fourth by the carrier gas supplied via the second gas supply pipe 27. The gas is transferred through the gas flow pipe 23, and the whole amount is injected into the separation column 20 through the injection port 21. The dissolved gas injected into the separation column 20 is sent to the detector 22 in a state of being separated for each single component, and each gas component is detected by the detector 22. Information on each gas component detected by the detector 22 is output to the data processing means 25 as an electric signal (detection signal), and the data processing means 25 performs arithmetic processing, and the result of the arithmetic processing is, for example, Is output as a chromatogram.

  In the present invention, since the dissolved gas is injected into the separation column 20 at a pressure larger than the inlet pressure of the separation column 20, a shock peak appears in the chromatogram due to the impact during the injection. The shock peak does not reach the position where the peak of acetylene to be detected in the invention appears. In the chromatogram, although the peak shape of acetylene does not become sensitive, the injection pressure is controlled so that the peak shape does not collapse significantly, so that acetylene can be quantified well from the peak area.

  Subsequently, when the analysis by the gas analyzing means 19 is completed, the first on-off valve 7 provided in the middle of the discharge pipe 6 is opened, and the sample oil 4 in the injection container 3 is discharged. Further, as shown in FIG. 6, the flow path switching means 26 is switched to a state where the gas storage pipe 12 communicates with the extraction means 2 and the exhaust means 15, and the three sides of the backwashing means 30 provided in the middle of the exhaust pipe 16. The valve 31 is switched to a state where the flow path switching means 26 and the third gas supply pipe 32 are in communication. In this state, when the fourth on-off valve 33 provided in the middle of the third gas supply pipe 32 is opened, the backwashing gas is supplied from a gas supply source (not shown) to the third gas supply pipe 32 → the three-way valve 31 → The exhaust pipe 16 → the flow path switching means 26 → the third gas flow pipe 14 b → the gas storage pipe 12 → the second gas flow pipe 14 a → the flow path switching means 26 → the first gas flow pipe 10 and the inside of the injection container 3 Flow into. As a result, the sample oil 4 that has entered the first to third gas flow pipes 10, 14a, 14b and the gas storage pipe 12 by capillary action or the like during extraction of the dissolved gas, or the sample oil 4 remaining in the injection container 3 is obtained. Is preferably discharged from the discharge pipe 6 to the outside of the injection container 3 by the backwash gas.

  When the first to third gas flow pipes 10, 14a, 14b, the gas storage pipe 12 and the backwashing in the injection container 3 (discharge of the sample oil 4) with the backwashing gas are completed as described above, The fourth on-off valve 33 provided in the middle of the third gas supply pipe 32 is closed to stop the supply of the backwash gas. Further, as shown in FIG. 4, the three-way valve 31 of the backwashing means 30 is switched to a state in which the flow path switching means 26 and the exhaust means 15 communicate with each other, and the first on-off valve 7 provided in the middle of the discharge pipe 6. To prepare for the next gas analysis. Thereafter, when gas analysis is performed, the above operation may be repeated.

  Thus, in the second embodiment of the present invention, as in the first embodiment, in addition to being able to detect a small amount of acetylene dissolved in the sample oil 4 quickly and with high sensitivity, After the completion, the backwashing gas is circulated from the gas storage pipe 12 side to the injection container 3 side, and the first to third gas circulation pipes 10, 14a, 14b and the gas storage pipe are extracted by capillary action or the like when extracting the dissolved gas. Since the sample oil 4 that has entered the interior 12 and the sample oil 4 that remains in the injection container 3 are discharged to the outside, the first to third gas flow pipes 10, 14 a, 14 b and the gas storage pipe 12 are used. By leaving the sample oil 4 in the injection container 3, it is possible to satisfactorily prevent the occurrence of contamination during the next gas analysis and to perform more accurate gas analysis. In addition, it is very convenient because it is not necessary to check for contamination each time gas analysis is performed. Moreover, the sample oil 4 diffuses and penetrates into the gas analysis means 19 side by flowing the backwash gas in the direction opposite to the flow direction of the dissolved gas (that is, from the gas storage pipe 12 side to the injection container 3 side). Can be prevented well.

  Next, a third embodiment of the present invention will be described. The difference between the third embodiment and the first and second embodiments is that the first and second embodiments switch the flow path switching means 26 when the inside of the gas storage pipe 12 reaches a predetermined pressure, The dissolved gas stored in the gas storage pipe 12 is injected into the separation column 20 of the total gas analysis means 19, whereas the third embodiment has a gas analysis means in the gas storage pipe 12. When a predetermined volume of dissolved gas exceeding the capacity of the separation column 20 in 19 is stored, the flow path switching means 26 is switched, and the dissolved gas stored in the gas storage pipe 12 is separated by the total gas analysis means 19. The point is that it is injected into the column 20.

  In other words, in the third embodiment, the dissolved gas storage capacity (capacity) of the gas storage pipe 12 is made larger than the injection capacity (column capacity) of the separation column 20. A predetermined volume of dissolved gas exceeding the column volume can be stored. In addition, when this inventor confirmed by experiment, as a capacity | capacitance of the gas storage pipe 12, the maximum of about 4 times the column capacity was the limit of analysis.

  The operation of the third embodiment will be described below. Since the basic operation is substantially the same as that of the first and second embodiments, detailed description is omitted, and only different portions will be described. Dissolved gas such as acetylene extracted from the sample oil 4 in the injection container 3 of the extraction means 2 is switched from the injection container 3 to the first gas flow pipe 10 → flow path by an inert gas (the same component as the carrier gas). The means 26 is transferred to the gas storage pipe 12 through the second gas flow pipe 14a, and stored in the gas storage pipe 12 until a predetermined capacity exceeding the capacity (column capacity) of the separation column 20 is reached. At this time, the amount (capacity) of the dissolved gas stored in the gas storage pipe 12 is controlled by monitoring the extraction time of the dissolved gas.

  When a predetermined volume of dissolved gas exceeding the column capacity is stored in the gas storage pipe 12, the second on-off valve 9 provided in the middle of the first gas supply pipe 8 is closed to supply the inert gas. While stopping (ie, stopping the extraction of dissolved gas), the flow path switching means 26 is switched to a state where the gas storage pipe 12 communicates with the second gas supply pipe 27 and the gas analysis means 19. Thereby, the dissolved gas stored in the gas storage pipe 12 is transferred from the third gas circulation pipe 14b to the flow path by the carrier gas (helium, argon, etc.) supplied via the second gas supply pipe 27. The switching means 26 is transferred via the fourth gas flow pipe 23, and the entire amount is injected into the separation column 20 through the inlet 21. At this time, the pressure in the gas storage pipe 12 is controlled to be the same as the column inlet pressure.

  As described above, in the third embodiment of the present invention, the extraction of the dissolved gas is continued until a predetermined volume of dissolved gas exceeding the column capacity is stored in the gas storage pipe 12, and the gas storage pipe 12 When a predetermined volume of dissolved gas is stored, the flow path switching means 26 is switched so that the dissolved gas stored in the gas storage pipe 12 is injected into the separation column 20 of the total gas analysis means 19. Therefore, it becomes possible to inject a large amount of dissolved gas into the separation column 20, and in combination with the use of a capillary column as the separation column 20, a small amount of acetylene dissolved in the sample oil 4 can be rapidly and It can be detected with high sensitivity and used as an index when performing abnormality diagnosis or deterioration diagnosis of oil-filled equipment. Further, the dissolved gas extracted from the sample oil 4 is injected into the separation column 20 of the gas analyzing means 19 when a fixed amount is always stored in the gas storage pipe 12, so that the injection amount into the separation column 20 is increased. Is always constant, and the repeatability of gas analysis can be improved.

  In the present invention, the gas analyzing means 19 includes only one separation column 20, but the present invention is not limited to this, and a plurality of separation columns may be provided. In this case, gas components other than acetylene can be detected simultaneously. Further, when a plurality of separation columns are provided, the dissolved gas stationed in one gas storage pipe may be branched and injected into each separation column, or a gas storage pipe corresponding to each separation column. The dissolved gas may be injected into each separation column from each gas storage pipe. Further, when a plurality of separation columns are provided, all the separation columns may be capillary columns, or a capillary column and a packed column may be combined. When a plurality of separation columns are provided, it goes without saying that a detector suitable for the gas component to be detected is connected to the outlet side of each separation column.

  Further, in the present invention, as shown in FIGS. 1 and 2 and FIGS. 4 to 6, the gas storage pipe 12 is provided with a pressure detection means 13 for detecting the pressure in the gas storage pipe 12. Although described as an example, the pressure detection means 13 is connected to any one of the first to third gas flow pipes 10, 14a, 14b and the exhaust pipe 16 that communicate with the gas storage pipe 12 when the dissolved gas is stored. You may make it attach.

In 1st Example of this invention, it is operation | movement explanatory drawing which shows the operation | movement which stores the dissolved gas extracted from the sample oil in a gas storage pipe. In 1st Example, it is operation | movement explanatory drawing which shows the operation | movement which inject | pours the dissolved gas stored in the gas storage pipe into a gas analysis means. It is a figure which shows the relationship between the extraction rate of dissolved gas, and extraction time. In 2nd Example of this invention, it is operation | movement explanatory drawing which shows the operation | movement which stores the dissolved gas extracted from the sample oil in a gas storage pipe. In 2nd Example, it is operation | movement explanatory drawing which shows the operation | movement which inject | pours the dissolved gas stored in the gas storage pipe into a gas analysis means. In 2nd Example, it is operation | movement explanatory drawing which shows the operation | movement which discharges | emits the sample oil which penetrate | invaded in the gas storage pipe and the gas distribution pipe outside.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas analyzer 2 Extraction means 3 Sample oil injection container 4 Sample oil 11 Gas storage means 12 Gas storage pipe 13 Pressure detection means 15 Exhaust means 19 Gas analysis means 20 Separation column 22 Detector 25 Data processing means 26 Flow path switching means 30 Backwashing means

Claims (7)

  A step of exhausting the residual air in the sample oil injection container, the gas storage pipe and the gas circulation pipe by the exhaust means, a step of injecting the sample oil into the sample oil injection container having a predetermined degree of vacuum by the exhaust, and the sample oil An inert gas is blown into the sample oil to extract a gas component dissolved in the sample oil, and the extracted gas component is stored in the gas storage pipe until the inside of the gas storage pipe reaches a predetermined pressure. A step of stopping extraction of gas components when the inside of the gas storage pipe reaches a predetermined pressure, and injecting a gas component stored in the gas storage pipe into the gas analysis means by a carrier gas, And analyzing the gas component injected into the gas analyzing means.   A step of exhausting the residual air in the sample oil injection container, the gas storage pipe and the gas circulation pipe by the exhaust means, a step of injecting the sample oil into the sample oil injection container having a predetermined degree of vacuum by the exhaust, and the sample oil The step of extracting the gas component dissolved in the sample oil by blowing an inert gas into the sample oil, and storing the extracted gas component in the gas storage pipe until the volume reaches a predetermined capacity exceeding the column capacity of the gas analysis means And the extraction of the gas component is stopped when a predetermined volume of the gas component is stored in the gas storage pipe, and the gas component stored in the gas storage pipe is converted into a total gas analysis means by the carrier gas. A method for analyzing a gas in oil, comprising: an injecting step; and a step of analyzing a gas component injected into the gas analyzing means.   A step of exhausting the residual air in the sample oil injection container, the gas storage pipe and the gas circulation pipe by the exhaust means, a step of injecting the sample oil into the sample oil injection container having a predetermined degree of vacuum by the exhaust, and the sample oil An inert gas is blown into the sample oil to extract a gas component dissolved in the sample oil, and the extracted gas component is stored in the gas storage pipe until the inside of the gas storage pipe reaches a predetermined pressure. A step of stopping extraction of gas components when the inside of the gas storage pipe reaches a predetermined pressure, and injecting a gas component stored in the gas storage pipe into the gas analysis means by a carrier gas, Analyzing the gas component injected into the gas analysis means, and after analyzing the gas component, the backwashing gas is circulated from the gas storage tube side to the sample oil injection container side, and the gas component is extracted by capillary action or the like. in front Sample oil and that has entered the gas reserve tube and the gas flow tube, the method analyzes the oil in the gas, characterized in that it consists of a step of discharging the oil sample remaining in the sample oil injection vessel to the outside.   A step of exhausting the residual air in the sample oil injection container, the gas storage pipe and the gas circulation pipe by the exhaust means, a step of injecting the sample oil into the sample oil injection container having a predetermined degree of vacuum by the exhaust, and the sample oil The step of extracting the gas component dissolved in the sample oil by blowing an inert gas into the sample oil, and storing the extracted gas component in the gas storage pipe until the volume reaches a predetermined capacity exceeding the column capacity of the gas analysis means And the extraction of the gas component is stopped when a predetermined volume of the gas component is stored in the gas storage pipe, and the gas component stored in the gas storage pipe is converted into a total gas analysis means by the carrier gas. A step of injecting, a step of analyzing the gas component injected into the gas analyzing means, and after analyzing the gas component, a gas for backwashing is circulated from the gas storage tube side to the sample oil injection container side to Analysis of gas in oil, characterized in that it comprises a step of discharging sample oil that has entered the gas storage pipe and gas distribution pipe due to capillarity during extraction and the sample oil remaining in the sample oil injection container to the outside. Method.   Extraction means for extracting dissolved gas in the sample oil, gas storage means for temporarily storing the extracted dissolved gas, and exhaust means for exhausting air remaining in the extraction means and gas storage means A gas analyzing means for analyzing the extracted dissolved gas, a data processing means for calculating a detection signal output from the gas analyzing means, and a state in which the gas storage means communicates with the extracting means or the gas analyzing means. In the oil-in-gas analyzer comprising the flow path switching means for switching to the gas storage means, the gas storage means includes a gas storage pipe for storing dissolved gas, and a pressure detection means for detecting the pressure in the gas storage pipe. And the flow path switching means is switched when the inside of the gas storage pipe reaches a predetermined pressure, and the total amount of the stored dissolved gas is injected into the gas analysis means. Analyzer of the medium gas.   Extraction means for extracting dissolved gas in the sample oil, gas storage means for temporarily storing the extracted dissolved gas, and exhaust means for exhausting air remaining in the extraction means and gas storage means A gas analyzing means for analyzing the extracted dissolved gas, a data processing means for calculating a detection signal output from the gas analyzing means, and a state in which the gas storage means communicates with the extracting means or the gas analyzing means. In the oil-in-gas analyzer comprising the flow path switching means for switching to the gas storage means, the gas storage means includes a gas storage pipe capable of storing a dissolved gas having a capacity exceeding the column capacity of the gas analysis means, and the inside of the gas storage pipe When a predetermined volume of dissolved gas exceeding the column capacity of the gas analyzing means is stored, the flow path switching means is switched to inject the stored dissolved gas into the gas analyzing means in its entirety. Configured analyzer oil gas, characterized in that the.   A backwashing means for circulating backwashing gas from the gas storage means side to the extraction means side is provided, and after the analysis of the dissolved gas by the gas analysis means is completed, the flow path switching means is switched, and when the dissolved gas is extracted due to capillary phenomenon The sample oil intruding into the gas storage means or the sample oil remaining in the extraction means is configured to be discharged to the outside by backwashing gas. Analysis equipment.

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