WO2017193707A1 - 一种变压器油介质损耗增大原因的分析方法 - Google Patents

一种变压器油介质损耗增大原因的分析方法 Download PDF

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WO2017193707A1
WO2017193707A1 PCT/CN2017/077649 CN2017077649W WO2017193707A1 WO 2017193707 A1 WO2017193707 A1 WO 2017193707A1 CN 2017077649 W CN2017077649 W CN 2017077649W WO 2017193707 A1 WO2017193707 A1 WO 2017193707A1
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transformer oil
phthalate
plasticizer
dielectric loss
mass spectrometry
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PCT/CN2017/077649
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English (en)
French (fr)
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张丽
钱艺华
苏伟
陈天生
范圣平
付强
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广东电网有限责任公司电力科学研究院
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Priority to AU2017262033A priority Critical patent/AU2017262033B2/en
Publication of WO2017193707A1 publication Critical patent/WO2017193707A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G01N2030/3076—Control of physical parameters of the fluid carrier of temperature using specially adapted T(t) profile

Definitions

  • the invention relates to the technical field of transformer oil detection and analysis, and establishes a quantitative detection method of a phthalate plasticizer in transformer oil, and more specifically relates to an analysis method for increasing the dielectric loss of a transformer oil.
  • Transformer oil is a liquid insulating medium that acts as a cooling, arc extinguishing and insulating function in a transformer. Since transformer oil is used as a liquid insulating medium, it is required to have excellent insulating properties. However, studies have shown that as the transformer running time is extended, the dielectric loss of the transformer oil will gradually increase. For a transformer with an average life of about three or forty years, the dielectric loss of the transformer oil will increase the safety of the transformer. Stable operation brings serious risks.
  • Plasticizer also known as plasticizer, is a widely used polymer material additive in the industry, which can significantly improve the flexibility of materials. It is widely used in various fields of the national economy, including plastics, rubber, adhesives, and cellulose. , tens of thousands of products such as resins, medical devices, and cables.
  • phthalates are the most common types of plasticizers, which are widely used in daily and industrial applications. Since phthalates are polar compounds, they affect the insulation properties of transformer oils.
  • the present invention detects phthalic acid in a plurality of running transformer oils having insulation problems.
  • An analytical method for increasing the dielectric loss of a transformer oil based on a formate plasticizer, the analysis method provided by the invention has good accuracy and simple operation, and plays an important role in further improving the quality standard of the transformer oil. effect.
  • the invention provides an analysis method for increasing the dielectric loss of a transformer oil, comprising the following steps:
  • Quantitative detection method of phthalate plasticizer in transformer oil is established to quantitatively detect the content of phthalate plasticizer in transformer oil in actual operation, and obtain transformer oil The concentration of the phthalate plasticizer contained in the medium;
  • the quantitative detection method of the phthalate plasticizer in the transformer oil established in the step a) is gas chromatography-mass spectrometry.
  • the column for gas chromatography-mass spectrometry in step a) is an HP-5MS chromatographic column.
  • the temperature increasing procedure of the gas chromatography-mass spectrometry in step a) is specifically:
  • the column is maintained at an initial temperature of 90 ° C to 110 ° C for 0 min to 0.5 min;
  • the first temperature is raised to 230 ° C ⁇ 250 ° C at a rate of 15 ° C / min ⁇ 25 ° C / min, maintained for 0.5 min ⁇ 1.5 min;
  • the temperature was raised to 270 ° C to 290 ° C for the second time at a rate of 3 ° C / min to 7 ° C / min for 1 min to 3 min.
  • the injection conditions of the gas chromatography-mass spectrometry in step a) are:
  • the carrier gas of the gas chromatography-mass spectrometry is helium gas, and the purity of the helium gas is ⁇ 99.999%;
  • the flow rate of the carrier gas by the gas chromatography-mass spectrometry is from 0.5 mL/min to 1.5 mL/min.
  • the mass spectrometric conditions of the gas chromatography-mass spectrometry in step a) are:
  • the electron bombards the ion source with an electron energy of 70 eV and operates in a selective ion detection mode.
  • the method further comprises:
  • the process of the pre-processing is specifically:
  • the transformer oil in actual operation is extracted and fixed to obtain the sample to be tested for the quantitative detection method of the phthalate plasticizer in the transformer oil.
  • the phthalate plasticizer in the step a) is selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, and phthalic acid.
  • di(2-ethyl)hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate and dinonyl phthalate is selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, and phthalic acid.
  • the step a) specifically comprises the following steps:
  • A1 preparing a series of standard solutions, the standard solution being a mixed standard of the phthalate plasticizer;
  • the invention also provides an application method for analyzing the cause of the increase of the dielectric loss of the transformer oil described in the above technical solution in the operation and maintenance work of the transformer oil.
  • the invention provides an analysis method for increasing the dielectric loss of a transformer oil, comprising the following steps: a) using a quantitative detection method of a phthalate plasticizer in a transformer oil to establish a plurality of sets of actual operation transformers Quantitative detection of the content of phthalate plasticizer in oil, the concentration of phthalate plasticizer contained in transformer oil is obtained; b) the known concentration of dibutyl phthalate is prepared by The transformer oil sample is used to detect the dielectric loss of the transformer oil, and the test results are compared with the dielectric loss value of the transformer oil without plasticizer. The dielectric loss of the transformer oil increases with the plasticizer content.
  • the law of increase further confirms that analyzing the content of plasticizer in transformer oil is an analysis method for analyzing the increase of dielectric loss of transformer oil.
  • the invention analyzes the cause of the increase of the dielectric loss of the transformer oil on the basis of detecting the phthalate plasticizer in the running transformer oil with a plurality of insulation problems, and the insulation problem exists through the logarithm Transport Quantitative detection of the content of plasticizer in transformer oil, the relationship between the content of plasticizer in transformer oil and its dielectric loss, and the method for analyzing the increase of transformer oil dielectric loss by testing the content of plasticizer in transformer oil At the same time, a quantitative detection method for plasticizer in transformer oil was established.
  • the analytical method provided by the invention has good accuracy and simple operation, and plays an important role in further improving the quality standard of the running transformer oil.
  • the analysis method provided by the invention is applied in the daily operation and maintenance work of the transformer oil, and can timely discover the cause of the increase of the dielectric loss of the transformer oil, find the root cause of the problem, and timely ensure the safe and stable operation of the equipment.
  • Figure 1 shows the selective ion chromatogram of 16 phthalate plasticizers.
  • the invention provides an analysis method for increasing the dielectric loss of a transformer oil, comprising the following steps:
  • Quantitative detection method of phthalate plasticizer in transformer oil is established to quantitatively detect the content of phthalate plasticizer in transformer oil in actual operation, and obtain transformer oil The concentration of the phthalate plasticizer contained in the medium;
  • the quantitative detection method of the phthalate plasticizer in the transformer oil is used to quantify the content of the phthalate plasticizer in the transformer oil in the actual operation.
  • the concentration of the phthalate plasticizer contained in the transformer oil was determined.
  • the quantitative detection method of the phthalate plasticizer in the established transformer oil is preferably gas chromatography-mass spectrometry.
  • the present invention employs a gas chromatography-mass spectrometer well known to those skilled in the art for quantitative detection by gas chromatography-mass spectrometry, preferably a Model 7890A-5975C GC/MS manufactured by Agilent, USA.
  • the transformer oil to be tested is preferably a running transformer oil having an insulation problem.
  • the type and source of the transformer oil are not particularly limited in the present invention, and the domestically produced 25-degree transformer oil well known to those skilled in the art may be used. .
  • the phthalate plasticizer is preferably selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, and dibutyl phthalate. Ester, di(2-methoxy)ethyl phthalate, di(4-methyl-2-pentyl) phthalate, di(2-ethoxy)ethyl phthalate, Dipentyl phthalate, dihexyl phthalate, butyl benzyl phthalate, di(2-butoxy)ethyl phthalate, dicyclohexyl phthalate, One or more of di(2-ethylhexyl) phthalate, diphenyl phthalate, di-n-octyl phthalate, and dinonyl phthalate.
  • the pretreatment process is preferably specifically: accurately measuring 25 mL of the transformer oil to be tested, extracting twice with methanol (10 mL ⁇ 2), and collecting the extract with a 25 mL volumetric flask, and diluting to the mark with methanol. Line, the sample to be tested for the quantitative detection method of the phthalate plasticizer in the transformer oil is obtained.
  • the present invention will quantitatively detect the sample to be tested for the quantitative detection method of the phthalate plasticizer in the transformer oil, and obtain the phthalate contained in the transformer oil.
  • the concentration of the formate plasticizer preferably includes the following steps:
  • A1 preparing a series of standard solutions, the standard solution being a mixed standard of the phthalate plasticizer;
  • the standard solution is preferably a mixed standard of the phthalate plasticizer.
  • the phthalate plasticizer is preferably selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, and dibutyl phthalate.
  • the standard solution is a methanol mixed solution of 16 phthalates; the standard solution has a concentration of 1000 mg/L.
  • the composition and purity of the standard solution are shown in Table 1.
  • the concentration of the series of standard solutions is preferably 20 mg / L, 50 mg / L and 100 mg / L.
  • the preparation method of the series standard solution of the present invention is not particularly limited, and is preferably formulated according to the ratio shown in Table 2, Store in a brown glass bottle and seal in a dark place.
  • Standard solution concentration mg/L 1000mg/L mixed standard added to volume mL Methanol is added to volume mL 20 0.02 0.98 50 0.05 0.95 100 0.1 0.9
  • the present invention separately performs gas chromatography-mass spectrometry on the series of standard solutions.
  • the apparatus used in the gas chromatography-mass spectrometry of the present invention is not particularly limited, and may be a gas chromatography-mass spectrometer well known to those skilled in the art, preferably a 7890A-5975C gas chromatography/mass spectrometer manufactured by Agilent, USA.
  • the column of the gas chromatography-mass spectrometry is preferably an HP-5MS chromatographic separation column.
  • the HP-5MS chromatographic separation column (30m ⁇ 0.25mm) has non-polarity, can eliminate interference during the detection process, and accurately separate the phthalate plasticizer in the series standard solution. .
  • the temperature increasing procedure of the gas chromatography-mass spectrometry is specifically preferably:
  • the column is maintained at an initial temperature of 90 ° C to 110 ° C for 0 min to 0.5 min;
  • the first temperature is raised to 230 ° C ⁇ 250 ° C at a rate of 15 ° C / min ⁇ 25 ° C / min, maintained for 0.5 min ⁇ 1.5 min;
  • the second temperature is raised to 270 ° C ⁇ 290 ° C at a rate of 3 ° C / min ⁇ 7 ° C / min, for 1 min ⁇ 3 min;
  • the column is maintained at an initial temperature of 100 ° C for 0 min to 0.5 min;
  • the first temperature was raised to 240 ° C at a rate of 20 ° C / min, held for 1 min;
  • the temperature was raised a second time to 280 ° C at a rate of 5 ° C / min for 2 min.
  • the injection conditions of the gas chromatography-mass spectrometry are preferably:
  • the carrier gas of the gas chromatography-mass spectrometry is helium gas, and the purity of the helium gas is ⁇ 99.999%;
  • the gas stream of the gas chromatography-mass spectrometry has a flow rate of 0.5 mL/min to 1.5 mL/min;
  • the carrier gas of the gas chromatography-mass spectrometry is helium gas, and the purity of the helium gas is ⁇ 99.999%;
  • the flow rate of the carrier gas of the gas chromatography-mass spectrometry was 1 mL/min.
  • the mass spectrometric conditions of the gas chromatography-mass spectrometry are preferably:
  • the electron bombards the ion source with an electron energy of 70 eV and operates in a selective ion detection mode.
  • the molecular ion mass charge in the selective ion detection mode is as shown in Table 3.
  • the present invention After completion of gas chromatography-mass spectrometry of a series of standard solutions, the present invention establishes a standard curve based on the test results and the concentration of the phthalate plasticizer in the series of standard solutions.
  • the abscissa of the standard curve is the concentration of the phthalate plasticizer
  • the ordinate is the detection result. According to the established standard curve, the standard curve equation is obtained.
  • gas chromatography-mass spectrometry is performed on a plurality of sets of transformer oils to be tested, and the content of the plasticizer in each group of transformers to be tested is obtained according to the detection results and the established standard curve analysis.
  • the method before the gas chromatography-mass spectrometry, the method further comprises: performing pre-treatment on the plurality of sets of transformer oils to be tested respectively; the function and specific process of the pre-treatment are the same as described in the above technical solution, I will not repeat them here.
  • the apparatus used in the gas chromatography-mass spectrometry of the present invention is not particularly limited, and may be a gas chromatography-mass spectrometer well known to those skilled in the art, preferably a 7890A-5975C gas chromatography/mass spectrometer manufactured by Agilent, USA.
  • the column of the gas chromatography-mass spectrometry is preferably an HP-5MS chromatographic separation column.
  • the HP-5MS chromatographic separation column (30m ⁇ 0.25mm) has non-polarity, can eliminate interference during the detection process, and accurately separate the phthalate plasticizer in the transformer oil.
  • the temperature increasing procedure of the gas chromatography-mass spectrometry is specifically preferably:
  • the column is maintained at an initial temperature of 90 ° C to 110 ° C for 0 min to 0.5 min;
  • the first temperature is raised to 230 ° C ⁇ 250 ° C at a rate of 15 ° C / min ⁇ 25 ° C / min, maintained for 0.5 min ⁇ 1.5 min;
  • the second temperature is raised to 270 ° C ⁇ 290 ° C at a rate of 3 ° C / min ⁇ 7 ° C / min, for 1 min ⁇ 3 min;
  • the column is maintained at an initial temperature of 100 ° C for 0 min to 0.5 min;
  • the first temperature was raised to 240 ° C at a rate of 20 ° C / min, held for 1 min;
  • the temperature was raised a second time to 280 ° C at a rate of 5 ° C / min for 2 min.
  • the injection conditions of the gas chromatography-mass spectrometry are preferably:
  • the carrier gas of the gas chromatography-mass spectrometry is helium gas, and the purity of the helium gas is ⁇ 99.999%;
  • the gas stream of the gas chromatography-mass spectrometry has a flow rate of 0.5 mL/min to 1.5 mL/min;
  • the carrier gas of the gas chromatography-mass spectrometry is helium gas, and the purity of the helium gas is ⁇ 99.999%;
  • the flow rate of the carrier gas of the gas chromatography-mass spectrometry was 1 mL/min.
  • the mass spectrometric conditions of the gas chromatography-mass spectrometry are preferably:
  • the electron bombards the ion source with an electron energy of 70 eV and operates in a selective ion detection mode.
  • the molecular ion mass charge in the selective ion detection mode is as shown in Table 3 above.
  • the present invention analyzes the test results and the established standard curve to obtain the content of the plasticizer in each group of transformer oil to be tested.
  • the dielectric loss detection of the transformer oil is separately performed by preparing a transformer oil sample of a known concentration of dibutyl phthalate, and the detection result is compared with the dielectric loss value of the transformer oil without the plasticizer.
  • the analysis shows that the dielectric loss of the transformer oil increases with the increase of the plasticizer content. It is further confirmed that the analysis of the plasticizer content in the transformer oil is an analysis method for analyzing the increase of the dielectric loss of the transformer oil.
  • the apparatus and method for performing the dielectric loss detection of the transformer oil are not particularly limited, and a standard test method (GB/T 5654) well known to those skilled in the art may be used.
  • the invention also provides an application method for analyzing the cause of the increase of the dielectric loss of the transformer oil described in the above technical solution in the operation and maintenance work of the transformer oil.
  • the control experiment can determine the medium with the increase of the plasticizer content by establishing the above quantitative detection method.
  • the loss is increased, and the analysis method provided by the invention can be used for daily transformer oil detection work and transformer oil failure and defect cause analysis.
  • the invention provides an analysis method for increasing the dielectric loss of a transformer oil, comprising the following steps: a) using a quantitative detection method of a phthalate plasticizer in a transformer oil to establish a plurality of sets of actual operation transformers Quantitative detection of the content of phthalate plasticizer in oil, the concentration of phthalate plasticizer contained in transformer oil is obtained; b) the known concentration of dibutyl phthalate is prepared by The transformer oil sample is used to detect the dielectric loss of the transformer oil, and the test results are compared with the dielectric loss value of the transformer oil without plasticizer. The dielectric loss of the transformer oil increases with the plasticizer content.
  • the law of increase further confirms that analyzing the content of plasticizer in transformer oil is an analysis method for analyzing the increase of dielectric loss of transformer oil.
  • the invention analyzes the cause of the increase of the dielectric loss of the transformer oil on the basis of detecting the phthalate plasticizer in the running transformer oil with a plurality of insulation problems, and the insulation problem exists through the logarithm Quantitative detection of the content of plasticizer in the running transformer oil, the relationship between the plasticizer content in the transformer oil and its dielectric loss is obtained, thereby determining the reason for the increase of the dielectric loss of the transformer oil by testing the plasticizer content in the transformer oil.
  • a quantitative detection method for plasticizer in transformer oil was established.
  • the analytical method provided by the invention has good accuracy and simple operation, and plays an important role in further improving the quality standard of the running transformer oil.
  • the analysis method provided by the invention is applied in the daily operation and maintenance work of the transformer oil, and can Timely discovery of the increase in transformer oil dielectric loss, find the root cause of the problem, and timely eliminate the need for safe and stable operation of the equipment.
  • phthalate plasticizer is dimethyl phthalate , diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di(2-methoxy)ethyl phthalate, di(4-methyl phthalate) Benzyl-2-pentyl)ester, di(2-ethoxy)ethyl phthalate, diamyl phthalate, dihexyl phthalate, butyl benzyl phthalate, Di(2-butoxy)ethyl phthalate, dicyclohexyl phthalate, di(2-ethyl)hexyl phthalate, diphenyl phthalate, phthalic acid Di-n-octyl ester and dinonyl phthalate.
  • the concentration of the standard solution in the mixed standard 1 is 20 mg/L
  • the concentration of the standard solution in the mixed standard 2 is 50 mg/L
  • the concentration of the standard solution in the mixed standard 3 is 100 mg/L
  • the mixed standard 1 to 3 is the series standard solution.
  • the temperature program is: the column is maintained at an initial temperature of 100 ° C for 0 min to 0.5 min; the first temperature is raised to 240 ° C at a rate of 20 ° C / min for 1 min; the second temperature is raised at a rate of 5 ° C / min To 280 ° C, hold for 2 min; then bombard the ion source with electrons with an electron energy of 70 eV, and operate in the selective ion detection mode to obtain a selective ion chromatogram of 16 phthalate plasticizers as shown in Figure 1.
  • the numbers in the chromatogram correspond to the numbers in Table 1 one-to-one.
  • the present invention establishes a standard curve according to the detection result and the concentration of the phthalate plasticizer in the series standard solution; the abscissa c of the standard curve is adjacent The concentration of the phthalate plasticizer, the ordinate A is the detection result; and according to the established standard curve, the standard curve equation is obtained.
  • Table 4 The linear equations and correlation coefficients of the mixed solutions of 16 phthalate plasticizers are shown in Table 4.
  • the present invention analyzes the test results and the standard curve established in Example 1 to obtain the content of the plasticizer in each group of transformer oil to be tested.
  • the contents of the phthalate plasticizers in the 6 sets of transformer oil to be tested are shown in Table 5.
  • the transformer oil of the known concentration of the phthalate plasticizer is prepared, and the test method provided in the embodiment 2 is used to detect the transformer oil of the known phthalate plasticizer concentration, as shown in the table. 6 is shown.
  • Table 6 shows the detection data of transformer oil with the concentration of phthalate plasticizer
  • Sample 1 Concentration mg/L Sample 2 Sample 3 Formulation concentration 30 60 80 DMP 29 61 79 DEP 30 60 80 DIBP 30 60 80 DBP 29 61 81 DMEP 30 59 81 BMPP 29 60 80 DEEP 28 60 83 DAP 30 62 80 DHXP 31 60 85 BBP 30 60 80 DBEP 30 57 82 DCHP 29 58 79 DEHP 30 62 83 DPP 30 60 80 DNOP 29 59 80
  • the experimental results show that the quantitative detection results of the phthalate plasticizer in the transformer oil provided by the invention have good accuracy.
  • the dielectric loss of transformer oil containing different concentrations of dibutyl phthalate was quantitatively tested, and the test results were compared with the dielectric loss values of transformer oil (white oil) without plasticizer.
  • the test results are as follows. Table 7 shows.

Abstract

一种变压器油介质损耗增大原因的分析方法，包括：a）采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度；b）通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。通过测试变压器油中塑化剂含量来分析变压器油介质损耗增大的原因。

Description

一种变压器油介质损耗增大原因的分析方法
本申请要求于2016年05月13日提交中国专利局、申请号为201610317621.1、发明名称为“一种变压器油介质损耗增大原因的分析方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及变压器油检测分析技术领域，建立了变压器油中邻苯二甲酸酯类塑化剂的定量检测方法，更具体地说，是涉及一种变压器油介质损耗增大原因的分析方法。
背景技术
变压器油是在变压器中起到冷却、灭弧和绝缘作用的液体绝缘介质，由于变压器油作为液体绝缘介质使用，因此要求其具有优良的绝缘性能。但是研究表明，随着变压器运行时间的延长，变压器油的介质损耗会逐渐增大，对于一台平均寿命约为三、四十年的变压器来说，变压器油的介质损耗增大会给变压器的安全稳定运行带来严重隐患。
目前，变压器生产过程中使用到大量的高分子材料，如橡胶件、内壁漆、绝缘漆、粘合剂等等，这些高分子材料中的塑化剂会逐渐溶解到变压器油中，可能是引起变压器油介质损耗增大的原因。塑化剂，又称增塑剂，是工业中被广泛使用的高分子材料助剂，可以明显提高材料的柔韧性，广泛应用于国民经济各领域，包括塑料、橡胶、粘合剂、纤维素、树脂、医疗器械、电缆等成千上万种产品中。其中，邻苯二甲酸酯类是最常见的塑化剂种类，在日常及工业上被广泛使用，由于邻苯二甲酸酯属于极性化合物，会影响变压器油的绝缘性能。
但是，目前国内外还没有通过检测变压器油中塑化剂的含量进一步对变压器油介质损耗增大原因进行分析的报道。
发明内容
有鉴于此，本发明在对数台存在绝缘问题的运行变压器油中检测出邻苯二 甲酸酯类塑化剂的基础上提出的一种变压器油介质损耗增大原因的分析方法，本发明提供的分析方法准确性好且操作简单，对运行变压器油的质量标准的进一步完善起到重要作用。
本发明提供了一种变压器油介质损耗增大原因的分析方法，包括以下步骤：
a)采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度；
b)通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。
优选的，步骤a)中所述建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法为气相色谱-质谱法。
优选的，步骤a)中所述气相色谱-质谱法的色谱柱为HP-5MS色谱分离柱。
优选的，步骤a)中所述气相色谱-质谱法的升温程序具体为：
色谱柱在初始温度90℃～110℃，保持0min～0.5min；
以15℃/min～25℃/min的速率第一次升温至230℃～250℃，保持0.5min～1.5min；
以3℃/min～7℃/min的速率第二次升温至270℃～290℃，保持1min～3min。
优选的，步骤a)中所述气相色谱-质谱法的进样条件为：
所述气相色谱-质谱法的载气为氦气，所述氦气的纯度≥99.999％；
所述气相色谱-质谱法的载气的流速为0.5mL/min～1.5mL/min。
优选的，步骤a)中所述气相色谱-质谱法的质谱条件为：
电子轰击离子源，电子能量为70eV，在选择离子检测模式下操作。
优选的，步骤a)中采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法进行检测前，还包括：
对所述多组实际运行中变压器油分别进行前处理；
所述前处理的过程具体为：
将实际运行中变压器油进行萃取定容，得到用于变压器油中邻苯二甲酸酯类塑化剂的定量检测方法检测的待测样品。
优选的，步骤a)中所述邻苯二甲酸酯类塑化剂选自邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯中的一种或多种。
优选的，所述步骤a)具体包括以下步骤：
a1)配制系列标准溶液，所述标准溶液为所述邻苯二甲酸酯类塑化剂的混标；
a2)分别对所述系列标准溶液进行气相色谱-质谱检测，根据检测结果和系列标准溶液中邻苯二甲酸酯类塑化剂的浓度建立标准曲线；
a3)分别对多组实际运行中变压器油进行气相色谱-质谱检测，根据检测结果和建立的标准曲线分析得到各组待测变压器油中塑化剂的含量。
本发明还提供了一种上述技术方案所述的变压器油介质损耗增大原因的分析方法在变压器油运行维护工作中的应用。
本发明提供了一种变压器油介质损耗增大原因的分析方法，包括以下步骤：a)采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度；b)通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。本发明在对数台存在绝缘问题的运行变压器油中检测出邻苯二甲酸酯类塑化剂的基础上提出的一种变压器油介质损耗增大原因的分析方法，通过对数台存在绝缘问题的运 行变压器油中塑化剂的含量进行定量检测，得到变压器油中塑化剂含量与其介质损耗的关系，从而确定了通过测试变压器油中塑化剂含量来分析变压器油介质损耗增大原因的方法；同时，建立了变压器油中塑化剂的定量检测方法。本发明提供的分析方法准确性好，操作简单，对运行变压器油的质量标准的进一步完善起到重要作用。
此外，本发明提供的分析方法应用在变压器油日常运行维护工作中，能够及时发现变压器油介质损耗增大原因，找到问题根源，及时消缺保障设备安全稳定运行。
附图说明
图1为16种邻苯二甲酸酯类塑化剂选择性离子色谱图。
具体实施方式
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种变压器油介质损耗增大原因的分析方法，包括以下步骤：
a)采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度；
b)通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。
在本发明中，采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量 检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度。在本发明中，所述建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法优选为气相色谱-质谱法。本发明采用本领域技术人员熟知的气质联用仪进行气相色谱-质谱法的定量检测，优选为美国Agilent公司生产的7890A-5975C型气质联用仪。在本发明中，所述待测变压器油优选为存在绝缘问题的运行变压器油，本发明对所述变压器油的种类和来源没有特殊限制，如可采用本领域技术人员熟知的国产25号变压器油。
在本发明中，所述邻苯二甲酸酯类塑化剂优选选自邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯中的一种或多种。
在本发明中，所述采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法进行检测前，优选还包括：对所述多组实际运行中变压器油分别进行前处理。在本发明中，所述前处理的目的是富集所述邻苯二甲酸酯类塑化剂，减小检测时的误差。在本发明中，所述前处理的过程优选具体为：准确量取25mL待测变压器油，用甲醇萃取两次(10mL×2)，再用25mL容量瓶收集萃取液，用甲醇定容至刻度线，得到用于变压器油中邻苯二甲酸酯类塑化剂的定量检测方法检测的待测样品。
完成所述前处理过程后，本发明将得到的用于变压器油中邻苯二甲酸酯类塑化剂的定量检测方法检测的待测样品进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度。在本发明中，所述检测的过程优选具体包括以下步骤：
a1)配制系列标准溶液，所述标准溶液为所述邻苯二甲酸酯类塑化剂的混标；
a2)分别对所述系列标准溶液进行气相色谱-质谱检测，根据检测结果和系列标准溶液中邻苯二甲酸酯类塑化剂的浓度建立标准曲线；
a3)分别对多组实际运行中变压器油进行气相色谱-质谱检测，根据检测结果和建立的标准曲线分析得到各组待测变压器油中塑化剂的含量。
在本发明中，首先配制系列标准溶液。在本发明中，所述标准溶液优选为所述邻苯二甲酸酯类塑化剂的混标。在本发明中，所述邻苯二甲酸酯类塑化剂优选选自邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯中的一种或多种。在本发明一个优选的实施例中，所述标准溶液为16种邻苯二甲酸酯的甲醇混标溶液；所述标准溶液的浓度为1000mg/L。在本发明中，所述标准溶液的组成及纯度如表1所示。
表1 16种邻苯二甲酸酯混标组成及纯度
Figure PCTCN2017077649-appb-000001
Figure PCTCN2017077649-appb-000002
在本发明中，所述系列标准溶液的浓度优选为20mg/L、50mg/L和100mg/L，本发明对系列标准溶液的配制方法没有特殊限制，优选按照表2所示的比例进行配制，储存在棕色玻璃瓶中并密封保存于阴暗处。
表2系列标准溶液的配制
标准溶液浓度mg/L 1000mg/L混标加入体积mL 甲醇加入体积mL
20 0.02 0.98
50 0.05 0.95
100 0.1 0.9
完成所述系列标准溶液的配制后，本发明分别对所述系列标准溶液进行气相色谱-质谱检测。本发明对所述气相色谱-质谱检测采用的仪器没有特殊限制，采用本领域技术人员熟知的气质联用仪即可，优选为美国Agilent公司生产的7890A-5975C型气质联用仪。
在本发明中，所述气相色谱-质谱法的色谱柱优选为HP-5MS色谱分离柱。在本发明中，所述HP-5MS色谱分离柱(30m×0.25mm)具有非极性，能够排除检测过程中的干扰，对系列标准溶液中的邻苯二甲酸酯类塑化剂进行准确分离。
在本发明中，所述气相色谱-质谱法的升温程序具体优选为：
色谱柱在初始温度90℃～110℃，保持0min～0.5min；
以15℃/min～25℃/min的速率第一次升温至230℃～250℃，保持0.5min～1.5min；
以3℃/min～7℃/min的速率第二次升温至270℃～290℃，保持1min～3min；
更优选为：
色谱柱在初始温度100℃，保持0min～0.5min；
以20℃/min的速率第一次升温至240℃，保持1min；
以5℃/min的速率第二次升温至280℃，保持2min。
在本发明中，所述气相色谱-质谱法的进样条件优选为：
所述气相色谱-质谱法的载气为氦气，所述氦气的纯度≥99.999％；
所述气相色谱-质谱法的载气的流速为0.5mL/min～1.5mL/min；
更优选为：
所述气相色谱-质谱法的载气为氦气，所述氦气的纯度≥99.999％；
所述气相色谱-质谱法的载气的流速为1mL/min。
在本发明中，所述气相色谱-质谱法的质谱条件优选为：
电子轰击离子源，电子能量为70eV，在选择离子检测模式下操作。在本发明中，所述选择离子检测模式下的分子离子质荷比如表3所示。
表3 16中邻苯二甲酸酯类塑化剂标准物质定量离子
化合物 保留时间/min 定量离子/m/z 辅助定量离子/m/z
DMP 4.7 163 194
DEP 5.6 149 177
DIBP 7.1 149 223
DBP 7.6 149 223
DMEP 7.8 59 149，207
BMPP 8.3 149 251
DEEP 8.5 72 149
DAP 8.8 149 237
DHXP 10.3 149 251
BBP 10.5 149 91
DBEP 11.5 149 193
DCHP 12.1 149 167
DEHP 12.3 149 167
DPP 12.4 225 77
DNOP 14.3 149 279
DNP 14.9 149 207
完成系列标准溶液的气相色谱-质谱检测后，本发明根据检测结果和系列标准溶液中邻苯二甲酸酯类塑化剂的浓度建立标准曲线。在本发明中，所述标准曲线的横坐标为邻苯二甲酸酯类塑化剂的浓度，纵坐标为检测结果。再根据建立的标准曲线，得到标准曲线方程。
在本发明中，分别对多组待测变压器油进行气相色谱-质谱检测，根据检测结果和建立的标准曲线分析得到各组待测变压器油中塑化剂的含量。在本发 明中，所述采用气相色谱-质谱检测前，优选还包括：对所述多组待测变压器油分别进行前处理；所述前处理的作用和具体过程与上述技术方案中所述的相同，在此不再赘述。
本发明对所述气相色谱-质谱检测采用的仪器没有特殊限制，采用本领域技术人员熟知的气质联用仪即可，优选为美国Agilent公司生产的7890A-5975C型气质联用仪。
在本发明中，所述气相色谱-质谱法的色谱柱优选为HP-5MS色谱分离柱。在本发明中，所述HP-5MS色谱分离柱(30m×0.25mm)具有非极性，能够排除检测过程中的干扰，对变压器油中的邻苯二甲酸酯类塑化剂进行准确分离。
在本发明中，所述气相色谱-质谱法的升温程序具体优选为：
色谱柱在初始温度90℃～110℃，保持0min～0.5min；
以15℃/min～25℃/min的速率第一次升温至230℃～250℃，保持0.5min～1.5min；
以3℃/min～7℃/min的速率第二次升温至270℃～290℃，保持1min～3min；
更优选为：
色谱柱在初始温度100℃，保持0min～0.5min；
以20℃/min的速率第一次升温至240℃，保持1min；
以5℃/min的速率第二次升温至280℃，保持2min。
在本发明中，所述气相色谱-质谱法的进样条件优选为：
所述气相色谱-质谱法的载气为氦气，所述氦气的纯度≥99.999％；
所述气相色谱-质谱法的载气的流速为0.5mL/min～1.5mL/min；
更优选为：
所述气相色谱-质谱法的载气为氦气，所述氦气的纯度≥99.999％；
所述气相色谱-质谱法的载气的流速为1mL/min。
在本发明中，所述气相色谱-质谱法的质谱条件优选为：
电子轰击离子源，电子能量为70eV，在选择离子检测模式下操作。在本发明中，所述选择离子检测模式下的分子离子质荷比如上述表3所示。
完成对多组待测变压器油的气相色谱-质谱检测后，本发明根据检测结果和建立的标准曲线分析得到各组待测变压器油中塑化剂的含量。
在本发明中，通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。本发明对所述进行变压器油的介质损耗检测的仪器和方法没有特殊限制，采用本领域技术人员熟知的标准测试方法(GB/T 5654)即可。
本发明还提供了一种上述技术方案所述的变压器油介质损耗增大原因的分析方法在变压器油运行维护工作中的应用。在本发明中，由于在多台介质损耗异常的变压器油中检测出邻苯二甲酸酯类塑化剂，通过建立上述定量检测方法，控制实验能够确定随着塑化剂含量的增大，介质损耗增大，采用本发明提供的分析方法能够用于日常的变压器油检测工作和变压器油故障及缺陷原因分析。
本发明提供了一种变压器油介质损耗增大原因的分析方法，包括以下步骤：a)采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度；b)通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。本发明在对数台存在绝缘问题的运行变压器油中检测出邻苯二甲酸酯类塑化剂的基础上提出的一种变压器油介质损耗增大原因的分析方法，通过对数台存在绝缘问题的运行变压器油中塑化剂的含量进行定量检测，得到变压器油中塑化剂含量与其介质损耗的关系，从而确定了通过测试变压器油中塑化剂含量来分析变压器油介质损耗增大原因的方法；同时，建立了变压器油中塑化剂的定量检测方法。本发明提供的分析方法准确性好，操作简单，对运行变压器油的质量标准的进一步完善起到重要作用。
此外，本发明提供的分析方法应用在变压器油日常运行维护工作中，能够 及时发现变压器油介质损耗增大原因，找到问题根源，及时消缺保障设备安全稳定运行。
为了进一步说明本发明，下面通过以下实施例进行详细说明。
实施例1
建立标准曲线：
(1)配制系列标准溶液：用甲醇(色谱纯)配制16种邻苯二甲酸酯类塑化剂的混标溶液，所述邻苯二甲酸酯类塑化剂为邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯。
混标1中标准溶液的浓度为20mg/L，混标2中标准溶液的浓度为50mg/L，混标3中标准溶液的浓度为100mg/L；混标1～3即为系列标准溶液。
(2)对混标1～3分别进行气相色谱-质谱检测，采用HP-5MS色谱分离柱(30m×0.25mm)，以纯度≥99.999％的氦气为载气，控制载气的流速为1mL/min，升温程序为：色谱柱在初始温度100℃，保持0min～0.5min；以20℃/min的速率第一次升温至240℃，保持1min；以5℃/min的速率第二次升温至280℃，保持2min；然后以电子能量为70eV的电子轰击离子源，在选择离子检测模式下操作，得到16种邻苯二甲酸酯类塑化剂选择性离子色谱图如图1所示，所述色谱图中编号与表1中的编号一一对应。
(3)完成系列标准溶液的气相色谱-质谱检测后，本发明根据检测结果和系列标准溶液中邻苯二甲酸酯类塑化剂的浓度建立标准曲线；所述标准曲线的横坐标c为邻苯二甲酸酯类塑化剂的浓度，纵坐标A为检测结果；再根据建立的标准曲线，得到标准曲线方程。16种邻苯二甲酸酯类塑化剂的混标溶液的线性方程及相关系数如表4所示。
表4 16种邻苯二甲酸酯类塑化剂的混标溶液的线性方程及相关系数
化合物 线性方程 相关系数
DMP A＝112000c+567000 0.997
DEP A＝101000c+476000 0.998
DIBP A＝130000c+43000 0.999
DBP A＝146000c+558000 0.998
DMEP A＝33100c-140000 0.999
BMPP A＝129000c+144000 0.999
DEEP A＝171000c+10300 0.999
DAP A＝164000c+544000 0.998
DHXP A＝186000c-3060000 0.985
BBP A＝48800c+23000 0.999
DBEP A＝168000c+387000 0.999
DCHP A＝98100c-81300 0.999
DEHP A＝79300c+57300 0.999
DPP A＝91400c+79600 0.999
DNOP A＝30400c-3000 0.999
DNP A＝12000c+21200 1.000
实施例2
测定变压器油中邻苯二甲酸酯类塑化剂的含量：
(1)对6组存在绝缘问题的运行变压器油分别进行前处理：分别准确量取25mL待测变压器油，用甲醇萃取两次(10mL×2)，再用25mL容量瓶收集萃取液，用甲醇定容至刻度线，分别得到6组待测变压器油。
(2)对上述6组待测变压器油分别进行气相色谱-质谱检测，采用HP-5MS色谱分离柱(30m×0.25mm)，以纯度≥99.999％的氦气为载气，控制载气的流速为1mL/min，升温程序为：色谱柱在初始温度100℃，保持0min～0.5min；以20℃/min的速率第一次升温至240℃，保持1min；以5℃/min的速率第二次升温至280℃，保持2min；然后以电子能量为70eV的电子轰击离子源，在选择离子检测模式下操作。
(3)完成对上述6组待测变压器油的气相色谱-质谱检测后，本发明根据检测结果和实施例1建立的标准曲线分析得到各组待测变压器油中塑化剂的含量。6组待测变压器油中邻苯二甲酸酯类塑化剂的含量如表5所示。
表5 6组待测变压器油中邻苯二甲酸酯类塑化剂的含量
化合物 第1组 第2组 第3组 第4组 第5组 第6组
DMP - - - - - -
DEP 4.34 5.54 4.66 8.25 6.23 -
DIBP 7.11 10.04 7.74 8.43 8.94 2.63
DBP 16.08 20.53 17.61 22.29 19.55 16.68
DMEP - - - - -  
BMPP 3.11 4.50 4.99 7.25 3.74 2.71
DEEP - - - - - -
DAP - - - - - -
DHXP - - - - - -
BBP - - - - - -
DBEP - - - -   -
DCHP - 2.20 0.88 1.43 0.91 0.90
DEHP 2.83 5.19 3.45 4.18 3.49 3.47
DPP - - -   - -
DNOP - - - - - -
DNP - - -   - -
实验结果表明，上述6组存在绝缘问题的运行变压器油中均发现邻苯二甲酸酯类塑化剂，且邻苯二甲酸二丁酯的含量达到了20mg/L。
实施例3
检测结果准确性考察：
配制已知邻苯二甲酸酯类塑化剂浓度的变压器油，按照实施例2提供的测定方法进行检测，得到已知邻苯二甲酸酯类塑化剂浓度的变压器油的检测数据，如表6所示。
表6已知邻苯二甲酸酯类塑化剂浓度的变压器油的检测数据
浓度mg/L 样品1 样品2 样品3
配制浓度 30 60 80
DMP 29 61 79
DEP 30 60 80
DIBP 30 60 80
DBP 29 61 81
DMEP 30 59 81
BMPP 29 60 80
DEEP 28 60 83
DAP 30 62 80
DHXP 31 60 85
BBP 30 60 80
DBEP 30 57 82
DCHP 29 58 79
DEHP 30 62 83
DPP 30 60 80
DNOP 29 59 80
DNP 29 58 79
实验结果表明，本发明提供的变压器油中邻苯二甲酸酯类塑化剂的定量检测结果准确性好。
实施例4
变压器油介质损耗增大原因分析：
对含有不同浓度的邻苯二甲酸二丁酯的变压器油的介质损耗进行定量检测，并将检测结果与不含塑化剂的变压器油(空白油)的介质损耗数值进行比较分析，检测结果如表7所示。
表7含有不同浓度的邻苯二甲酸二丁酯的变压器油的介质损耗数据
Figure PCTCN2017077649-appb-000003
实验结果表明，随着邻苯二甲酸二丁酯浓度的增大，介损逐渐增大，体积电阻率逐渐降低，界面张力逐渐减小。由此可见，邻苯二甲酸酯类塑化剂会导致变压器油介损增大且对变压器油性能影响较大。
所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种变压器油介质损耗增大原因的分析方法，其特征在于，包括以下步骤：
    a)采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法分别对多组实际运行中变压器油中邻苯二甲酸酯类塑化剂的含量进行定量检测，得出变压器油中所含邻苯二甲酸酯类塑化剂的浓度；
    b)通过配制邻苯二甲酸二丁酯已知浓度的变压器油样品，分别进行变压器油的介质损耗检测，并将检测结果与不含塑化剂的变压器油的介质损耗数值进行比较分析，得到变压器油介质损耗会随塑化剂含量的增大而增大的规律，进一步确认通过分析变压器油中塑化剂含量是分析变压器油介质损耗增大原因的一种分析方法。
  2. 根据权利要求1所述的分析方法，其特征在于，步骤a)中所述建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法为气相色谱-质谱法。
  3. 根据权利要求2所述的分析方法，其特征在于，步骤a)中所述气相色谱-质谱法的色谱柱为HP-5MS色谱分离柱。
  4. 根据权利要求2所述的分析方法，其特征在于，步骤a)中所述气相色谱-质谱法的升温程序具体为：
    色谱柱在初始温度90℃～110℃，保持0min～0.5min；
    以15℃/min～25℃/min的速率第一次升温至230℃～250℃，保持0.5min～1.5min；
    以3℃/min～7℃/min的速率第二次升温至270℃～290℃，保持1min～3min。
  5. 根据权利要求2所述的分析方法，其特征在于，步骤a)中所述气相色谱-质谱法的进样条件为：
    所述气相色谱-质谱法的载气为氦气，所述氦气的纯度≥99.999％；
    所述气相色谱-质谱法的载气的流速为0.5mL/min～1.5mL/min。
  6. 根据权利要求2所述的分析方法，其特征在于，步骤a)中所述气相色谱-质谱法的质谱条件为：
    电子轰击离子源，电子能量为70eV，在选择离子检测模式下操作。
  7. 根据权利要求1所述的分析方法，其特征在于，步骤a)中采用建立的变压器油中邻苯二甲酸酯类塑化剂的定量检测方法进行检测前，还包括：
    对所述多组实际运行中变压器油分别进行前处理；
    所述前处理的过程具体为：
    将实际运行中变压器油进行萃取定容，得到用于变压器油中邻苯二甲酸酯类塑化剂的定量检测方法检测的待测样品。
  8. 根据权利要求1所述的分析方法，其特征在于，步骤a)中所述邻苯二甲酸酯类塑化剂选自邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯中的一种或多种。
  9. 根据权利要求8所述的分析方法，其特征在于，所述步骤a)具体包括以下步骤：
    a1)配制系列标准溶液，所述标准溶液为所述邻苯二甲酸酯类塑化剂的混标；
    a2)分别对所述系列标准溶液进行气相色谱-质谱检测，根据检测结果和系列标准溶液中邻苯二甲酸酯类塑化剂的浓度建立标准曲线；
    a3)分别对多组实际运行中变压器油进行气相色谱-质谱检测，根据检测结果和建立的标准曲线分析得到各组待测变压器油中塑化剂的含量。
  10. 一种权利要求1～9任一项所述的变压器油介质损耗增大原因的分析方法在变压器油运行维护工作中的应用。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007327877A (ja) * 2006-06-08 2007-12-20 Meidensha Corp ポリ塩化ビニル組成物の分析方法
CN101858897A (zh) * 2010-07-05 2010-10-13 深圳出入境检验检疫局玩具检测技术中心 邻苯二甲酸酯类增塑剂的检测方法
CN103852535A (zh) * 2014-03-26 2014-06-11 昆山洛丹伦生物科技有限公司 一种电子元器件塑料部件中邻苯二甲酸酯的检测方法
CN104698109A (zh) * 2015-03-31 2015-06-10 中国科学院长春应用化学研究所 一种食用油中邻苯二甲酸酯类塑化剂的检测方法
CN105784877A (zh) * 2016-05-13 2016-07-20 广东电网有限责任公司电力科学研究院 一种变压器油介质损耗增大原因的分析方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016009553A (ja) * 2014-06-23 2016-01-18 出光興産株式会社 電気絶縁油組成物
CN105004818A (zh) * 2015-07-29 2015-10-28 齐国良 一种含油脂食品中塑化剂的检测方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007327877A (ja) * 2006-06-08 2007-12-20 Meidensha Corp ポリ塩化ビニル組成物の分析方法
CN101858897A (zh) * 2010-07-05 2010-10-13 深圳出入境检验检疫局玩具检测技术中心 邻苯二甲酸酯类增塑剂的检测方法
CN103852535A (zh) * 2014-03-26 2014-06-11 昆山洛丹伦生物科技有限公司 一种电子元器件塑料部件中邻苯二甲酸酯的检测方法
CN104698109A (zh) * 2015-03-31 2015-06-10 中国科学院长春应用化学研究所 一种食用油中邻苯二甲酸酯类塑化剂的检测方法
CN105784877A (zh) * 2016-05-13 2016-07-20 广东电网有限责任公司电力科学研究院 一种变压器油介质损耗增大原因的分析方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHANG, CHANG: "Analysis and Treatment of Oil Dielectric Loss Increasing Behind Main Transformer Hanging Hood", CHINA SCIENCE AND TECHNOLOGY INFORMATION, 15 January 2007 (2007-01-15) *
HUANG, YISONG: "Necessity of Properties Inspection for Transformer Oil", ELECTRIC POWER STANDARDIZATION & CONSTRUCTION COST CONTROL INFORMATION, 30 June 2006 (2006-06-30) *
LI, XINSHENG: "Compatibility Test Report of Transformer Oil for Insulating Material of Jinliao Power Transmission Project", THERMAL POWER GENERATION, 14 March 1986 (1986-03-14) *
LIAN, YUYING: "Properties and Inspection of Transformer Oil", GUANGDONG ELECTRIC POWER, 25 August 1997 (1997-08-25) *
ZHOU, JIEHUA: "Cause Analysis and Treatment of Serious Decline of Main Insulation and Main Increase of Oil Dielectric Loss in Main Transformer of ShaoguanMabaNo.l", GUANGDONG ELECTRIC POWER, 15 May 1995 (1995-05-15) *

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