AU2017262033B2 - Method for analyzing causes of increase in dielectric loss of transformer oil - Google Patents
Method for analyzing causes of increase in dielectric loss of transformer oil Download PDFInfo
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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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
- 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
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Abstract
A method for analyzing causes of an increase in dielectric loss of transformer oil, comprising: a) separately performing quantitative measurement on the contents of phthalate plasticizers in transformer oil of multiple sets of transformers during actual operation by using an established method for quantitative measurement of phthalate plasticizers in transformer oil, to obtain the concentrations of the phthalate plasticizers contained in the transformer oil; and (b) separately measuring the dielectric loss of the transformer oil by preparing a transformer oil sample in which the concentration of a di-n-butyl phthalate is known, and comparing the measurement results with a dielectric loss value of transformer oil containing no plasticizer for analysis to obtain a rule following which the dielectric loss of transformer oil increases with the increase of plasticizer content, thereby further confirming that analyzing the plasticizer content of transformer oil is a method for analyzing causes of an increase in dielectric loss of transformer oil. Therefore, the causes of an increase in dielectric loss of transformer oil can be analyzed by testing the plasticizer content of the transformer oil.
Description
English translation of PCT/CN2017/077649 OP1817-08-0240
[0001] The present application claims priority to Chinese Patent Application No. 201610317621.1, titled "METHOD FOR ANALYZING CAUSES OF INCREASE IN DIELECTRIC LOSS OF TRANSFORMER OIL", fled on May 13, 2016 with the State Intellectual Property Office of People's Republic of China, the entire contents of which are incorporated herein by reference.
[0002] The present invention relates to the technical field of measurement and analysis of transformer oil and establishes a method for quantitative measurement of phthalate plasticizer in transformer oil, and more specifically, a method for analyzing a cause of an increase in dielectric loss of transformer oil.
[0003] Transformer oil is a liquid isolating medium serving for cooling, arc extinguishing, and isolation in a transformer, and is required to have excellent isolating properties since the transformer oil is used as a liquid isolating medium. However, studies have shown that as the operation time of a transformer is extended, the dielectric loss of the transformer oil will gradually increase, and for a transformer having an average lifetime of about three or four decades, the increase in dielectric loss of the transformer oil will bring serious hidden troubles to the safe and stable operation of the transformer.
[0004] Currently, during the production process of transformers, a large amount of polymer materials are used, such as rubber parts, inner wall paints, isolating varnishes, adhesives, etc., and plasticizers in such polymer materials will gradually dissolve into the transformer oil, which might be the cause of the increase in dielectric loss of the transformer oil. Plasticizers, also known as plasticizing agents, are polymer material aids widely used in industries, which can significantly improve the flexibility of a material, and are widely applied in various fields of national economy, including thousands of products such as plastics, rubbers, adhesives,
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English translation of PCT/CN2017/077649 OP1817-08-0240
celluloses, resins, medical instruments, cables, etc. Here, phthalates are the most common type of plasticizers and are widely used in daily life and industries because the phthalates belong to polar compounds and will influence the isolating properties of transformer oil.
[0005] However, up till now, it has not yet been reported at home and abroad that the content of plasticizer in transformer oil are measured so as to further analyze causes of an increase in dielectric loss of transformer oil.
[0006] In view of this, on the basis that phthalate plasticizer is detected in transformer oil of several transformers in operation suffering from insulation problems, the present invention proposes a method for analyzing a cause of an increase in dielectric loss of transformer oil. The method provided in the present invention is accurate and simple in operation, and plays an important role in further perfecting the quality standards for transformer oil in operation.
[0007] The present invention provides a method for analyzing a cause of an increase in dielectric loss of transformer oil, comprising the steps of:
a) performing quantitative measurement on the content of phthalate plasticizer in multiple sets of transformer oil in actual operation by using an established method for quantitative measurement of phthalate plasticizer in transformer oil respectively, to obtain the concentration of the phthalate plasticizer contained in the transformer oil; and
b) measuring the dielectric loss of the transformer oil by preparing transformer oil samples having known concentrations of di-n-butyl phthalate respectively, and comparing the measurement results with the dielectric loss value of a transformer oil containing no plasticizer to obtain a rule that the dielectric loss of the transformer oil increases with the increase of the content of the plasticizer, thereby further confirming that analysis of the plasticizer content in the transformer oil is a method for analyzing a cause of an increase in dielectric loss of transformer oil.
[0008] Preferably, the established method for quantitative measurement of phthalate plasticizer in transformer oil in step a) is gas chromatography-mass spectrometry.
[0009] Preferably, a chromatographic column in the gas chromatography-mass spectrometry of step a) is a HP-5MS chromatographic separation column. -2 12419235_1 (GHMatter) P109787.AU
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[0010] Preferably, a temperature programming in the gas chromatography-mass spectrometry of step a) is specifically by:
maintaining the chromatographic column at an initial temperature of 90°C-110°C for 0 min-0.5 min;
performing a first temperature raising up to 230°C-250°C at a rate of °C/min-25°C/min and then maintaining the temperature for 0.5 min-1.5 min; and
performing a second temperature raising up to 270°C-290°C at a rate of 3°C/min-7°C/min and then maintaining the temperature for 1 min-3 min.
[0011] Preferably, sample injection in the gas chromatography-mass spectrometry of step a) is performed under conditions:
carrier gas in the gas chromatography-mass spectrometry is helium gas having a purity of>99.999%; and
the carrier gas in the gas chromatography-mass spectrometry has a flow rate of 0.5 mL/min~1.5 m/mmin.
[0012] Preferably, mass spectrometry in the gas chromatography-mass spectrometry of step a) is:
an electron-bombardment ion source having an electron energy of 70 eV in a selected ion monitoring mode.
[0013] Preferably, prior to the measurement by using an established method for quantitative measurement of phthalate plasticizer in transformer oil, the step a) further comprises:
pretreating the multiple sets of transformer oil in actual operation respectively;
wherein the procedure of the pretreating is:
extracting the transformer oil in actual operation and adjusting the volume thereof to obtain samples to be measured by the method for quantitative measurement of phthalate plasticizer in transformer oil.
[0014] Preferably, the phthalate plasticizer in step a) is one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, bis(2-methoxyethyl) phthalate, bis(4-methyl-2-pentyl) phthalate, bis(2-ethoxyethyl) phthalate,
-3 12419235_1 (GHMatters) P109787.AU
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diamyl phthalate, di-n-hexyl phthalate, butyl benzyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, bis(2-ethylhexyl) phthalate, diphenyl phthalate, di-n-octyl phthalate, and di-nonyl phthalate.
[0015] Preferably, step a) specifically comprises the steps of:
al) preparing a series of standard solutions, wherein the standard solutions are standard solutions of a mixed phthalate plasticizer;
a2) subjecting the series of standard solutions to gas chromatography-mass spectrometry respectively, and establishing a standard curve based on the measurement results and the concentration of the phthalate plasticizer in the series of standard solutions; and
a3) subjecting the multiple sets of transformer oil in actual operation to gas chromatography-mass spectrometry respectively, and analyzing based on the measurement results and the established standard curve to obtain the content of the plasticizer in each of the sets of transformer oil to be measured.
[0016] The present invention further provides use of the method for analyzing a cause of an increase in dielectric loss of transformer oil as described in the above technical solutions in operation and maintenance of transformer oil.
[0017] The present invention provides a method for analyzing a cause of an increase in dielectric loss of transformer oil, comprising the steps of: a) performing quantitative measurement on the content of phthalate plasticizer in multiple sets of transformer oil in actual operation by using an established method for quantitative measurement of phthalate plasticizer in transformer oil respectively, to obtain the concentration of the phthalate plasticizer contained in the transformer oil; and b) measuring the dielectric loss of the transformer oil by preparing transformer oil samples having known concentrations of di-n-butyl phthalate respectively, and comparing the measurement results with the dielectric loss value of a transformer oil containing no plasticizer to obtain a rule that the dielectric loss of the transformer oil increases with the increase of the content of the plasticizer, thereby further confirming that analysis of the plasticizer content in the transformer oil is a method for analyzing a cause of an increase in dielectric loss of transformer oil. The method for analyzing a cause of an increase in dielectric loss of transformer oil proposed in the present invention on the basis that phthalate plasticizer is detected in transformer oil of several
-4 12419235_1 (GHMatters) P109787.AU
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transformers in operation suffering from insulation problems, gives the relationship between the content of the plasticizer and the dielectric loss of transformer oil by quantitative measurement on the content of the phthalate plasticizer in the transformer oil of several transformers in operation suffering from insulation problems, thereby confirming a method for analyzing a cause of an increase in dielectric loss of transformer oil by measuring the content of the plasticizer in the transformer oil; and meanwhile, establishes a method for quantitative measurement of plasticizers in the transformer oil. The method provided in the present invention has good accuracy and simple operation, and plays an important role in further perfecting the quality standards for transformer oil in operation.
[0018] In addition, the method provided in the present invention is applied in daily operation and maintenance of transformer oil, and is capable of timely discovering the causes of an increase in dielectric loss of the transformer oil, finding the source of the problem, and timely eliminating defects to ensure the safe and stable operation of the device.
[0019] Figure 1 is a selected ion chromatogram of 16 phthalate plasticizers.
[0020] Hereinafter, the technical solutions of the present invention will be described clearly and completely in combination with embodiments of the present invention. Obviously, the embodiments to be described are merely a part rather than all of embodiments of the present invention. Based on the embodiments in the present invention, all the other embodiments obtained by those of ordinary skill in the art without any creative work fall within the scope as claimed in the present invention.
[0021] The present invention provides a method for analyzing a cause of an increase in dielectric loss of transformer oil, comprising the steps of:
a) performing quantitative measurement on the content of phthalate plasticizer in multiple sets of transformer oil in actual operation by using an established method for quantitative measurement of phthalate plasticizer in transformer oil respectively, to obtain the concentration of the phthalate plasticizer contained in the transformer oil; and
-5 12419235_1 (GHMatters) P109787.AU
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b) measuring the dielectric loss of the transformer oil by preparing transformer oil samples having known concentrations of di-n-butyl phthalate respectively, and comparing the measurement results with the dielectric loss value of a transformer oil containing no plasticizer to obtain a rule that the dielectric loss of the transformer oil increases with the increase of the content of the plasticizer, thereby further confirming that analysis of the plasticizer content in the transformer oil is a method for analyzing a cause of an increase in dielectric loss of transformer oil.
[0022] In the present invention, the step a) is performing quantitative measurement on the content of phthalate plasticizer in multiple sets of transformer oil in actual operation by using an established method for quantitative measurement of phthalate plasticizer in transformer oil respectively, to obtain the concentration of the phthalate plasticizer contained in the transformer oil. In the present invention, the established method for quantitative measurement of phthalate plasticizer in transformer oil is preferably gas chromatography-mass spectrometry. In the present invention, the quantitative measurement by means of gas chromatography-mass spectrometry is performed with a gas chromatograph-mass spectrometer well known to those skilled in the art, preferably with a Model 7890A-5975C gas chromatograph-mass spectrometer manufactured by Agilent Co., USA. In the present invention, the transformer oil to be measured is preferably transformer oil in operation suffering from insulation problems, and the type and source of the transformer oil are not particularly limited in the present invention, for example, the domestic transformer oil No. 25 well known to those skilled in the art may be used.
[0023] In the present invention, the phthalate plasticizer is preferably one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, bis(2-methoxyethyl) phthalate, bis(4-methyl-2-pentyl) phthalate, bis(2-ethoxyethyl) phthalate, diamyl phthalate, di-n-hexyl phthalate, butyl benzyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, bis(2-ethylhexyl) phthalate, diphenyl phthalate, di-n-octyl phthalate, and di-nonyl phthalate
[0024] In the present invention, prior to the measurement by using an established method for quantitative measurement of phthalate plasticizer in transformer oil, the step a) preferably further comprises pretreating the multiple sets of transformer oil in actual operation. In the present invention, the pretreating serves to enrich the phthalate plasticizer so as to reduce
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errors during the measurement. In the present invention, the pretreating is preferably performed by a specific process, in which 25 ml of transformer oil to be measured is accurately measured and extracted with methanol twice (10 mL x 2), and then, the extract is collected in a 25 ml volumetric flask, and the volume is made up to the scale mark with methanol, to obtain samples to be measured by the method for quantitative measurement of phthalate plasticizer in transformer oil.
[0025] In the present invention, after the pretreating is completed, the resulting samples to be measured by the method for quantitative measurement of phthalate plasticizer in transformer oil are subjected to the quantitative measurement, to obtain the concentration of
the phthalate plasticizer contained in the transformer oil. In the present invention, the measurement preferably and specifically comprises the steps of:
al) preparing a series of standard solutions, wherein the standard solutions are standard solutions of a mixed phthalate plasticizer;
a2) subjecting the series of standard solutions to gas chromatography-mass spectrometry respectively, and establishing a standard curve based on the measurement results and the concentration of the phthalate plasticizer in the series of standard solutions; and
a3) subjecting the multiple sets of transformer oil in actual operation to gas chromatography-mass spectrometry respectively, and analyzing based on the measurement results and the established standard curve to obtain the content of the plasticizer in each of the sets of transformer oil to be measured.
[0026] In the present invention, a series of standard solutions are prepared at first. In the present invention, the standard solutions are preferably mixed standards of the phthalate plasticizer. In the present invention, the phthalate plasticizer is preferably one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, bis(2-methoxyethyl) phthalate, bis(4-methyl-2-pentyl) phthalate, bis(2-ethoxyethyl) phthalate, diamyl phthalate, di-n-hexyl phthalate, butyl benzyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, bis(2-ethylhexyl) phthalate, diphenyl phthalate, di-n-octyl phthalate, and di-nonyl phthalate. In a preferred embodiment of the present invention, the standard solution- is a mixed standard solution of 16 phthalates in methanol, which has a concentration of 1000 mg/L. In the present invention, the compositions and purities thereof in the standard solutions are shown in Table 1. -7 12419235_1 (GHMatters) P109787.AU
English translation of PCT/CN2017/077649 OP1817-08-0240
Table 1. Compositions and purities thereof in the mixed standards of 16 phthalates
Chinese name of Prt No. English name of Compound Abbreviation Purity Compound (%)
1 Dimethyl phthalate 4 A T fe DMP 99.9
2 Diethyl phthalate 4 A L Ni DEP 99.9
3 Diisobutyl phthalate DIBP 99.7
4 Di-n-butyl phthalate 4V AX, T fil DBP 99.8
fA'(2-vT 5 Bis(2-methoxyethyl) phthalate DMEP 98.2
6 Bis(4-methyl-2-pentyl)phthalate 4 Ti-TA -::(4-VT BMPP 99 (mixture of isomers) A-2-AA) i
fA'(2-L 7 Bis(2-ethoxyethyl) phthalate DEEP 99.4
8 Diamyl phthalate 4 T AA MWe DAP 99
9 Di-n-hexyl phthalate 4 TA2-V:: Ci DHXP 98.9
10 Butyl benzyl phthalate BBP 98.2
11 Bis(2-butoxyethyl) phthalate DBEP 99.3
~AX - c
12 Dicyclohexyl phthalate DCHP 99.9
fA'(2-L 13 Bis(2-ethylhexyl) phthalate DEHP 99.5
14 Diphenyl phthalate 4X, DPP 98.6
15 Di-n-octyl phthalate 4p Ay DNOP 99.2
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16 Di-nonyl phthalate (mixture of 4 AX, TI DNP 98 isomers)
[0027] In the present invention, the series of standard solutions preferably have concentrations of 20 mg/L, 50 mg/L and 100 mg/L, which are prepared with a method without particular limitation in the present invention, preferably at ratios as shown in Table 2, and stored in brown glass bottles and airtightly kept in the shadows.
Table 2. Preparation of series of standard solutions
Concentration of Volume of 1000 mg/L mixed Volume of methanol added standard solution standard added (mL) (mL) (mg/L)
20 0.02 0.98
50 0.05 0.95
100 0.1 0.9
[0028] In the present invention, after the preparation of the series of standard solutions is completed, the series of standard solutions are measured by means of gas chromatography-mass spectrometry. In the present invention, the instrument used in the gas chromatography-mass spectrometry measurement is not particularly limited, provided that it is a gas chromatograph-mass spectrometer well known to those skilled in the art, and preferably, a Model 7890A-5975C gas chromatograph-mass spectrometer manufactured by Agilent Co., USA may be used.
[0029] In the present invention, a chromatographic column in the gas chromatography-mass spectrometry is preferably a HP-5MS chromatographic separation column. In the present invention, the HP-5MS chromatographic separation column (30 m x 0.25 mm) is non-polar, is capable of excluding interferences during the measurement, and can accurately separate the phthalate plasticizer from the series of standard solutions.
[0030] In the present invention, the gas chromatography-mass spectrometry is performed with a temperature programming preferably by:
maintaining the chromatographic column at an initial temperature of 90°C-110°C -9 12419235_1 (GHMatter) P109787.AU
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for 0 min-0.5 min;
performing a first temperature raising up to 230°C-250°C at a rate of °C/min-25°C/min and then maintaining the temperature for 0.5 min-1.5 min; and
performing a second temperature raising up to 270°C-290°C at a rate of 3°C/min-7°C/min and then maintaining the temperature for 1 min-3 min;
more preferably by:
maintaining the chromatographic column at an initial temperature of 100°C for 0 min-0.5 min;
performing a first temperature raising up to 240°C at a rate of 20°C/min and then
maintaining the temperature for 1 min; and
performing a second temperature raising up to 280°C at a rate of 5°C/min and then maintaining the temperature for 2 min.
[0031] In the present invention, sample injection in the gas chromatography-mass spectrometry of step a) is performed preferably under conditions:
carrier gas in the gas chromatography-mass spectrometry is helium gas having a purity of>99.999%; and
the carrier gas in the gas chromatography-mass spectrometry has a flow rate of 0.5 mL/min-1.5 mL/min;
more preferably under conditions:
carrier gas in the gas chromatography-mass spectrometry is helium gas having a purity of>99.999%; and
the carrier gas in the gas chromatography-mass spectrometry has a flow rate of 1 mL/min.
[0032] In the present invention, mass spectrometry in the gas chromatography-mass spectrometry of step a) is preferably :
an electron-bombardment ion source having an electron energy of 70 eV in a selected ion monitoring mode.. In the present invention, the mass-to-charge ratio of molecular ions in the selected ion monitoring mode is shown in Table 3.
- 10 12419235_1 (GHMatters) P109787.AU
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Table 3. Quantitative ions in 16 phthalate plasticizer standard materials
Assisted quantitative Compound Retention time/min Quantitative ion/m/z ion/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
[0033] In the present invention, after the measurement on the series of standard solutions by means of gas chromatography-mass spectrometry is completed, standard curves are established based on the measurement results and the concentrations of the phthalate plasticizers in the series of standard solutions. In the present invention, the abscissa of the standard curves is the concentrations of the phthalate plasticizer, and the ordinate thereof is the measurement results. Subsequently, equations of the standard curves are obtained according to the established standard curve.
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[0034] In the present invention, the multiple sets of the transformer oil to be measured are separately measured by means of gas chromatography-mass spectrometry, and analyzed based on the measurement results and the established standard curves, to obtain the content of the plasticizer in each of the sets of transformer oil to be measured. In the present invention, prior to the measurement by means of gas chromatography-mass spectrometry, the method preferably further comprises pretreating the multiple sets of transformer oil to be measured. The action and specific process of the pretreating are the same as those described in the above technical solutions, and a detailed description thereof will be omitted.
[0035] In the present invention, the instrument used in the gas chromatography-mass spectrometry measurement is not particularly limited, provided that it is a gas chromatograph-mass spectrometer well known to those skilled in the art, and preferably, a Model 7890A-5975C gas chromatograph-mass spectrometer manufactured by Agilent Co., USA may be used.
[0036] In the present invention, a chromatographic column in the gas chromatography-mass spectrometry is preferably a HP-5MS chromatographic separation column. In the present invention, the HP-5MS chromatographic separation column (30 m x 0.25 mm) is non-polar, is capable of excluding interferences during the measurement, and can accurately separate the phthalate plasticizer from the transformer oil.
[0037] In the present invention, a temperature programming in the gas chromatography-mass spectrometry is performed preferably by:
maintaining the chromatographic column at an initial temperature of 90°C-110°C for 0 min0.5 min;
performing a first temperature raising up to 230°C-250°C at a rate of °C/min-25°C/min and then maintaining the temperature for 0.5 min-1.5 min; and
performing a second temperature raising up to 270°C-290°C at a rate of 3°C/min-7°C/min and then maintaining the temperature for 1 min-3 min;
more preferably by:
maintaining the chromatographic column at an initial temperature of 100°C for 0 min-0.5 min;
performing a first temperature raising up to 240°C at a rate of 20°C/min and then - 12 12419235_1 (GHMatter) P109787.AU
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maintaining the temperature for 1 min; and
performing a second temperature raising up to 280°C at a rate of 5°C/min and then maintaining the temperature for 2 min.
[0038] In the present invention, sample injection in the gas chromatography-mass spectrometry of step a) is performed preferably under conditions:
carrier gas in the gas chromatography-mass spectrometry is helium gas having a purity of>99.999%; and
the carrier gas in the gas chromatography-mass spectrometry has a flow rate of 0.5 mL/min-1.5 mL/min;
more preferably under conditions:
a carrier gas in the gas chromatography-mass spectrometry is helium gas having a purity of>99.999%; and
the carrier gas in the gas chromatography-mass spectrometry has a flow rate of 1 mL/min.
[0039] In the present invention, mass spectrometry in the gas chromatography-mass spectrometry of step a) is preferably:
an electron-bombardment ion source having an electron energy of 70 eV in a selected ion monitoring mode. In the present invention, the mass-to-charge ratio of molecular ions in the selected ion monitoring mode is shown in Table 3 below.
[0040] In the present invention, after the measurement on the multiple sets of transformer oil to be measured by means of gas chromatography-mass spectrometry is completed, the content of the plasticizer in each of the sets of transformer oil to be measured are obtained by analyzing based on the measurement results and the established standard curves.
[0041] In the present invention, the step b) is measuring the dielectric loss of the transformer oil by preparing transformer oil samples having known concentrations of di-n-butyl phthalate, and comparing the measurement results with a dielectric loss value of transformer oil containing no plasticizer for analysis to obtain a rule that the dielectric loss of the transformer oil increases with the increase of the content of the plasticizer, thereby further confirming that analysis of the plasticizer content in transformer oil is a method for analyzing - 13 12419235_1 (GHMatters) P109787.AU
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a cause of an increase in dielectric loss of transformer oil. In the present invention, the instrument and method used for the measuring the dielectric loss of the transformer oil are not particularly limited, provided that it is a standard test method (GB/T 5654) well known to those skilled in the art.
[0042] The present invention further provides use of the method for analyzing a cause of an increase in dielectric loss of transformer oil as described in the above technical solutions in operation and maintenance of transformer oil. In the present invention, since phthalate plasticizer is detected in transformer oil of multiple transformers having abnormal dielectric loss, it can be confirmed that the dielectric loss increases with the increase of the contents of the plasticizer, by establishing the above method for quantitative measurement and controlling the experiment. The method for analyzing a cause of an increase in dielectric loss of transformer oil provided in the present invention can be applied in daily measurement of transformer oil, as well as analysis of causes of failure and defects of transformer oil.
[0043] The present invention provides a method for analyzing a cause of an increase in dielectric loss of transformer oil, comprising the steps of: a) performing quantitative measurement on the contents of phthalate plasticizer in multiple sets of transformer oil in actual operation by using an established method for quantitative measurement of phthalate plasticizer in transformer oil, to obtain the concentration of the phthalate plasticizer contained in the transformer oil; and b) measuring the dielectric loss of the transformer oil by preparing transformer oil samples having known concentrations of di-n-butyl phthalate, and comparing the measurement results with a dielectric loss value of transformer oil containing no plasticizer for analysis to obtain a rule that the dielectric loss of the transformer oil increases with the increase of the content of the plasticizer, thereby further confirming that analysis of the plasticizer content in transformer oil is a method for analyzing a cause of an increase in dielectric loss of transformer oil. The method for analyzing a cause of an increase in dielectric loss of transformer oil proposed in the present invention on the basis that phthalate plasticizer is detected in transformer oil of several transformers in operation suffering from insulation problems, gives the relationship between the content of the plasticizer and the dielectric loss of transformer oil by quantitative measurement on the contents of the phthalate plasticizers in the transformer oil of several transformers in operation suffering from insulation problems, thereby confirming a method for analyzing a cause of an increase in dielectric loss of transformer oil by measuring the content of the plasticizer in the transformer oil; and - 14 12419235_1 (GHMatters) P109787.AU
English translation of PCT/CN2017/077649 OP1817-08-0240
meanwhile, establishes a method for quantitative measurement of plasticizers in the transformer oil. The method provided in the present invention has good accuracy and simple operation, and plays an important role in further perfecting the quality standards for transformer oil in operation.
[0044] In addition, the method provided in the present invention is applied in daily operation and maintenance of transformer oil, and is capable of timely discovering the causes of an increase in dielectric loss of the transformer oil, finding the source of the problem, and timely eliminating defects to ensure the safe and stable operation of the device.
[0045] Hereinafter, the following examples will be explained in detail in order to further illustrate the present invention.
Example 1
[0046] Establishment of standard curves
[0047] (1) Preparation of a series of standard solutions: 16 phthalate plasticizers were mixed in methanol (chromatographically pure) to prepare the mixed standard solutions, in which the phthalate plasticizers were dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, bis(2-methoxyethyl) phthalate, bis(4-methyl-2-pentyl) phthalate, bis(2-ethoxyethyl) phthalate, diamyl phthalate, di-n-hexyl phthalate, butyl benzyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, bis(2-ethylhexyl) phthalate, diphenyl phthalate, di-n-octyl phthalate, and di-nonyl phthalate;
[0048] wherein the standard solution as mixed standard 1 has a concentration of 20 mg/L, the standard solution as mixed standard 2 has a concentration of 50 mg/L, the standard solution as mixed standard 3 has a concentration of 100 mg/L, and the mixed standards 1-3 were the series of standard solutions.
[0049] (2) The mixed standards 1-3 were measured separately by means of gas chromatography-mass spectrometry in which a HP-5MS chromatographic separation column (30 m x 0.25 mm) was used and helium gas having purity of >99.999% was used as a carrier gas at a flow rate controlled to1 m/min. The temperature programming was: maintaining the
chromatographic column at an initial temperature of 100°C for 0 min-0.5 min, performing a first temperature raising up to 240°C at a rate of 20°C/min and then maintaining the - 15 12419235_1 (GHMatter) P109787.AU
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temperature for 1 min, and performing a second temperature raising up to 280°C at a rate of
°C/min and then maintaining the temperature for 2 min; and then, the mass spectrometry was
operated with an electron-bombardment ion source having an electron energy of 70 eV in an selected ion monitoring mode to obtain a selected ion chromatogram of 16 phthalate plasticizers as shown in Figure 1. The numbers in the chromatogram correspond to the numbers in Table 1.
[0050] (3) After the measurement of the series standard solutions by gas chromatography-mass spectrometry was completed, standard curves were established based on the measurement results and the concentrations of the phthalate plasticizers in the series of standard solutions in the present invention. The abscissa c of the standard curves was the concentrations of phthalate plasticizers, and the ordinate A thereof was the measurement results. Subsequently, equations of the standard curves were obtained according to the established standard curves. The linear equations and correlation coefficients of the mixed standard solutions of the 16 phthalate plasticizers are shown in Table 4.
Table 4. Linear equations and correlation coefficients of the mixed standard solutions with 16 phthalate plasticizers
Compound Linear equation Correlation coefficient
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
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English translation of PCT/CN2017/077649 OP1817-08-0240
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
Example 2
[0051] Measurement of contents of phthalate plasticizers in transformer oil
[0052] (1) 6 sets of transformer oil in operation suffering from insulation problems were subjected to pretreatment respectively: 25 ml of transformer oil to be measured was accurately measured and extracted with methanol twice (10 mL x 2); the extract was collected in a 25 ml volumetric flask, and the volume was made up to the scale mark with methanol; and 6 sets of transformer oil to be measured were obtained.
[0053] (2) The above 6 sets of transformer oil to be measured were subjected to gas chromatography-mass spectrometry by using a HP-5MS chromatographic separation column (30 m x 0.25 mm); helium gas having purity of >99.999% was used as a carrier gas at a flow rate controlled to 1 mL/min; the temperature programming was: maintaining the
chromatographic column at an initial temperature of 100°C for 0 min-0.5 min, performing a first temperature raising up to 240°C at a rate of 20°C/min and then maintaining the
temperature for 1 min, and performing a second temperature raising up to 280°C at a rate of
°C/min and then maintaining the temperature for 2 min; and then, the mass spectrometry was
operated with an electron-bombardment ion source having an electron energy of 70 eV in an selected ion monitoring mode.
[0054] (3) After the measurement of the above 6 sets of transformer oil to be measured by gas chromatography-mass spectrometry was completed, the content of the plasticizer in each of the sets of transformer oil to be measured were obtained by analyzing based on the measurement results and the standard curve established in Example 1 in the present invention. The contents of phthalate plasticizers in the 6 sets of transformer oil to be measured are - 17 12419235_1 (GHMatter) P109787.AU
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shown in Table 5.
Table 5. Contents of phthalate plasticizers in 6 sets of transformer oil
Compound Set I Set 2 Set 3 Set 4 Set 5 Set 6
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
BMPP 3.11 4.50 4.99 7.25 3.74 2.71
DCHP - 2.20 0.88 1.43 0.91 0.90
DEHP 2.83 5.19 3.45 4.18 3.49 3.47
[0055] The experimental results show that, phthalate plasticizers were found in all of the above 6 sets of transformer oil in operation suffering from insulation problems, and the content of di-n-butyl phthalate reached up to 20 mg/L.
Example 3
[0056] Evaluation of the measurement results
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[0057] Transformer oil having known concentrations of phthalate plasticizers was prepared and measured in accordance with the measurement method provided in Example 2. Measurement data of the transformer oil having known concentrations of phthalate plasticizers was obtained and shown in Table 6.
Table 6. Measurement data of transformer oil having known concentrations of phthalate plasticizers
Concentration (mg/L) Sample 1 Sample 2 Sample 3
Preparation 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
DNP 29 58 79
[0058] The experimental results show that, the quantitative measurement results of the phthalate plasticizers in the transformer oil provided in the present invention are quite - 19 12419235_1 (GHMatter) P109787.AU
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accurate.
Example 4
[0059] Analysis of causes of increase in dielectric loss of transformer oil
[0060] Transformer oil containing di-n-butyl phthalate at different concentrations was subjected to quantitative measurement for the dielectric loss, and the measurement results were compared with a dielectric loss value of transformer oil containing no plasticizer (blank oil). The measurement results are shown in Table 7 below.
Table 7. Dielectric loss data of transformer oil containing di-n-butyl phthalate at different concentrations
Volume Dielectric loss Interfacial Sample C(DBP)/mg/L resistivity (90°C) tension (mN/in) (90°C/ m)
Blank oil - 0.000677 1.23x1012 53
1 50 0.000779 1.13x1012 51.4
2 100 0.000893 9.11x10" 50.9
3 200 0.001025 6.73x10" 49
4 500 0.001631 3.89x10" 47.4
[0061] The experimental results show that, with the increase of the concentration of di-n-butyl phthalate, the dielectric loss gradually increased, the volume resistivity gradually reduced, and the interfacial tension gradually decreased. It can be seen that, the phthalate plasticizer will lead to an increase in dielectric loss of transformer oil and significantly influence the properties of transformer oil.
[0062] The previous description of the disclosed examples enables those skilled in the art to implement or use the present invention. Various modifications to these examples will be obvious for those skilled in the art, and the general principles as defined herein can be implemented in other examples without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these examples as
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English translation of PCT/CN2017/077649 OP1817-08-0240
exemplified herein, but is to be accorded the broadest scope consistent with the principles and novel features as disclosed herein.
[0063] In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
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Claims (10)
1. A method for analyzing a cause of an increase in dielectric loss of transformer oil, comprising the steps of:
a) performing quantitative measurement on the content of phthalate plasticizer in multiple sets of transformer oil in actual operation by using an established method for quantitative measurement of phthalate plasticizer in transformer oil respectively, to obtain the concentration of the phthalate plasticizer contained in the transformer oil; and
b) measuring the dielectric loss of the transformer oil by preparing transformer oil samples having known concentrations of di-n-butyl phthalate respectively, and comparing the measurement results with the dielectric loss value of a transformer oil containing no plasticizer, to obtain a rule that the dielectric loss of the transformer oil increases with the increase of the content of the plasticizer, thereby further confirming that analysis of the plasticizer content in the transformer oil is a method for analyzing a cause of an increase in dielectric loss of transformer oil.
2. The method according to claim 1, wherein the established method for quantitative measurement of phthalate plasticizer in transformer oil in step a) is gas chromatography-mass spectrometry.
3. The method according to claim 2, wherein a chromatographic column in the gas chromatography-mass spectrometry of step a) is a HP-5MS chromatographic separation column.
4. The method according to claim 2 or claim 3, wherein a temperature programming in the gas chromatography-mass spectrometry of step a) is:
maintaining the chromatographic column at an initial temperature of 90°C~110°C for 0 min0.5 min;
performing a first temperature raising up to 230°C-250°C at a rate of
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English translation of PCT/CN2017/077649 OP1817-08-0240
°C/min-25°C/min and then maintaining the temperature for 0.5 min-1.5 min; and
performing a second temperature raising up to 270°C-290°C at a rate of 3°C/min-7°C/min and then maintaining the temperature for 1 min-3 min.
5. The method according to any one of claims 2 to 4, wherein conditions for sample injection in the gas chromatography-mass spectrometry of step a) is:
carrier gas in the gas chromatography-mass spectrometry is helium gas having a purity of> 99.999%; and
the carrier gas in the gas chromatography-mass spectrometry has a flow rate of 0.5 mL/min-1.5 m/mmin.
6. The method according to any one of claims 2 to 5, wherein conditions for mass spectrometry in the gas chromatography-mass spectrometry of step a) is:
an electron-bombardment ion source having an electron energy of 70 eV in a selected ion monitoring mode.
7. The method according to any one of claims 1 to 6, wherein prior to the measurement by using the established method for quantitative measurement of phthalate plasticizer in transformer oil, step a) further comprises:
pretreating the multiple sets of transformer oil in actual operation respectively;
wherein the procedure of the pretreating is:
extracting the transformer oil in actual operation and adjusting the volume thereof to obtain samples to be measured by the method for quantitative measurement of phthalate plasticizer in transformer oil.
8. The method according to any one of claims 1 to 7, wherein the phthalate plasticizer in step a) is one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, bis(2-methoxyethyl) phthalate, -23 12419235_1 (GHMatter) P109787.AU
English translation of PCT/CN2017/077649 OP1817-08-0240
bis(4-methyl-2-pentyl) phthalate, bis(2-ethoxyethyl) phthalate, diamyl phthalate, di-n-hexyl phthalate, butyl benzyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, bis(2-ethylhexyl) phthalate, diphenyl phthalate, di-n-octyl phthalate, and di-nonyl phthalate.
9. The method according to any one of claims 1 to 8, wherein step a) specifically comprises the steps of:
al) preparing a series of standard solutions, wherein the standard solutions are standard solutions of a mixed phthalate plasticizer;
a2) subjecting the series of standard solutions to gas chromatography-mass spectrometry respectively, and establishing a standard curve based on the measurement results and the concentration of the phthalate plasticizer in the series of standard solutions; and
a3) subjecting the multiple sets of transformer oil in actual operation to gas chromatography-mass spectrometry respectively, and analyzing based on the measurement results and the established standard curve to obtain the content of the plasticizer in each of the sets of transformer oil to be measured.
10. Use of the method for analyzing a cause of an increase in dielectric loss of transformer oil according to any one of claims 1 to 9 in operation and maintenance of transformer oil.
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