CN103954520A - Method for testing content of corrosive sulphur in insulating oil - Google Patents
Method for testing content of corrosive sulphur in insulating oil Download PDFInfo
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- CN103954520A CN103954520A CN201410172101.7A CN201410172101A CN103954520A CN 103954520 A CN103954520 A CN 103954520A CN 201410172101 A CN201410172101 A CN 201410172101A CN 103954520 A CN103954520 A CN 103954520A
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Abstract
The invention discloses a method for testing content of corrosive sulphur in insulating oil. The method comprises the following steps: (1) taking insulating oil samples or mixing the insulating samples with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid to form a transformer oil mixed solution; (2) coating a quartz crystal resonance oscillation piece by the samples or the mixed solution and connecting with a test workstation; (3) recording the frequency f1; (4) carrying out an electrochemical polarization test and recording the frequency f2; (5) calculating the frequency change delta f according to the formula that delta f=f1-f2; (6) calculating the content of the corrosive sulphur in the insulating oil used in the transformer by using the formula that delta f= -2f0<2>delta m/A(muqrhoq)<1/2>. According to the method, the content of the corrosive sulphur in the insulating oil used in the transformer can be accurately and quantitatively tested, and the device is easy and convenient to operate, and has the important guiding significance on judgment of incipient faults of transformers and development of state maintenance work of the transformers.
Description
Technical field
The present invention relates to a kind of method that detects oil property, especially a kind of method that detects active sulfur content in transformer use insulating oil.
Background technology
Transformer is directly connected to safe operation and the serviceable life of electrical equipment by the quality of insulating oil performance.And the sulfide in insulating oil for transformer can form cuprous sulfide copper coil is produced to corrosive attack in transformer operational process on insulating paper.First this sulfide can make the insulating property of insulating paper reduce, and cause the insulating paper of transformer breakdown, thereby it is damaged to cause transformer.So, strengthen the supervision of active sulfur in insulating oil to detect outstanding aobvious necessary.Yet, up to the present, in insulating oil the detection of active sulfur still adopt traditional ASTM D (wherein " ASTM " be English full name is the abbreviation of " American Society for Testing and Materials ", and its Chinese translation is " American Society Testing and Materials "; " D " is Sort Code, mean and comprise petroleum products, and fuel, low strong plastics are at the code of interior material.) 1275 quilitative methods, or IEC (English full name is the abbreviation of " International Electro technical Commission ", and its Chinese translation is " International Electrotechnical Commission ".) (German full name is the abbreviation of " Deutsches Institut f ü r Normung e.V. ", and its Chinese translation is " meeting of DIN chemistry " for 62535 quilitative methods, DIN.) (wherein " GB " is the abbreviation of Chinese pinyin " GUO JIA BIAO ZHUN ", and its Chinese is " national standard ", and " T " represents to recommend for 51353 quilitative methods, GB/T.) 25961 quilitative methods.Above-mentioned these traditional quilitative method ubiquities length consuming time, inefficient defect.For example the judgement of test findings is mainly relied on to the intuitive judgment to color, therefore cannot give quantificational description to the corrosive nature of oil product.For insulating oil corrosion condition being carried out to the accurate judgement that quantizes, be extremely necessary to design as early as possible a kind of method of active sulfur content in insulating oil for transformer that detects, to provide safeguard for the safe operation of electrical equipment.
Summary of the invention
The technical problem to be solved in the present invention is, the ubiquitous defect of detection method for traditional transformer with active sulfur content in insulating oil, the method of active sulfur content in a kind of improved detection insulating oil is provided, require that the method required detection time is short, efficiency is high, can carry out accurate quantification to insulating oil corrosion condition and judge, thereby can provide safeguard for the safe operation of electrical equipment.
Technical scheme of the present invention is that a kind of method that detects active sulfur content in insulating oil providing comprises following processing step:
(1), get and entrust transformer insulating oil sample used 0.05ml～0.5ml; Or get and entrust transformer insulating oil sample used 0.05ml～0.5ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid or potassium hydroxide aqueous solution or sodium sulphate ethanolic solution 0.05ml～0.5ml to be hybridly prepared into transformer oil mixed solution;
(2), get 1 of QCM (Quartz Crystal Microbalance).(1) step is got and entrusted transformer insulating oil sample used or step (1) to obtain on the quartz crystal resonance piece that transformer oil mixed solution is evenly coated in got QCM (Quartz Crystal Microbalance).Then this quartz crystal resonance piece is inserted in the sensor stand of got QCM (Quartz Crystal Microbalance), and by wire, described quartz crystal resonance piece is connected with peripheral hardware electrochemical quartz crystal microbalance testing workstation.Use QCM (Quartz Crystal Microbalance) (QCM) detection limit can arrive nanogram level.Electrochemical techniques YuQCM technical battery is used, set up into electrochemical quartz crystal microbalance (EQCM) technology, can obtain the information that quartz crystal electrode surface quality changes by the detection of QCM frequency on the one hand, quartz crystal electrode is as the working electrode of electro-chemical test system on the other hand, can realize the measurement to electrochemical parameter, thereby obtain the various information of electrode surface galvanochemistry and non-electrochemical process simultaneously; The QCM (Quartz Crystal Microbalance) using in this step (QCM) is the piezoelectric property of utilizing quartz-crystal resonator, the frequency change that the variation of quartz crystal oscillator electrode surface quality is converted into quartz crystal oscillator circuit output electrical signals is measured, there is the advantages such as highly sensitive, equipment is simple, detectability can arrive nanogram level, the fields such as chemistry, physics, biology, medical science and material science have been widely used in, but QCM technology is not applied to active sulfur detection field before this always, for people stay many sorry.
(3), recording step is inserted the frequency f 1 of the quartz crystal resonance piece of described sensor stand in (2);
(4), using described quartz crystal resonance piece as working electrode, using platinum electrode be to be the conventional three-electrode system that is contrast electrode to electrode, silver/silver chloride electrode to routine two electrode systems of electrode or platinum electrode, with conventional potentiostatic method or conventional linear scanning method or conventional galvanostatic method or conventional pulse voltammetry or regular circulation voltammetry, this quartz crystal resonance piece is implemented to activation polarization test.When this quartz crystal resonance piece obtains activation polarization, the frequency f 2 while recording this quartz crystal resonance piece acquisition activation polarization;
(5), according to formula Δ f=f1-f2, in formula, Δ f is frequency change, f1 is the frequency of quartz crystal resonance piece before activation polarization, f2 is the frequency of quartz crystal resonance piece after activation polarization, calculates step and (4) quartz crystal resonance piece is implemented to the activation polarization test described quartz crystal resonance piece frequency change Δ f in front and back;
(6), use formula Δ f=-2f
0 2Δ m/A (μ
qρ
q)
1/2, in formula, Δ f is frequency change, f
0for quartz crystal resonance piece fundamental frequency, Δ m is mass change, and A is the reaction area of quartz crystal resonance piece, μ
qfor modulus of shearing constant, ρ
qfor crystalline density, calculate the quality that (4) step corrode sulfur product to the mass change Δ m of described quartz crystal resonance piece before and after the test of quartz crystal resonance piece enforcement activation polarization, (1) the value of this mass change Δ of gained m is got and is entrusted transformer insulating oil sample volume used divided by step, is the content of active sulfur in described trust transformer insulating oil used.
The invention has the beneficial effects as follows: can easily and accurately quantitatively detect the content of active sulfur in transformer oil, device is simple, easy to operate, for the latency fault of diagnosis transformer and repair based on condition of component work how to carry out transformer, there is very important directive significance.
Embodiment
Embodiment 1:
(1), get and entrust 220kV transformer insulating oil sample used 0.05ml;
(2), get 1 of the silver-colored type QCM (Quartz Crystal Microbalance) of commercially available two-sided quilt.(1) step is got and entrusted 220kV transformer insulating oil sample used to be evenly coated on the quartz crystal resonance piece of got QCM (Quartz Crystal Microbalance).Then this quartz crystal resonance piece is inserted in the sensor stand of got QCM (Quartz Crystal Microbalance), and by wire, described quartz crystal resonance piece is connected with peripheral hardware electrochemical quartz crystal microbalance testing workstation;
(3), recording step is inserted the frequency f 1 of the quartz crystal resonance piece of described sensor stand in (2);
, using described quartz crystal resonance piece as working electrode, use conventional platinum electrode for to two electrode systems of electrode and conventional potentiostatic method, this quartz crystal resonance piece is implemented to activation polarization and tests, current potential 1.5V.When this quartz crystal resonance piece obtains activation polarization, the frequency f 2 while recording this quartz crystal resonance piece acquisition activation polarization;
(5), according to formula Δ f=f1-f2, in formula, Δ f is frequency change, f1 is the frequency of quartz crystal resonance piece before activation polarization, f2 is the frequency of quartz crystal resonance piece after activation polarization, calculates step and (4) quartz crystal resonance piece is implemented to the activation polarization test described quartz crystal resonance piece frequency change Δ f in front and back;
(6), use formula Δ f=-2f
0 2Δ m/A (μ
qρ
q)
1/2, in formula, Δ f is frequency change, f
0for quartz crystal resonance piece fundamental frequency, Δ m is mass change, and A is the reaction area of quartz crystal resonance piece, μ
qfor modulus of shearing constant, ρ
qfor crystalline density, calculate step and (4) quartz crystal resonance piece is implemented the mass change Δ m of the described quartz crystal resonance piece in activation polarization test front and back, (1) the value of this mass change Δ of gained m is got and is entrusted transformer insulating oil sample volume used divided by step, is the content of entrusting active sulfur in transformer insulating oil used.
Embodiment 2:
(1), get and entrust 110kV transformer insulating oil sample used 0.5ml, sodium sulphate ethanolic solution 0.5ml to be hybridly prepared into transformer oil mixed solution;
(2), get 1 of commercially available QCM type QCM (Quartz Crystal Microbalance).(1) step is obtained on the quartz crystal resonance piece that transformer oil mixed solution is evenly coated in got QCM (Quartz Crystal Microbalance).Then this quartz crystal resonance piece is inserted in the sensor stand of got QCM (Quartz Crystal Microbalance), and by wire, described quartz crystal resonance piece is connected with peripheral hardware electrochemical quartz crystal microbalance testing workstation;
Step is (3) with embodiment 1;
(4), using described quartz crystal resonance piece as working electrode, conventional three-electrode system and regular circulation voltammetry that use platinum electrode is is contrast electrode to electrode, silver/silver chloride electrode, this quartz crystal resonance piece is implemented to activation polarization test, initial voltage-0.5V, final voltage 2.0V, sweep velocity 0.05V/s.When this quartz crystal resonance piece obtains activation polarization, the frequency f 2 while recording this quartz crystal resonance piece acquisition activation polarization;
Step (5)～(6) with embodiment 1.
Claims (1)
1. a method that detects active sulfur content in insulating oil, the method comprises the steps:
(1), get and entrust transformer insulating oil sample used 0.05ml～0.5ml; Or get and entrust transformer insulating oil sample used 0.05ml～0.5ml, 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid or potassium hydroxide aqueous solution or sodium sulphate ethanolic solution 0.05ml～0.5ml to be hybridly prepared into transformer oil mixed solution;
(2), get 1 of QCM (Quartz Crystal Microbalance), (1) step is got and entrusted transformer insulating oil sample used or step (1) to obtain on the quartz crystal resonance piece that transformer oil mixed solution is evenly coated in got QCM (Quartz Crystal Microbalance), then this quartz crystal resonance piece is inserted in the sensor stand of got QCM (Quartz Crystal Microbalance), and by wire, described quartz crystal resonance piece is connected with peripheral hardware electrochemical quartz crystal microbalance testing workstation;
(3), recording step is inserted the frequency f 1 of the quartz crystal resonance piece of described sensor stand in (2);
(4), using described quartz crystal resonance piece as working electrode, using platinum electrode be to be the conventional three-electrode system that is contrast electrode to electrode, silver/silver chloride electrode to routine two electrode systems of electrode or platinum electrode, with conventional potentiostatic method or conventional linear scanning method or conventional galvanostatic method or conventional pulse voltammetry or regular circulation voltammetry, this quartz crystal resonance piece is implemented to activation polarization test, when this quartz crystal resonance piece obtains activation polarization, the frequency f 2 while recording this quartz crystal resonance piece acquisition activation polarization;
(5), according to formula Δ f=f1-f2, in formula, Δ f is frequency change, f1 is the frequency of quartz crystal resonance piece before activation polarization, f2 is the frequency of quartz crystal resonance piece after activation polarization, calculates step and (4) quartz crystal resonance piece is implemented to the activation polarization test described quartz crystal resonance piece frequency change Δ f in front and back;
(6), use formula Δ f=-2f
0 2Δ m/A (μ
qρ
q)
1/2, in formula, Δ f is frequency change, f
0for quartz crystal resonance piece fundamental frequency, Δ m is mass change, and A is the reaction area of quartz crystal resonance piece, μ
qfor modulus of shearing constant, ρ
qfor crystalline density, calculate step and (4) quartz crystal resonance piece is implemented the mass change Δ m of the described quartz crystal resonance piece in activation polarization test front and back, (1) the value of this mass change Δ of gained m is got and is entrusted transformer insulating oil sample volume used divided by step, is the content of active sulfur in described trust transformer insulating oil used.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104535449A (en) * | 2015-01-21 | 2015-04-22 | 山东师范大学 | Non-contact electrode piezoelectric transducer device for monitoring strongly-corrosive gas and method |
| CN104807902A (en) * | 2015-04-27 | 2015-07-29 | 广东电网有限责任公司电力科学研究院 | Detection method of dibenzyl disulfide and antioxidant in insulating oil |
| CN105092458A (en) * | 2015-08-13 | 2015-11-25 | 国家电网公司 | Method for evaluating sulfur corrosion state of transformer copper coil |
| CN105181940A (en) * | 2015-10-29 | 2015-12-23 | 大庆市日上仪器制造有限公司 | Anti-explosion automatic ventilation insulating oil corrosive sulfur determination instrument |
| CN105388227A (en) * | 2015-10-29 | 2016-03-09 | 山东中实易通集团有限公司 | Quantitative detection method of benzyl disulfide in oil in oil-filled electrical equipment oil |
| CN108693223A (en) * | 2017-04-06 | 2018-10-23 | 北京至感传感器技术研究院有限公司 | The on-line monitoring method and system of active sulfur in liquid oil |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104535449A (en) * | 2015-01-21 | 2015-04-22 | 山东师范大学 | Non-contact electrode piezoelectric transducer device for monitoring strongly-corrosive gas and method |
| CN104535449B (en) * | 2015-01-21 | 2017-02-22 | 山东师范大学 | Non-contact electrode piezoelectric transducer device for monitoring strongly-corrosive gas and method |
| CN104807902A (en) * | 2015-04-27 | 2015-07-29 | 广东电网有限责任公司电力科学研究院 | Detection method of dibenzyl disulfide and antioxidant in insulating oil |
| CN104807902B (en) * | 2015-04-27 | 2016-06-08 | 广东电网有限责任公司电力科学研究院 | The detection method of benzyldithio toluene and antioxidant in insulating oil |
| CN105092458A (en) * | 2015-08-13 | 2015-11-25 | 国家电网公司 | Method for evaluating sulfur corrosion state of transformer copper coil |
| CN105181940A (en) * | 2015-10-29 | 2015-12-23 | 大庆市日上仪器制造有限公司 | Anti-explosion automatic ventilation insulating oil corrosive sulfur determination instrument |
| CN105388227A (en) * | 2015-10-29 | 2016-03-09 | 山东中实易通集团有限公司 | Quantitative detection method of benzyl disulfide in oil in oil-filled electrical equipment oil |
| CN108693223A (en) * | 2017-04-06 | 2018-10-23 | 北京至感传感器技术研究院有限公司 | The on-line monitoring method and system of active sulfur in liquid oil |
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