CN110018190A - A kind of X-fluorescence surveys the quantitative evaluation method of active sulfur - Google Patents
A kind of X-fluorescence surveys the quantitative evaluation method of active sulfur Download PDFInfo
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- CN110018190A CN110018190A CN201910359922.4A CN201910359922A CN110018190A CN 110018190 A CN110018190 A CN 110018190A CN 201910359922 A CN201910359922 A CN 201910359922A CN 110018190 A CN110018190 A CN 110018190A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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Abstract
The invention discloses the quantitative evaluation methods that a kind of X-fluorescence surveys active sulfur, comprising the following steps: 1) sample is put into container；2) the copper test piece of not sulfur-bearing is put into the container for having taken sample, it is ensured that copper test piece is totally submerged in oil, and container is sealed；3) container containing copper test piece in step 2) is put into 150 DEG C ± 3 DEG C of baking oven, 24~72h of constant temperature takes out container after experiment；4) to be heated to pour out sample after the completion, copper test piece is taken out, and immerses in cleaning solvent, washes away the attachment sample in copper test piece；5) copper test piece is subjected to sulfur content test with X-fluorescence；6) result judges.The present invention is after being chemically reacted by experiment progress copper and sulphur and its compound, by determining to whether there is active sulfur compound in oil the case where X-fluorescence copper test test piece sulfur-containing compound, method of the invention can accurate judgement active sulfur and the case where non-aggressive sulphur, concrete operations are practical.
Description
Technical field
The present invention relates to transformer oil active sulfur detection technique fields, and in particular to a kind of X-fluorescence surveys active sulfur
Quantitative evaluation method.
Background technique
The active sulfur detection method of oil for electric power (referring mainly to transformer oil) has at present: SH/T 0304, SH/T 0804,
GB/T 25961, DL/T 285 etc., basic principle be all by under different condition, the copper product of different size and electric insulation oil
In sulfide react, by experiment after copper product appearance, surface is shown in graphite ash, dark brown or black
Any result is it is determined that the sulphur that is corrosive, other colors are non-corrosive.
Sulphur is one of component of petroleum, and the existing forms in crude oil have elementary sulfur, hydrogen sulfide and mercaptan, sulphur
The organic sulfur compounds such as ether, disulphide, thiophene can be divided into active sulfide and inactive sulfur compound by property.The former is main
It is elementary sulfur, hydrogen sulfide and mercaptan etc., activity, which is embodied in, has stronger corrosiveness to metal equipment.But above to activity,
Inactive sulfur compound division not be it is unalterable, some inactive sulfur compounds be subjected to thermal decomposition after just will become active sulfur
Compound, such as H2S。
The method of the prior art mainly has the disadvantage that:
1) more subjective to the appearance color judgement of copper product, the complicated multiplicity of surface color determines difficulty, is easy to appear mistake
The case where sentencing corrosivity and non-aggressive.
2) when copper product surface is judged as non-aggressive, it is understood that there may be less amount of active sulfur, end can embody, lead
The case where causing corrosion equipment occurs.The variation of copper product surface color is that a quantitative change reaches degree of pledging love and just shows, to equipment
Failure is meaningful, but is difficult to determine to the initial stage incipient fault of equipment.
3) when sample have black suspension object it is more when, can in one layer of atrament that can not be cleaned of copper product adsorption,
So as to cause the false judgment of result, the false judgment that the atraments such as copper oxide also easily lead to result is generated.
Existing Chinese patent 201510434614.5 discloses multiple sulfide qualitative and quantitative point in a kind of transformer oil
Analysis method, pass through sulfur chemiluminescent detector and gas chromatograph the advantages of, the two is united and applied in analysis transformer oil
In sulfide that may be present, be that can generate the type and content of corrosive sulphur compound by detecting and analyzed, but corruption
The sulphur compound of corrosion is many kinds of, needs to detect determination one by one, and technical difficulty increases, detection while the n-compound needed
Many kinds of (detection compound and n-compound will correspond) closes as detection cannot cover all corrosive vulcanizations
Object will appear the corrosive sulphur compound of missing inspection just so as to cause qualitative analysis inaccuracy.
Summary of the invention
There is provided one kind it is an object of the invention to overcome in place of the shortcomings of the prior art can be easy, practical, quasi-
Really, the method that efficiently copper product after evaluation experimental carries out X-fluorescence test active sulfur.Testing result can be improved in this method
Accuracy, and it is more significant to the initial stage or potential problems of equipment fault.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of X-fluorescence surveys the quantitative assessment side of active sulfur
Method, comprising the following steps:
1) it samples: sample is put into container；
2) copper product prepares: the copper test piece of not sulfur-bearing being put into the container for having taken sample, it is ensured that copper test piece is totally submerged
Into oil, container is sealed；
3) it heats: the container containing copper test piece in step 2) being put into 150 DEG C ± 3 DEG C of environment and reacted, constant temperature 24~
72h, extracting container after experiment；
4) cleaning of copper test piece: sample is poured out after the completion of to be heated, copper test piece is taken out, and immerses in cleaning solvent, is washed
Remove the attachment sample in copper test piece；
5) X-fluorescence of copper test piece tests active sulfur: copper test piece is carried out sulfur content test with X-fluorescence；
6) result judges.
The present invention is that (the assessment side after corrosion generation after copper is chemically reacted with sulphur and its compound is carried out by experiment
Method) generate CuS, Cu2S etc., by being determined in oil the case where X-fluorescence copper test test piece sulfur-containing compound with the presence or absence of activity vulcanization
Close object, can accurate judgement active sulfur and the case where non-aggressive sulphur, concrete operations are practical.The present invention is based on corrosion
The quantitative analysis method detected after generation to corrosive sulphur such as sulphur and its compound, can be avoided the judgement of active sulfur
Error situation has more reliability to testing result.The present invention is by developing a judgment value (such as > 250mg/kg), ability
Simply, quickly, the presence of accurate judgement active sulfur, a judgment value (such as 0- is also developed to the initial stage incipient fault of equipment
It could 250mg/kg) instruct initial stage or the potential problems of equipment fault.And the present invention can exactly solve the above problems.
The preferred embodiment of the quantitative evaluation method of active sulfur is surveyed as X-fluorescence of the invention, the container uses
Closed container.It is highly preferred that the closed container uses ml headspace bottle.
The preferred embodiment of the quantitative evaluation method of active sulfur, the cleaning solvent are surveyed as X-fluorescence of the invention
For petroleum ether III.
The preferred embodiment of the quantitative evaluation method of active sulfur is surveyed as X-fluorescence of the invention, in the step 2)
Sealing the metal cover containing rubber gasket can be used covered.
The preferred embodiment of the quantitative evaluation method of active sulfur is surveyed as X-fluorescence of the invention, the step 3) mentions
It is preceding that temperature is set in 150 ± 3 DEG C, and constant temperature 30min or more by baking oven.The chemistry of copper and sulphur can more preferably be accelerated in this temperature
Reaction.
The preferred embodiment of the quantitative evaluation method of active sulfur is surveyed as X-fluorescence of the invention, it is described by copper test piece
Polishing is bright, and is cleaned up with cleaning solvent, whether contains sulphur with X-fluorescence sulfur detector detection copper test piece, no sulphur can be copper
Test piece is put into the container for having taken sample.Preferably, the copper test piece is polished using sand paper.
Result judgment method of the present invention are as follows: if the non-corrosive sulphur of sample exists, test result 0, be corrosive sulphur
The concrete content of sulfur content can be directly tested out in the presence of if.
The beneficial effects of the present invention are:
1) quantitative analysis of the invention can pass through though cannot really reflect the active sulfur content in transformer oil sample
Active sulfur and copper product occur to chemically react and the sulfur content that stays on copper product surface carrys out the active sulfur in indirect reaction sample
The accuracy of testing result can be improved in content, while also can reflect active sulfur to the corrosion tendency of copper product.
2) present invention can effectively reduce the copper test piece result after sampling test by the sulfur content of X-fluorescence copper test test piece
The case where judging active sulfur by accident.
3) when the present invention can test quantitative analysis non-aggressive sulphur with X-fluorescence, it is understood that there may be less amount of active sulfur situation,
Simultaneously also can quantitative analysis active sulfur when active sulfur content situation.
4) present invention can effectively exclude to generate one layer of atrament that can not be cleaned of copper oxide and copper product adsorption
The judgement of equal non-aggressives sulphur.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the outside drawing of the sample a of the embodiment of the present invention 1, sample b, sample c, sample d, sample e, sample f.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to the present invention
It further illustrates.It will be appreciated by those skilled in the art that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
In embodiment, used experimental method is conventional method unless otherwise specified, material used, reagent etc.,
It is commercially available unless otherwise specified.
Main agents and instrument of the invention are as follows:
1) baking oven: temperature is controlled at 150 DEG C ± 3 DEG C；
2) ml headspace bottle: 20mL, internal diameter of the bottleneck are not less than 12mm, there is the metal cover of rubber gasket；
3) copper product: copper product meets the requirement of the T2 in GB/T3952, specification: 12mm × 30mm；
4) tweezers: stainless steel, graduated cylinder: 100mL, beaker: 100mL；
5) polishing material: the sand paper of 240 mesh；
5) cleaning solvent: pure petroleum ether III (60 DEG C -90 DEG C) is analyzed, it is desirable that not sulfur-bearing；
6) X-fluorescence sulfur detector: LAB-X3500SC1.
Embodiment 1
A kind of X-fluorescence of the invention surveys the quantitative evaluation method of active sulfur, the method the following steps are included:
1) 15mL homogeneous sample is taken with 100mL graduated cylinder, be put into the ml headspace bottle of 20mL；
2) copper test piece sample a, sample b, sample c, sample d, sample e, sample f are used respectively the sand paper polishing light of 240 mesh
It is bright, and cleaned up with petroleum ether III, whether contain sulphur with X-fluorescence sulfur detector detection copper test piece, no sulphur can put copper test piece
Enter and taken in the container of sample, it is ensured that copper test piece is totally submerged in oil, and covers the metal cover containing rubber gasket；
3) baking oven is opened in advance to set at 150 ± 3 DEG C temperature, and constant temperature 30min or more, said vesse is put into
In 150 DEG C ± 3 DEG C of baking oven, constant temperature for 24 hours or 48h or 72h, every the appearance and color for passing through ml headspace bottle for 24 hours and observing copper test piece
Variation such as finds that surface shows that any one of graphite ash, dark brown or black can stop testing；After experiment
Take out container；The container uses closed container, such as ml headspace bottle.
4) sample is poured out after the completion of experiment, is immediately taken out copper test piece with tweezers, and immerse in cleaning solvent petroleum ether III,
The attachment sample for washing away sample a in copper test piece, sample b, sample c, sample d, sample e, sample f takes out copper examination immediately after cleaning
Piece is dried, and can be blotted with filter paper, and carries out visual examination.
5) copper test piece sample a, sample b, sample c, sample d, sample e, sample f are put into the specimen cup of X-fluorescence test
Carry out sulfur content test.X-fluorescence equipment uses existing parameter；
6) if the non-corrosive sulphur of sample exists, test result 0, the sulphur that is corrosive can be tested out directly if existing
The concrete content of sulfur content.
Visual inspection result is as shown in Figure 2 and Table 1, and it is as shown in table 1 that X-fluorescence tests test result:
Table 1
As can be seen from Figure 2 and table 1 is it is found that after by appearance and color change judgement sample a, sample b, sample c test
Copper test piece result is non-corrosive sulphur, and the copper test piece result after sample d, sample e, sample f test is the sulphur that is corrosive.Pass through X
The sulfur content of fluorometric investigation copper test piece, as the result is shown sample c, sample d, sample e number sampling test after copper test piece have corruption
Corrosion sulphur, the copper test piece after sample b test have that the risk of potential corrosion sulphur is significant to equipment potential corrosion failure, sample a,
The non-corrosive sulphur of copper test piece after the sampling test of sample f, the copper test piece after the sampling test of sample f may generate copper oxide and
It turns black, to reduce the erroneous judgement of sample c, sample f.
The precision (repeatability) of 2 method of embodiment
In the same experiment, same test sample is carried out according to 1 method of embodiment by the same experimenter, experiment is at least
It is repeated 6 times, investigates the repeatability of method, the results are shown in Table 2:
Table 2
As known from Table 2, the precision of the X-fluorescence test active sulfur quantitative analysis method of copper test piece of the invention is
13.8%, it is seen that this method precision is high, reproducible.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (8)
1. the quantitative evaluation method that a kind of X-fluorescence surveys active sulfur, which comprises the following steps:
1) it samples: sample is put into container；
2) copper product prepares: the copper test piece of not sulfur-bearing being put into the container for having taken sample, it is ensured that copper test piece is totally submerged oil
In, and container is sealed；
3) it heats: the container containing copper test piece in step 2) being put into 150 DEG C of ± 3 DEG C of environment and is reacted, 24~72h of constant temperature is real
Container is taken out after testing；
4) cleaning of copper test piece: sample is poured out after the completion of to be heated, copper test piece is taken out, and immerses in cleaning solvent, washes away copper
Attachment sample in test piece；
5) X-fluorescence of copper test piece tests active sulfur: copper test piece is carried out sulfur content test with X-fluorescence；
6) result judges.
2. the quantitative evaluation method that X-fluorescence according to claim 1 surveys active sulfur, which is characterized in that the container is adopted
Use closed container.
3. the quantitative evaluation method that X-fluorescence according to claim 2 surveys active sulfur, which is characterized in that the closed appearance
Device uses ml headspace bottle.
4. the quantitative evaluation method that X-fluorescence according to claim 1 surveys active sulfur, which is characterized in that the washing is molten
Agent is petroleum ether III.
5. the quantitative evaluation method that X-fluorescence according to claim 1 surveys active sulfur, which is characterized in that the step 3)
Temperature is set in 150 ± 3 DEG C, and constant temperature 30min or more by baking oven in advance.
6. the quantitative evaluation method that X-fluorescence according to claim 1 surveys active sulfur, which is characterized in that described to try copper
Piece polishing is bright, and is cleaned up with cleaning solvent, whether contains sulphur with X-fluorescence sulfur detector detection copper test piece, and no sulphur can be
Copper test piece is put into the container for having taken sample.
7. the quantitative evaluation method that X-fluorescence according to claim 6 surveys active sulfur, which is characterized in that the copper test piece
It is polished using sand paper.
8. the quantitative evaluation method that X-fluorescence according to claim 1 surveys active sulfur, which is characterized in that the step 6)
Middle result judgment method are as follows: if the non-corrosive sulphur of sample exists, test result 0, the sulphur that is corrosive can be straight if existing
Connect the concrete content for testing out sulfur content.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101995376A (en) * | 2009-08-18 | 2011-03-30 | 华东电力试验研究院有限公司 | Judgment method of sulfur corrosion of coil material in oil-filled electrical equipment |
| CN104838456A (en) * | 2012-11-20 | 2015-08-12 | 三菱电机株式会社 | Method for diagnosing oil-filled electrical apparatus, and maintenance method |
-
2019
- 2019-04-29 CN CN201910359922.4A patent/CN110018190A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101995376A (en) * | 2009-08-18 | 2011-03-30 | 华东电力试验研究院有限公司 | Judgment method of sulfur corrosion of coil material in oil-filled electrical equipment |
| CN104838456A (en) * | 2012-11-20 | 2015-08-12 | 三菱电机株式会社 | Method for diagnosing oil-filled electrical apparatus, and maintenance method |
Non-Patent Citations (3)
| Title |
|---|
| INTERNATIONAL ELECTROTECHNICAL COMMISSION: "《INTERNATIONAL STANDARD IEC 62535》", 31 December 2008 * |
| 曹凯: "用铜粉腐蚀法测定石油馏分中腐蚀性硫的含量", 《石油化工腐蚀与防护》 * |
| 陆国俊等: "《电力化学试验技能培训教程》", 31 December 2014, 华南理工大学出版社 * |
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Application publication date: 20190716 |