CN106139641A - The processing method of aminophenazone in a kind of transformer oil - Google Patents
The processing method of aminophenazone in a kind of transformer oil Download PDFInfo
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- CN106139641A CN106139641A CN201610727909.6A CN201610727909A CN106139641A CN 106139641 A CN106139641 A CN 106139641A CN 201610727909 A CN201610727909 A CN 201610727909A CN 106139641 A CN106139641 A CN 106139641A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/265—Adsorption chromatography
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- G—PHYSICS
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- 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
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Abstract
Compared with prior art, the invention provides the processing method of aminophenazone in a kind of transformer oil, including: including: with physical absorbent, the transformer oil containing aminophenazone is processed, the transformer oil after being processed；Described physical absorbent is silicic acid class adsorbent, kieselguhr, silicon dioxide and one or more in aluminate class adsorbent.Compared with prior art, the present invention utilizes physical absorbent can remove the aminophenazone in transformer oil, and method is simple and easy to operate.
Description
Technical field
The invention belongs to technical field of petrochemical industry, particularly relate to the processing method of aminophenazone in a kind of transformer oil.
Background technology
Transformer oil is the liquid insulating medium playing cooling, arc extinguishing and insulating effect in transformator, therefore it is required that its
There are excellent insulating properties.Transformer oil can add some additives in process of production, such as antioxidant T501, and i.e. 2,6-
Toluene di-tert-butyl phenol, T501 can delay transformator oil deterioration well.Due to the complexity of inside transformer, add
Agent add later impact be long-range be also unknown.In one's early years in order to improve the antioxygen of oil product in certain import brand transformer oil
The benzyldithio toluene changing performance and add, proved that this material had corrosivity to copper conductor later, result in generation both at home and abroad
The transformer fault that a lot of active sulfurs cause.In order to solve active sulfur problem, the most all use to containing active sulfur
The method adding matal deactivator in transformer oil.As it has been described above, T501, benzyldithio toluene and matal deactivator belong to become
Depressor oil additive.
At the beginning of 2016, Guangdong Power Grid finds that in preventive trial certain brand main change insulated resistance a lot of is decreased obviously, and exceedes
Preventive trial standard, through investigation, defect main transformer concentrates on about 2000 main transformers dispatched from the factory.Find through deep study and analysis:
Defect main transformer contains aminophenazone (also referred to as aminopyrin) material of high concentration, shown in analytical structure formula such as formula (I).
Aminophenazone belongs to organonitrogen compound, molecular formula: C13H17N3O, molecular weight 231, fusing point 107 DEG C～109 DEG C, belong to
In a kind of antibiotics.Investigating interpretation of result by this defect cause, source has two kinds, and one is that Oil Production producer adds
Add, it may be possible to as a kind of antioxidant or for the biocide suppressing growth of microorganism to add, then be contemplated to press down
Oil flow electrification processed and the inhibitor that adds；Two is containing this material in inside transformer material therefor, through long-time fortune
OK, entrance transformer oil is gradually dissolved.Link up by with transformer oil manufacturer, determine that aminophenazone adds for anti-water absorbing agent
Add.
Aminophenazone belongs to basic nitrogen material, and along with transformator runs the increase of the time limit, transformer oil can produce due to aging
Raw acid, aminophenazone is met acid and is become salt, the most charged；Salts substances dissolubility in nonpolar transformer oil is non-
The most limited, the most easily assemble and form charged microenvironment, thus reduce the insulating properties of insulating oil.
At present, the processing method the most also not having aminophenazone in transformer oil is reported.The present invention is to deposit at logarithm platform
Propose on the basis of detecting aminophenazone in the operating transformer oil of Insulation Problems.
Summary of the invention
In view of this, the technical problem to be solved is to provide the process of aminophenazone in a kind of transformer oil
Method, the method can remove the aminophenazone in transformer oil.
The invention provides the processing method of aminophenazone in a kind of transformer oil, including:
With physical absorbent, the transformer oil containing aminophenazone is processed, the transformer oil after being processed；Described
Physical absorbent is silicic acid class adsorbent, kieselguhr, silicon dioxide and one or more in aluminate class adsorbent.
Preferably, described physical absorbent is 801 adsorbents.
Preferably, the quality of described physical absorbent is the A% of quality of the transformer oil containing aminophenazone；Described A is big
In equal to 0.1.
Preferably, in described transformer oil containing aminophenazone or the transformer oil after processing the content of aminophenazone according to
Following methods detects:
Transformer oil after extracting the transformer oil containing aminophenazone or processing, obtains transformer oil testing sample solution；
Transformer oil testing sample solution is detected through gas chromatography-mass spectrography, obtain data from gas chromatography with
Mass spectrometric data, according to standard curve and the mass spectrometric data of the data from gas chromatography of aminophenazone standard solution, obtains transformer oil
The content of middle aminophenazone；
The chromatographic column of described gas chromatography-mass spectrography is HP-5MS chromatography column.
Preferably, in described gas chromatography-mass spectrography, the carrier of gas chromatogram is helium；Flow velocity is 0.5～2ml/
min。
Preferably, the chromatograph heating schedule of described gas chromatography-mass spectrography is: initial temperature 120 DEG C～180 DEG C, protects
Hold 0min, be warming up to 220 DEG C～260 DEG C with 8～12 DEG C/min, be warming up to 270 DEG C～300 DEG C with 13～17 DEG C/min, keep
2min。
Preferably, in the described transformer oil containing aminophenazone, the content of aminophenazone detects in accordance with the following methods:
Transformer oil after extracting the transformer oil containing aminophenazone or processing, obtains transformer oil testing sample solution；
Transformer oil testing sample solution is detected through high performance liquid chromatography, obtains Liquid Chromatography data, according to ammonia
The standard curve of the Liquid Chromatography data of Ji Bilin standard solution, obtains the content of aminophenazone in transformer oil；
The fixing of described high performance liquid chromatography is C18 chromatography column mutually.
Preferably, the column temperature of the fixing phase of described high performance liquid chromatography is 25 DEG C～45 DEG C.
Preferably, described high performance liquid chromatography is isocratic elution；Flowing is the mixed liquor of organic solvent and water mutually.
Preferably, described organic solvent is (45～60) with the volume ratio of water: (55～40).
Compared with prior art, the invention provides the processing method of aminophenazone in a kind of transformer oil, including: bag
Include: with physical absorbent, the transformer oil containing aminophenazone is processed, the transformer oil after being processed；Described physics is inhaled
Attached dose is silicic acid class adsorbent, kieselguhr, silicon dioxide and one or more in aluminate class adsorbent.With prior art phase
Ratio, the present invention utilizes physical absorbent can remove the aminophenazone in transformer oil, and method is simple and easy to operate.
Accompanying drawing explanation
Fig. 1 provides employing gas chromatography-mass spectrography detection aminophenazone quantitation curves figure for the present invention；
Fig. 2 provides employing high performance liquid chromatography detection aminophenazone quantitation curves figure for the present invention.
Detailed description of the invention
The invention provides the processing method of aminophenazone in a kind of transformer oil, including: with physical absorbent to containing ammonia
The transformer oil of Ji Bilin processes, the transformer oil after being processed；Described physical absorbent is silicic acid class adsorbent, silicon
Diatomaceous earth, silicon dioxide and one or more in aluminate class adsorbent.
Wherein, described physical absorbent is preferably 801 adsorbents；The Functionality, quality and appealing design of described physical absorbent is elected as containing amino ratio
The A% of the quality of the transformer oil of woods；Described A is more than or equal to 0.1, more preferably physical absorbent and the transformator containing aminophenazone
The mass volume ratio of oil is (0.1～10) g:500ml, is further preferably (0.5～8) g:500ml, is further preferably (0.5～5) g:
500ml, is further preferably (0.5～3) g:500ml, is further preferably (1～2) g:500ml, most preferably 1g:500ml.
With physical absorbent, the transformer oil containing aminophenazone is processed, preferably physical absorbent is added containing amino
Ratio, in the transformer oil of woods, is stirred, and more preferably carries out magnetic agitation, to ensure to be sufficiently mixed uniformly, improves adsorbent
Adsorption efficiency；The time of described stirring is preferably 10min～10h, more preferably 30min～5h, is further preferably 1～5h, more excellent
Elect 2～4h as, most preferably 3h.
According to the present invention, before to transformer's oil-treatment, preferably the transformer oil containing aminophenazone is detected, with really
Fixed its contains aminophenazone；After treatment, preferably the content of aminophenazone in the transformer oil after processing is detected, to determine
Aminophenazone therein is completely removed.
Wherein, in described transformer oil containing aminophenazone or the transformer oil after processing, the content of aminophenazone is preferably pressed
Detect according to following methods: the transformer oil after extracting the transformer oil containing aminophenazone or processing, obtain transformer oil and treat
Survey sample solution；Transformer oil testing sample solution is detected through gas chromatography-mass spectrography, obtains data from gas chromatography
With mass spectrometric data, according to standard curve and the mass spectrometric data of the data from gas chromatography of aminophenazone standard solution, obtain transformator
The content of aminophenazone in oil.
Transformer oil after extracting the transformer oil containing aminophenazone or processing, the method for described extraction is art technology
Extracting process known to personnel, there is no special restriction, can be Solid-Phase Extraction, it is possible to for liquid-liquid extraction, in the present invention
The method preferably employing liquid-liquid extraction, more preferably uses the organic solvent immiscible with transformer oil to extract；Described containing ammonia
Transformer oil after the transformer oil of Ji Bilin or process is preferably (1～5) g:1ml, more with the mass volume ratio of organic solvent
It is preferably (2～5) g:1ml, is further preferably (3～4) g:1ml, most preferably 4g:1ml；Described organic solvent is art technology
The organic solvent not mixed with transformer oil known to personnel, there is no special restriction, in the present invention be preferably acetonitrile or
Methanol, more preferably methanol；The method that the method for described liquid-liquid extraction is well known to those skilled in the art, it is special to there is no
Limit, after the most preferably the transformer oil after the transformer oil containing aminophenazone or process being mixed with organic solvent often
Temperature vibration, after being centrifuged, extracts the supernatant；The time of described vibration is preferably 5～20min, more preferably 5～15min, more excellent
Elect 10～15min as, most preferably 10min；Described centrifugal rotating speed is preferably 3000～5000r/min, more preferably 3500
～4500r/min, it is further preferably 4000r/min；The described centrifugal time is preferably 3～7min, more preferably 4～6min, then
It is preferably 5min；In the present invention, after the extraction supernatant, preferably with membrane filtration, transformer oil testing sample solution is obtained；
The aperture of described filter membrane is preferably 0.45 μm.
Transformer oil testing sample solution is detected through gas chromatography-mass spectrography, obtain data from gas chromatography with
Mass spectrometric data；The chromatographic column of described gas chromatography-mass spectrography is preferably HP-5MS chromatography column；The carrier of gas chromatogram is excellent
Elect helium as, more preferably the purity helium higher than 99.999%；The flow velocity of carrier gas is preferably 0.5～2ml/min, more preferably
1～1.5ml/min, it is further preferably 1.0ml/min；The operable temperature range of chromatographic column of described gas chromatogram is 30 DEG C～300
℃；The heating schedule that the intensification degree of described gas chromatogram is well known to those skilled in the art, preferably comprise 225 DEG C ±
5 DEG C (temperature that near amino, mass spectrum absworption peak is corresponding), more preferably: initial temperature room temperature～225 DEG C ± 5 DEG C, programming rate
More than 0 less than instrument arrange maximum, most preferably, in the present invention, the heating schedule of chromatograph is: initial temperature 120 DEG C～
180 DEG C, keep 0min, be warming up to 220 DEG C～260 DEG C with 8～12 DEG C/min, be warming up to 270 DEG C～300 with 13～17 DEG C/min
DEG C, keep 2min；More preferably: initial temperature 130 DEG C～160 DEG C, keep 0min, with 9～11 DEG C/min be warming up to 240 DEG C～
260 DEG C, it is warming up to 270 DEG C～290 DEG C with 14～16 DEG C/min, keeps 2min；It is further preferably: initial temperature 140 DEG C～160
DEG C, keep 0min, be warming up to 250 DEG C～260 DEG C with 10 DEG C/min, be warming up to 280 DEG C with 15 DEG C/min, keep 2min；Optimum
Elect as: initial temperature 150 DEG C, keep 0min, be warming up to 250 DEG C with 10 DEG C/min, be warming up to 280 DEG C with 15 DEG C/min, keep
2min。
In the gas chromatography-mass spectrography that the present invention uses, mass spectrum is preferably quadrupole mass spectrometer；Ion source is preferably electricity
Son bombardment ion source (EI)；Electron energy is preferably 70eV；Detection pattern preferably selects ion detection mode (SIM).
By the data from gas chromatography obtained, mass spectrometric data according to the standard of the data from gas chromatography of aminophenazone standard solution
Curve and mass spectrometric data, i.e. can get the content of aminophenazone in transformer oil.
Described aminophenazone standard solution is preferably prepared according to following steps: by standard substance aminophenazone and blank transformation
Device oil mixes, and obtains standard solution mother solution；Extract described standard solution mother solution, obtain aminophenazone standard solution.
Wherein, the blank transformer oil without aminophenazone that blank transformer oil is well known to those skilled in the art is i.e.
Can, there is no special restriction；In described standard solution mother solution, the concentration of aminophenazone is preferably 500～2000mg/kg, more preferably
It is 1000～1500mg/kg, is further preferably 1000mg/kg.
Extract described standard solution mother solution, the present invention preferably employs the organic solvent immiscible with transformer oil and extracts
Take；More preferably the concentration of aminophenazone in standard solution mother solution being prepared aminophenazone concentration respectively in the present invention is 10mg/kg,
The standard solution of 50mg/kg Yu 100mg/kg, extracts with organic solvent the most again；Described organic solvent is same as above, at this not
Repeat again；The method that the method for described extraction is well known to those skilled in the art, there is no special restriction, excellent in the present invention
After standard solution mother solution is mixed by choosing with organic solvent, room temperature vibrates, and after being centrifuged, extracts the supernatant；The time of described vibration is excellent
Electing 5～20min as, more preferably 5～15min, be further preferably 10～15min, most preferably 10min；Described centrifugal rotating speed
Being preferably 3000～5000r/min, more preferably 3500～4500r/min, be further preferably 4000r/min；Described centrifugal time
Between be preferably 3～7min, more preferably 4～6min, be further preferably 5min；In the present invention, after the extraction supernatant, preferably use
Membrane filtration, obtains aminophenazone standard solution；The aperture of described filter membrane is preferably 0.45 μm.
Described standard curve is preferably set up according to following steps: by aminophenazone standard solution through gas chromatography-mass spectrometry
With detecting, the peak area of record aminophenazone, according to response value and the concentration of aminophenazone standard solution of aminophenazone
Criterion curve.The condition of described gas chromatography-mass spectrography is same as above, does not repeats them here.
The standard curve of the data from gas chromatography according to aminophenazone standard solution and mass spectrometric data, obtain in transformer oil
The content of aminophenazone.
In this way can the content of aminophenazone in detection by quantitative transformer oil, method is simple and easy to operate.
In the present invention, the content of aminophenazone in described transformer oil containing aminophenazone or the transformer oil after processing
Also preferably detect in accordance with the following methods: the transformer oil after extracting the transformer oil containing aminophenazone or processing, obtain
Transformer oil testing sample solution；Transformer oil testing sample solution is detected through high performance liquid chromatography, obtains liquid phase color
Modal data, according to the standard curve of the Liquid Chromatography data of aminophenazone standard solution, obtains aminophenazone in transformer oil
Content；The fixing of described high performance liquid chromatography is C18 chromatography column mutually.
Transformer oil after extracting the transformer oil containing aminophenazone or processing, the method for described extraction is art technology
Extracting process known to personnel, there is no special restriction, can be Solid-Phase Extraction, it is possible to for liquid-liquid extraction, in the present invention
The method preferably employing liquid-liquid extraction, more preferably uses the organic solvent immiscible with transformer oil to extract；Described containing ammonia
Transformer oil after the transformer oil of Ji Bilin or process is preferably (1～5) g:1ml, more with the mass volume ratio of organic solvent
It is preferably (2～5) g:1ml, is further preferably (3～4) g:1ml, most preferably 4g:1ml；Described organic solvent is art technology
Organic solvent known to personnel, there is no special restriction, is preferably acetonitrile and/or methanol in the present invention；Described liquid liquid extracts
The method that the method taken is well known to those skilled in the art, there is no special restriction, the most preferably will contain amino
Than woods transformer oil or process after transformer oil mix with organic solvent after room temperature vibration, be centrifuged after, extraction the supernatant；
The time of described vibration is preferably 5～20min, and more preferably 5～15min, be further preferably 10～15min, most preferably
10min；Described centrifugal rotating speed is preferably 3000～5000r/min, and more preferably 3500～4500r/min are further preferably
4000r/min；The described centrifugal time is preferably 3～7min, and more preferably 4～6min, be further preferably 5min；In the present invention
In, after the extraction supernatant, preferably with membrane filtration, obtain transformer oil testing sample solution；The aperture of described filter membrane is preferred
It it is 0.45 μm.
Being detected through high performance liquid chromatography by transformer oil testing sample solution, its sample size is preferably 10～20 μ l,
More preferably 15～20 μ l, are further preferably 20 μ l.
In the present invention, the fixing of described high performance liquid chromatography is C18 chromatography column mutually, preferably Sun Fire TM
C18 chromatography column；Described fixing phase column temperature is preferably 25 DEG C～45 DEG C；More preferably 25 DEG C～40 DEG C, it is further preferably 25 DEG C
～35 DEG C, most preferably room temperature.
Present invention preferably employs isocratic elution；Wherein, flowing is preferably the mixed liquor of organic solvent and water mutually；Wherein said
The organic solvent that organic solvent is well known to those skilled in the art, there is no special restriction, and the present invention is always preferably acetonitrile
And/or methanol, more preferably methanol；Described organic solvent is preferably (45～60) with the volume ratio of water: (55～40), more preferably
For (45～50): (55～50), most preferably 50:50.
In the present invention, the flow velocity of described flowing phase is preferably 0.8～1.2ml/min, more preferably 0.9～1.1ml/
Min, is further preferably 1.0ml/min.
After gradient elution, obtain Liquid Chromatography data, preferably at the liquid chromatograph number of detection wavelength 210～300nm record
According to.
By the Liquid Chromatography data that obtains according to the standard curve of the Liquid Chromatography data of aminophenazone standard solution,
Obtain the content of aminophenazone in transformer oil.
Described aminophenazone standard solution is preferably prepared according to following steps: by standard substance aminophenazone and blank transformation
Device oil mixes, and obtains standard solution mother solution；Extract described standard solution mother solution, obtain aminophenazone standard solution.
Wherein, the blank transformer oil without aminophenazone that blank transformer oil is well known to those skilled in the art is i.e.
Can, there is no special restriction, the impact of other impurity during detection can be reduced；Aminophenazone in described standard solution mother solution
Concentration is preferably 500～2000mg/kg, and more preferably 1000～1500mg/kg, be further preferably 1000mg/kg.
Extract described standard solution mother solution use, the present invention preferably employs the organic solvent immiscible with transformer oil and carries out
Extraction；Described organic solvent is same as above, does not repeats them here；More preferably by aminophenazone in standard solution mother solution in the present invention
Concentration prepare the standard solution that aminophenazone concentration is 10mg/kg, 50mg/kg and 100mg/kg respectively, the most again with organic
Solvent extraction；The method that the method for described extraction is well known to those skilled in the art, there is no special restriction, in the present invention
Preferably by room temperature vibration after standard solution mother solution and methanol mixed, after being centrifuged, extract the supernatant；The time of described vibration is preferred
Being 5～20min, more preferably 5～15min, be further preferably 10～15min, most preferably 10min；Described centrifugal rotating speed is excellent
Electing 3000～5000r/min as, more preferably 3500～4500r/min, be further preferably 4000r/min；The described centrifugal time
Being preferably 3～7min, more preferably 4～6min, be further preferably 5min；In the present invention, after the extraction supernatant, preferably with filter
Membrane filtration, obtains aminophenazone standard solution；The aperture of described filter membrane is preferably 0.45 μm.
Described standard curve is preferably set up according to following steps: carried out through high performance liquid chromatography by aminophenazone standard solution
Detection, the peak area of record aminophenazone, set up mark according to the response value of aminophenazone and the concentration of aminophenazone standard solution
Directrix curve.The condition of described high performance liquid chromatography is same as above, does not repeats them here.
The most also can the content of aminophenazone in detection by quantitative transformer oil, method is simple and easy to operate.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
Gas chromatography-mass spectrography detection embodiment
1, instrument and reagent
1.1 gas chromatography system
Gas chromatograph-mass spectrometer: 7890A-5975C, Agilent company of the U.S. produces；HP-5MS chromatography column (30m ×
0.25mm)；Carrier gas is the helium that purity is higher than 99.999%, and flow velocity is 1.0mL/min；The operable temperature range of column oven is 30
～300 DEG C, column temperature rise program is as shown in table 1.
Table 1 column temperature rise program parameter
1.2 mass spectrometer system
Level Four bar mass spectrograph, electron impact ion source (EI), electron energy 70eV, selecting ion detection mode (SIM)
Lower operation, molecular ion mass-to-charge ratio is as shown in table 2.
Table 2 aminophenazone standard substance quota ion
1.3 reagent
Methanol: chromatographically pure.Standard substance: aminophenazone, purity 99.99%.Blank oil: without domestic the 25 of aminophenazone
Number transformer oil.
2, the formulation of standard curve
The configuration of 2.1 standard solution
Accurately weighing standard substance aminophenazone 0.04g, add blank oily to 40g, being configured to concentration is 1000mg/kg's
Standard solution mother solution, is stored in Brown Glass Brown glass bottles and jars only and seals and be stored in shady place.
According to the standard solution (such as 10mg/kg, 50mg/kg, 100mg/kg) of the proportions desired concn of table 3, store
In Brown Glass Brown glass bottles and jars only and seal be stored in shady place.
The configuration of table 3 standard solution
The pre-treatment of 2.2 standard solution
In 50mL centrifuge tube, weigh 20g standard solution, be accurate to 0.0001g, add 5mL methanol, stopper pipe close, level
After being placed on mechnical oscillator room temperature vibration 10min, it is centrifuged in high speed centrifuge to biphase being kept completely separate of methanol and oil and (preferably selects
Use rotating speed 4000r/min, time 5min), take out the 1.5mL supernatant with syringe, filter by 0.45 μm needle cylinder type filter membrane and treat
With.
The formulation of 2.3 standard curves
According to the 2.2 each standard solution of step process, the standard solution taking the variable concentrations that 1 μ L handles well injects makings connection
Use instrument analysis, the peak area of record aminophenazone.Response value according to aminophenazone and concentration Criterion curve, such as Fig. 1 institute
Show.As shown in Figure 1, aminophenazone quantitation curves: response value=3.98e+004 × content-1.03e+005, correlation coefficient
=1.000.
The mensuration of 2.4 testing samples
In 50mL centrifuge tube, weigh 20g testing sample, be accurate to 0.0001g, locate before carrying out sample according to 2.2 steps
Reason.
The calculating of 2.5 testing sample aminophenazone content
According to the standard curve set up, directly being read the aminophenazone concentration of sample by data system, result is with dense
Degree (mg/kg) represents.
2.6 preparation concentration known standard solution parallel assays five times, the results are shown in Table 4.
Table 4 replicate experiments result
3, choose six operation oil samples and carry out assay
The content of aminophenazone in 56 operating transformer oil samples of table
By the detection of transformer oil sample at fortune main transformer defective to 6 insulation resistances chosen, find aminophenazone
Content is all higher than 50mg/kg.
4, treatment measures
For the disadvantages described above feature having now been found that, in laboratory, carry out insulating oil adsorption treatment regeneration research work
Make.After 801 adsorbents that this experiment is used are in table 5,6 main transformer oil samples carry out adsorption treatment, (50ml main transformer oil sample adds
Enter 0.1g 801 adsorbent, 3h is stirred at room temperature)；Testing result is shown in Table 6, and in insulating oil, aminophenazone content is as shown in Table 6
Do not detect.
66 main change insulated resistance of table are decreased obviously aminophenazone content after main transformer adsorption treatment
801 adsorbents that this laboratory uses have good adsorption to aminophenazone material, and this is such defect
Main change insulated oil adsorption regeneration treating method provides strong foundation.
Use kieselguhr that 6 main transformer oil samples in table 5 are carried out adsorption treatment, (50ml main transformer oil sample adds 0.3g diatom
Soil, is stirred at room temperature 3h)；Testing result is shown in Table 7, and in insulating oil, aminophenazone content is and does not detects as shown in Table 7.
76 main change insulated resistance of table are decreased obviously aminophenazone content after main transformer adsorption treatment
Using kieselguhr that aminophenazone material is also had good adsorption, this is that such defect main change insulated oil is inhaled
Attached regeneration treating method provides strong foundation.
Mesoporous aluminoshilicate adsorbent is used 6 main transformer oil samples in table 5 to be carried out adsorption treatment, (in 50ml main transformer oil sample
Add 0.5g mesoporous aluminoshilicate adsorbent, 3h is stirred at room temperature)；Testing result is shown in Table 8, as shown in Table 8 amino ratio in insulating oil
Woods content is and does not detects.
86 main change insulated resistance of table are decreased obviously aminophenazone content after main transformer adsorption treatment
Using mesoporous aluminoshilicate adsorbent that aminophenazone material is also had good adsorption, this is such defect
Main change insulated oil adsorption regeneration treating method provides strong foundation.
High performance liquid chromatography detection embodiment
1, instrument and reagent
1.1 liquid chromatographic system
High performance liquid chromatograph: Waters e2695,2998PDA detector, Waters, US produces；Sun Fire
TM C18 chromatography column；Chromatographic work station.
1.2 reagent
Methanol: chromatographically pure.Water: meet the requirement of one-level water in GB/T 6682.Standard substance: aminophenazone, purity
99.99%.Blank oil: without domestic No. 25 transformer oil of aminophenazone.
2, test optimum condition
Table 9 mobile phase ratio and appearance time
According to table 9, determine that mobile phase ratio is methanol: water=50%:50%.
3, the formulation of standard curve
The configuration of 3.1 standard solution
Accurately weighing standard substance aminophenazone 0.04g, add blank oily to 40g, being configured to concentration is 1000mg/kg's
Standard solution mother solution, is stored in Brown Glass Brown glass bottles and jars only and seals and be stored in shady place.
According to the standard solution (such as 10mg/kg, 50mg/kg, 100mg/kg) of the proportions desired concn of table 10, store
In Brown Glass Brown glass bottles and jars only and seal be stored in shady place.
The configuration of table 10 standard solution
The pre-treatment of 3.2 standard solution
In 50mL centrifuge tube, weigh 20g standard solution, be accurate to 0.0001g, add 5mL methanol, stopper pipe close, level
After being placed on mechnical oscillator room temperature vibration 10min, it is centrifuged in high speed centrifuge to biphase being kept completely separate of methanol and oil and (preferably selects
Use rotating speed 4000r/min, time 5min), take out the 1.5mL supernatant with syringe, filter by 0.45 μm needle cylinder type filter membrane and treat
With.
The formulation of 3.3 standard curves
According to the 3.2 each standard solution of step process, the standard solution taking the variable concentrations that 20 μ L handle well injects liquid phase
Chromatograph is analyzed, the peak area of record aminophenazone, as shown in table 11.Response value according to aminophenazone and concentration Criterion
Curve, as shown in Figure 2.As shown in Figure 2, response value=1.4819e+005 × content+2e+006, correlation coefficient=1.000).
Table 11 aminophenazone Liquid Chromatography data result
4, the mensuration of testing sample
In 50mL centrifuge tube, weigh 20g testing sample, be accurate to 0.0001g, locate before carrying out sample according to 3.2 steps
Reason.
5, the calculating of testing sample aminophenazone content
According to the standard curve set up, directly being read the aminophenazone concentration of sample by data system, result is with dense
Degree (mg/kg) represents.
6, preparation concentration known standard solution parallel assay five times, the results are shown in Table 12.
Table 12 replicate experiments result
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. the processing method of aminophenazone in a transformer oil, it is characterised in that including:
With physical absorbent, the transformer oil containing aminophenazone is processed, the transformer oil after being processed；Described physics
Adsorbent is silicic acid class adsorbent, kieselguhr, silicon dioxide and one or more in aluminate class adsorbent.
Processing method the most according to claim 1, it is characterised in that described physical absorbent is 801 adsorbents.
Processing method the most according to claim 1, it is characterised in that the quality of described physical absorbent is containing aminophenazone
The A% of quality of transformer oil；Described A is more than or equal to 0.1.
Processing method the most according to claim 1, it is characterised in that described transformer oil containing aminophenazone or after processing
Transformer oil in the content of aminophenazone detect in accordance with the following methods:
Transformer oil after extracting the transformer oil containing aminophenazone or processing, obtains transformer oil testing sample solution；
Transformer oil testing sample solution is detected through gas chromatography-mass spectrography, obtains data from gas chromatography and mass spectrum
Data, according to standard curve and the mass spectrometric data of the data from gas chromatography of aminophenazone standard solution, obtain ammonia in transformer oil
The content of Ji Bilin；
The chromatographic column of described gas chromatography-mass spectrography is HP-5MS chromatography column.
Processing method the most according to claim 4, it is characterised in that gas chromatogram in described gas chromatography-mass spectrography
Carrier be helium；Flow velocity is 0.5～2ml/min.
Processing method the most according to claim 4, it is characterised in that the chromatograph of described gas chromatography-mass spectrography heats up
Program is: initial temperature 120 DEG C～180 DEG C, keeps 0min, is warming up to 220 DEG C～260 DEG C with 8～12 DEG C/min, with 13～17
DEG C/min is warming up to 270 DEG C～300 DEG C, keeps 2min.
Processing method the most according to claim 1, it is characterised in that amino ratio in the described transformer oil containing aminophenazone
The content of woods detects in accordance with the following methods:
Transformer oil after extracting the transformer oil containing aminophenazone or processing, obtains transformer oil testing sample solution；
Transformer oil testing sample solution is detected through high performance liquid chromatography, obtains Liquid Chromatography data, according to amino ratio
The standard curve of the Liquid Chromatography data of woods standard solution, obtains the content of aminophenazone in transformer oil；
The fixing of described high performance liquid chromatography is C18 chromatography column mutually.
Processing method the most according to claim 7, it is characterised in that the column temperature of the fixing phase of described high performance liquid chromatography is
25 DEG C～45 DEG C.
Processing method the most according to claim 1, it is characterised in that described high performance liquid chromatography is isocratic elution；Flowing
It is the mixed liquor of organic solvent and water mutually.
Processing method the most according to claim 9, it is characterised in that the volume ratio of described organic solvent and water be (45～
60): (55～40).
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