CN-122016947-A - Click chemistry-based transformer oil acetylene degassing-free detection method and system

CN122016947ACN 122016947 ACN122016947 ACN 122016947ACN-122016947-A

Abstract

The invention provides a click chemistry-based transformer oil acetylene degassing-free detection method and a click chemistry-based transformer oil acetylene degassing-free detection system, which relate to the technical field of gas detection analysis, and utilize a first product generated by a first click chemistry reaction and a second product generated by a second click chemistry reaction to serve as catalysts to trigger subsequent identical cascade chemical amplification reactions, so that single product molecules can catalyze hydrolysis of a large number of acid-sensitive substrates, the conductivity of a mixed solution is obviously and measurably changed, accurate detection of extremely low-concentration acetylene is realized, meanwhile, the second click chemistry reaction which synchronously occurs by utilizing an internal standard reagent and a trigger agent is independent of the existence of the acetylene concentration detection process, calculation of acetylene detection is performed, the ratio of a first electric signal value to a second electric signal value which is finally output is calculated, the signal ratio is obtained, interference factors are offset, online self-correction of acetylene detection is realized, and high consistency and accuracy of detection results under different time and different batches of reagents are ensured.

Inventors

LIU XIYIN
JIANG YACHAO
XIA JIANGQIAO
Fang Yunzheng
LI HUIQIANG
HUANG WEIDONG
RONG LEI
XIA XIN

Assignees

武汉豪迈光电科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260413

Claims (10)

1. The method for detecting the acetylene of the transformer oil based on click chemistry without degassing is characterized by comprising the following steps of: obtaining a transformer oil sample to be tested, mixing the transformer oil sample with the ionic liquid in a mixing reaction cavity, and separating out an ionic liquid phase containing acetylene; simultaneously adding a measuring reagent and an internal standard reagent into the ionic liquid phase, generating a first product based on a first click chemical reaction of the measuring reagent in the ionic liquid phase, and generating a second product based on a second click chemical reaction of a trigger in the internal standard reagent and a second azide component; Triggering the same cascade chemical amplification reaction on the first product and the second product respectively to release hydrogen ions, and measuring the conductivity change after the reaction to obtain a first conductivity change value and a second conductivity change value; Calculating a first electrical signal value based on the acquired first conductivity change value, calculating a second electrical signal value based on the acquired second conductivity change value, and calculating the ratio of the first electrical signal value to the second electrical signal value to obtain a signal ratio; And calculating to obtain the acetylene concentration value in the transformer oil sample to be measured based on the signal ratio based on a standard curve of the corresponding relation between the pre-established signal ratio and the acetylene concentration.
2. The method for detecting acetylene in transformer oil based on click chemistry according to claim 1, wherein the step of obtaining the transformer oil sample to be detected and mixing the obtained transformer oil sample with the ionic liquid in a mixing reaction chamber to separate an ionic liquid phase containing acetylene comprises the steps of: Measuring a first volume of transformer oil sample to be measured, and injecting the transformer oil sample into a mixed reaction cavity filled with a second volume of ionic liquid; Heating and maintaining the mixed reaction cavity at a preset first temperature, and stirring for a first preset time to balance the distribution of acetylene in the transformer oil sample to be tested between an oil phase and an ionic liquid phase; Stopping stirring, standing for a second preset time, and taking out all ionic liquid phases after the ionic liquid phases are completely layered with the oil phase.
3. The click chemistry-based transformer oil acetylene degassing-free detection method according to claim 2, wherein the simultaneous addition of the measurement reagent and the internal standard reagent to the ionic liquid phase comprises: Adding a third solution containing a copper catalyst to the removed whole ionic liquid phase, and simultaneously adding a measuring reagent containing a first azide component with a known concentration and an internal standard reagent containing a second azide component with a known concentration and a trigger; controlling the temperature of the ionic liquid phase at a preset second temperature, and carrying out a first click chemical reaction and a second click chemical reaction, wherein the reaction time is a third preset time; The first click chemical reaction is carried out in an ionic liquid phase in the presence of a copper catalyst, a first azide component with the same molar quantity as acetylene is consumed, a first product is generated, the second click chemical reaction is synchronously carried out in the same reaction environment in the presence of a trigger, and a preset quantity of a second azide component is consumed, so that a second product is generated.
4. The method for detecting acetylene in transformer oil based on click chemistry according to claim 1, wherein the step of obtaining the first conductivity change value and the second conductivity change value by measuring the conductivity change after the reaction comprises the steps of: Before the cascade chemical amplification reaction starts, an initial baseline conductivity measurement value in an ionic liquid phase is obtained, a mixed solution containing a first product and a second product is transferred to a signal amplification reaction tank, and an acid-sensitive substrate is preset in the signal amplification reaction tank; The first product and the second product are used as catalysts to respectively catalyze acid-sensitive substrates to carry out hydrolysis reaction and continuously release hydrogen ions, a total steady-state conductivity measurement value of the current mixed solution after the cascade chemical amplification reaction is stable is obtained, and a blank correction experiment is set to obtain a second steady-state conductivity measurement value only contributed by the second product; and measuring the total variation of steady-state conductivity measurement values before and after the reaction, and calculating a first conductivity variation value and a second conductivity variation value by a difference method.
5. The click chemistry based transformer oil acetylene de-gassing free detection method of claim 4, wherein calculating a first electrical signal value based on the acquired first conductivity change value and a second electrical signal value based on the acquired second conductivity change value comprises: Performing linear conversion on the obtained first conductivity change value to obtain a first electric signal value; After the first electric signal value is obtained, adding an alkaline neutralization solution into the mixed solution to terminate the cascade chemical amplification reaction and reset the system, obtaining a second steady-state conductivity measured value independently generated by a second product under the blank condition without acetylene, subtracting the initial baseline conductivity measured value from the second steady-state conductivity measured value to obtain a second conductivity change value, and linearly converting the obtained second conductivity change value to obtain a second electric signal value; And calculating the quotient of the first voltage signal and the second voltage signal to obtain a signal ratio.
6. The method for detecting acetylene in transformer oil based on click chemistry without degassing according to claim 1, wherein the step of calculating the acetylene concentration value in the transformer oil sample to be detected based on the signal ratio comprises the steps of: Obtaining N standard oil samples with known acetylene concentration, calculating the signal ratio of each standard oil sample, taking the quantity of the known acetylene substance of each standard oil sample as an abscissa, taking the measured signal ratio as an ordinate, and performing linear regression fitting to obtain a linear equation as a standard curve of the corresponding relation between the signal ratio and the acetylene concentration; Substituting the signal ratio measured by the transformer oil sample to be measured into a linear equation of a marked curve, and calculating to obtain the amount of the substance of the extracted acetylene in the ionic liquid phase; according to the first volume of the transformer oil sample to be tested, converting the amount of the acetylene substance into the acetylene concentration value in the transformer oil sample to be tested.
7. The click chemistry-based transformer oil acetylene degassing-free detection method of claim 3, wherein the first azide component is a tetrazole derivative capable of generating an azide group in situ by tautomerization in an ionic liquid phase in the presence of a copper catalyst and undergoing a first click chemistry reaction with acetylene.
8. The method for non-degassing detection of acetylene in transformer oil based on click chemistry according to claim 3, wherein the second azide component is an azide compound connected with a cleavable fluorescent reporter group, the second click chemistry reaction is a strain-promoted azide-alkyne cycloaddition reaction, the trigger is a ring-tensioning alkyne, and the cleavable fluorescent reporter group is quantitatively released after the reaction.
9. The click chemistry based transformer oil acetylene de-gassing free detection method of claim 8, wherein said calculating a second electrical signal value further comprises: after the second product is generated, carrying out fluorescence detection on the ionic liquid phase; and measuring the fluorescence intensity value of the quantitatively released cleavable fluorescence reporter group, and taking the fluorescence intensity value as a second electric signal value.
10. Click chemistry-based transformer oil acetylene degassing-free detection system, characterized in that the system comprises: the sample flow path and the reaction control module are used for obtaining a transformer oil sample to be tested and the ionic liquid to be mixed in the mixing reaction cavity, and separating out an ionic liquid phase containing acetylene; The reagent feeding and driving module is used for simultaneously adding a measuring reagent and an internal standard reagent into the ionic liquid phase to perform click chemical reaction to generate a first product and a second product; The signal amplifying and converting module is used for triggering the same cascade chemical amplifying reaction on the first product and the second product respectively and then releasing hydrogen ions, and obtaining a first conductivity change value and a second conductivity change value by measuring the conductivity change after the reaction; The signal acquisition and data processing module is used for calculating a first electric signal value based on the acquired first conductivity change value, calculating a second electric signal value based on the acquired second conductivity change value, calculating the ratio of the first electric signal value to the second electric signal value to obtain a signal ratio, and calculating the acetylene concentration value in the transformer oil sample to be tested through a standard curve based on the signal ratio; and the system control and man-machine interaction module is used for inputting, controlling and displaying parameters of the sample flow path and reaction control module, the reagent adding and driving module, the signal amplifying and converting module and the signal collecting and data processing module.

Description

Click chemistry-based transformer oil acetylene degassing-free detection method and system Technical Field The invention relates to the technical field of gas detection and analysis, in particular to a click chemistry-based transformer oil acetylene degassing-free detection method and system. Background The transformer is core equipment of a power system, early warning of internal faults is important, and acetylene gas dissolved in transformer oil is a key characteristic gas for diagnosing serious faults such as arc discharge and the like. At present, on-line monitoring of acetylene mainly depends on technologies such as gas chromatography and photoacoustic spectrometry, and the technologies need to remove dissolved gas from oil firstly, then analyze the gas, and the modes of first degassing and then detecting lead to the monitoring device to comprise complex degassing modules (such as a vacuum pump, a permeable membrane and the like), so that the system is huge, the structure is complex, the maintenance cost is high, and the degassing process itself can introduce delay to influence the instantaneity; In order to simplify the system and realize the in-situ rapid detection, a detection method without degassing appears in the prior art, such as the detection with degassing optics, the chemical detection, the material detection and the like, for example, in the application of the metal organic framework material for rapidly detecting acetylene and the preparation method thereof disclosed in the publication No. CN116199898A to the detection of dissolved acetylene in transformer oil, the detection of acetylene is carried out through the color change caused by the action of acetylene and the material, but the detection precision is insufficient and the color quantification is easy to be disturbed, in the method with the chemical detection, electrolyte is consumed by the cycloaddition reaction of acetylene and sodium azide, and the acetylene concentration is calculated through the measurement of the conductivity change of a solution. In addition, any detection method relying on a single physical quantity (such as an absolute conductivity measurement value) is difficult to overcome systematic errors caused by fluctuation of reaction conditions, attenuation of catalyst activity and the like, and stability and accuracy of long-term monitoring cannot be guaranteed. In summary, the following technical problems exist in the prior art when in use: firstly, when acetylene is detected by a chemical method, the existing deaeration-free click chemical conductivity method fails due to too weak signal change, has low sensitivity and poor stability for acetylene detection, and cannot provide stable and reliable quantitative measurement; and secondly, when acetylene is detected by a chemical method, measurement errors caused by common factors such as environmental fluctuation, reagent consumption, device drift and the like in long-term operation lead to deviation of the detection result of the acetylene concentration, and the accuracy and the precision are low, so that the requirement of measurement precision cannot be met. Disclosure of Invention The invention aims at realizing the technical scheme that the method for detecting the acetylene of the transformer oil without degassing based on click chemistry comprises the following steps: obtaining a transformer oil sample to be tested, mixing the transformer oil sample with the ionic liquid in a mixing reaction cavity, and separating out an ionic liquid phase containing acetylene; simultaneously adding a measuring reagent and an internal standard reagent into the ionic liquid phase, generating a first product based on a first click chemical reaction of the measuring reagent in the ionic liquid phase, and generating a second product based on a second click chemical reaction of a trigger in the internal standard reagent and a second azide component; Triggering the same cascade chemical amplification reaction on the first product and the second product respectively to release hydrogen ions, and measuring the conductivity change after the reaction to obtain a first conductivity change value and a second conductivity change value; Calculating a first electrical signal value based on the acquired first conductivity change value, calculating a second electrical signal value based on the acquired second conductivity change value, and calculating the ratio of the first electrical signal value to the second electrical signal value to obtain a signal ratio; And calculating to obtain the acetylene concentration value in the transformer oil sample to be measured based on the signal ratio based on a standard curve of the corresponding relation between the pre-established signal ratio and the acetylene concentration. Further, the step of obtaining the transformer oil sample to be measured and mixing the transformer oil sample with the ionic liquid in the mixing reaction chamber to separate out