CN111398232B - Fluorescence detection method for concentration of ions to be detected in transformer oil - Google Patents
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Abstract
The invention discloses a fluorescence detection method for concentration of ions to be detected in transformer oil. The specific method comprises the following steps: the metal-organic framework material capable of specifically detecting the fluorescence ions is matched with a solvent to obtain a detection reagent, and the detection reagent is fully mixed with the transformer oil to be detected to test the change of the fluorescence intensity of the solution, so that the detection of the ions to be detected and the content thereof in the oil is realized. The method is simple and convenient to operate, low in cost, accurate in measurement result, free of interference of complex electromagnetic environment, capable of effectively avoiding interference of autofluorescence of oil and the problem that a fluorescent material is difficult to dissolve in oil, and has good practical application prospect.
Description
Technical Field
The invention relates to an operation method for detecting ions in transformer oil, in particular to a method for detecting the concentration of ions to be detected in the transformer oil by using a fluorescent luminous metal-organic framework material solution.
Background
In the industrial field, the detection of ions in transformer oil is of great importance. The content of copper ions and iron ions in the insulating oil of the transformer is an important basis for directly judging the insulation aging of the transformer. When the copper and iron ions in the transformer oil rise abnormally, the insulation aging is accelerated, and the transformer oil needs to be overhauled in time. Although no latent fault occurs in the transformer in operation, the analysis of the metal content in the primary oil is used as the original data, and when the transformer has a fault later, the analysis of the copper and iron ion content in the oil can be used for comparison and judgment of the fault part. However, the current detection means for the ion content in oil has large limitation, such as inductively coupled plasma emission spectrometry, atomic absorption spectrometry, electrophoresis and other methods, the pre-operation steps are complicated, and especially the organic substances in oil can seriously interfere with the test sensitivity. In the complicated electromagnetic environment of transformer operation, methods such as electrochemical detection methods are also easily interfered. Therefore, it is very important to develop a simple and convenient method for detecting ions in transformer oil in real time.
As a novel detection means, compared with the traditional chemical and mechanical sensors, the fluorescence sensor has the advantages of high sensitivity, non-contact measurement, passive measurement, electromagnetic interference resistance, remote real-time monitoring and the like. In recent years, the metal-organic framework material gradually shows the advantages of the metal-organic framework material on fluorescence sensing, and as the metal-organic framework material is a porous material and has a large specific surface area, the metal-organic framework material can generate a large interaction area with detected molecules, so that the fluorescence detection effect of the metal-organic framework material is enhanced. With the further development of metal-organic framework material sensors, there are a variety of mature fluorescence sensing mechanisms: static fluorescence quenching, dynamic fluorescence quenching, frame destruction, energy resonance transfer, and the like.
Based on the above advantages, the metal-organic framework material is a very practical material for detecting ions. But it is difficult to detect ions directly in the transformer oil. On the one hand, transformer oil is a very poor solvent, and the particle size of the metal-organic framework material is at least tens to hundreds of nanometers, and is difficult to be uniformly dispersed in the transformer oil, resulting in inaccurate test results. On the other hand, since transformer oil has autofluorescence, the effect of fluorescence detection is affected. Therefore, no method for detecting the ion concentration in the transformer oil by fluorescence is reported, and the development of a method for detecting the ion concentration in the transformer oil by utilizing the fluorescence of the metal-organic framework material has very important significance.
Disclosure of Invention
The invention aims to provide a fluorescence detection method for the concentration of ions to be detected in transformer oil, which can effectively detect the concentration of the ions in the transformer oil by using a fluorescence luminescent metal-organic framework material.
The technical scheme adopted by the invention is as follows:
a fluorescence detection method for concentration of ions to be detected in transformer oil comprises the steps of firstly transferring the ions in the transformer oil into a detection reagent through an extraction method, and then analyzing fluorescence intensity in the detection reagent to obtain the concentration of the ions to be detected in the transformer oil; the detection reagent is a solution prepared from a specific metal-organic framework material and a solvent, wherein the specific metal-organic framework material is a metal-organic framework material capable of generating specific fluorescent response to ions to be detected.
In the above technical solution, further, the size of the specific metal-organic framework material is in the nanometer level; which does not precipitate in a solvent for a short time but forms a suspension, more preferably with a size of 1-500 nm.
Further, the solvent is selected from water, ethanol, methanol, N ' -dimethylformamide, N ' -dimethylacetamide, N ' -diethylformamide and acetonitrile.
Further, the ions to be detected include, but are not limited to, hydrogen ions, hydroxide ions, sodium ions, magnesium ions, aluminum ions, sulfur ions, hydrogen sulfide ions, chloride ions, hypochlorite ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, tin ions, mercury ions, and lead ions.
Further, the specific metal-organic framework material comprises MOF-525, R101@ ZIF-67, Eu3+@UiO-66-(COOH)2，DMASM@ZIF-90，UiO-67-bpydc，Eu3+@MIL-53-COOH(Al)，Eu3+/Ag+@UiO-66-(COOH)2And the like, which can generate specific fluorescence response to specific ions. For example, MOF-525 can generate specific fluorescence response to copper ions, R101@ ZIF-67, Eu3+@UiO-66-(COOH)2、DMASM@ZIF-90、UiO-67-bpydc、Eu3+@ MIL-53-COOH (Al) can generate specific fluorescence response to iron ions, Eu3+/Ag+@UiO-66-(COOH)2Can generate specific fluorescent response to the sulfhydryl ions.
Further, the extraction method specifically comprises the following steps: and (3) dripping the transformer oil to be detected into the prepared detection reagent, fully oscillating and standing, wherein when the color of the transformer oil to be detected is light and the color of the detection reagent is dark, the extraction is finished, and the ions in the transformer oil are extracted into the detection reagent.
In the invention, the transformer oil can be insulating oil used by all levels of transformers.
Compared with the prior art, the invention has the specific beneficial effects that:
1. the invention provides an extraction method for realizing the fluorescence detection of ions to be detected in the transformer oil in the solution, and successfully solves the problems of interference of autofluorescence luminescence of the transformer oil and difficulty in dissolving a fluorescent material in the transformer oil.
2. The invention uses metal-organic frame material solution as fluorescent probe, the operation method is simple, the concentration of certain ion, such as copper ion with concentration more than 1ppm, iron ion with concentration more than 20ppm, etc. can be accurately measured when the ion concentration in the transformer oil is abnormally increased, and the fluorescent probe has high stability and can be stored for more than three months at normal temperature.
3. The invention utilizes the metal-organic framework material solution as the fluorescent probe, has strong anti-interference performance when being used for detecting ions in the transformer oil, only aims at the specific recognition of one ion in the oil, and is not interfered by other ions with normal content in the oil.
4. The metal-organic framework material solution of the invention has very low concentration, has the characteristic of economy and economy, and is suitable for large-scale industrial production.
5. The method for detecting the ion concentration in the transformer oil by the extraction method has quick detection response, about 1-5s, avoids using complex operation steps and detection instruments, and has strong practicability.
6. The metal-organic framework material solution can realize the detection of common ions in the transformer oil, such as iron ions, copper ions and the like, and the detection limit is the concentration of various ions when the transformer normally operates.
7. The metal-organic framework material capable of generating specific fluorescent response to ions utilized by the invention is very rich in types, and the ions capable of being detected are extremely various, so that the metal-organic framework material has a wide application range.
Drawings
FIG. 1 is a photograph of a layer after mixing the detection reagent of the present invention with transformer oil, extracting and standing;
FIG. 2 is a graph of the fluorescence emission intensity of MOF-525 metal-organic framework solutions of the invention with varying concentrations of copper ions in transformer oil;
FIG. 3 is a graph showing the fluorescence intensity of the R101@ ZIF-67 metal-organic framework solution of the present invention in transformer oil with different concentrations of ferric ions.
Detailed Description
The method of the invention utilizes an extraction method to extract ions in the transformer oil into a detection reagent, and realizes the detection of the ions in the oil through the specific fluorescent response of the detection reagent to the ions to be detected. The specific method comprises the following steps: the metal-organic framework material capable of specifically detecting the fluorescence ions is matched with a solvent to obtain a detection reagent, and the detection reagent is fully mixed with the transformer oil to be detected to test the change of the fluorescence intensity of the solution, so that the detection of the ions to be detected and the content thereof in the oil is realized. The method is simple and convenient to operate, low in cost, accurate in measurement result, free of interference of complex electromagnetic environment, capable of effectively avoiding interference of autofluorescence of oil and the problem that a fluorescent material is difficult to dissolve in oil, and has good practical application prospect.
Example 1:
the method for detecting the concentration of copper ions in transformer oil by utilizing the DMF solution of MOF-525 through an extraction method comprises the following specific steps:
1.35g of benzoic acid and 105mg of zirconyl chloride were accurately weighed out, dissolved in 8mL of DMF, and the resulting solution was placed in an oven at 80 ℃ for 2 hours. After cooling to room temperature 47mg of tetrakis (4-carboxyphenyl) porphyrin (TCPP) were dissolved by sonication. The mixed solution was then heated to 80 ℃ and reacted for 24 hours, cooled, centrifuged and washed three times with DMF. After the washing is completed, 10mL of DMF is added into the centrifuge tube, and after ultrasonic treatment, a 6000mg/L MOF-525 solution is obtained. Then, the MOF-525 solution is diluted to 6mg/L by DMF solvent, and the DMF solution of the MOF-525 for detecting copper ions in the transformer oil is obtained.
Mixing the solution with transformer oil containing copper ions with different concentrations in a cuvette, fully shaking, performing ultrasonic treatment, and standing for five minutes. Under the excitation of 512nm light, the solution has two fluorescence peaks at 651nm and 716 nm. In the range of 0.06-0.6 ppm of copper ion concentration, the luminous peak intensity at 651nm linearly decreases with the increase of copper ion concentration, and the relationship between them can be fitted by the following formula:
I/I0＝7432.53-7622.89CCu2+
wherein, I0The emission peak intensity of the 651nm fluorescence emission peak is the emission peak intensity of the transformer oil without any ion, I is the actual emission intensity of the 651nm fluorescence emission peak, CCu2+Is the concentration of copper ions (in ppm) in the transformer oil.
According to the detection standard commonly used in transformer oil, when the concentration of copper ions exceeds 0.6ppm, it can be concluded that there is a certain possibility of failure. The DMF solution of the MOF-525 meets the actual detection requirement of the transformer oil.
Example 2:
the method for detecting the concentration of copper ions in transformer oil by using the aqueous solution of MOF-525 through an extraction method comprises the following specific synthetic route:
1.35g of benzoic acid and 105mg of zirconyl chloride were accurately weighed out, dissolved in 8mL of DMF, and the resulting solution was placed in an oven at 80 ℃ for 2 hours. After cooling to room temperature 47mg of tetrakis (4-carboxyphenyl) porphyrin (TCPP) were dissolved by sonication. The mixed solution was then heated to 80 ℃ and reacted for 24 hours, cooled, centrifuged and washed three times with deionized water. After the washing is finished, 10mL of deionized water is added into the centrifuge tube, and the mixture is subjected to ultrasonic treatment to obtain 6000mg/L of MOF-525 solution. And then, diluting the MOF-525 solution to 6mg/L by using deionized water to obtain an MOF-525 aqueous solution for detecting copper ions in the transformer oil.
Mixing the solution with transformer oil containing copper ions with different concentrations in a cuvette, fully shaking, performing ultrasonic treatment, and standing for five minutes. Under the excitation of 512nm light, the solution has two fluorescence peaks at 651nm and 716 nm. In the range of 0.06-0.6 ppm of copper ion concentration, the luminous peak intensity at 651nm decreases linearly with the increase of copper ion concentration.
According to the detection standard commonly used in transformer oil, when the concentration of copper ions exceeds 0.6ppm, it can be concluded that there is a certain possibility of failure. The aqueous solution of the MOF-525 meets the actual detection requirement of the transformer oil.
Example 3:
the concentration of iron ions in the transformer oil is detected by using an aqueous solution of R101@ ZIF-67 through an extraction method, and the specific synthetic route is as follows:
accurately weighing 0.1g of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 8mL of deionized water, adding 300 mu L of 1mg/mL rhodamine 101 aqueous solution, stirring for 20 minutes, accurately weighing 0.2g of 2-methylimidazole, dissolving the two solutions in 8mL of deionized water, mixing the two solutions, stirring for 6 hours at room temperature, centrifugally collecting after the reaction is finished, and washing for three times by using the deionized water. After cleaning, 6mg of sample is taken, 10mL of deionized water is added, and ultrasonic treatment is carried out to obtain a high-concentration R101@ ZIF-67 aqueous solution. And then diluting the R101@ ZIF-67 solution to 6mg/L by using deionized water to obtain an aqueous solution of the R101@ ZIF-67 for detecting iron ions in the transformer oil.
Mixing the solution with transformer oil containing iron ions with different concentrations in a cuvette, fully shaking, performing ultrasonic treatment, and standing for five minutes. Under the excitation of light at 580nm, the solution shows a fluorescence emission peak with the wavelength of 618 nm. In the range of 0-33 ppm of copper ion concentration, the luminous peak intensity at 618nm linearly increases with the increase of iron ion concentration, and the relationship between the luminous peak intensity and the iron ion concentration can be fitted by the following formula:
I＝-659.9+258.9CFe3+
wherein, IActual luminous intensity of fluorescence peak at 618nm, CFe3+Is the concentration of iron ions (in ppm) in the transformer oil.
According to the detection standard commonly used in transformer oil, when the concentration of iron ions exceeds 33ppm, it can be concluded that there is a certain possibility of failure. The water solution of the R101@ ZIF-67 meets the actual detection requirements of transformer oil.
Example 4:
using Eu3+@UiO-66-(COOH)2The ethanol solution detects the concentration of copper ions in the transformer oil by an extraction method, and the specific synthetic route is as follows:
2.54g of 1,2,4, 5-pyromellitic acid and 2.43g of zirconium tetrachloride were dispersed in 60mL of distilled water and 40mL of acetic acid with stirring at room temperature, and then heated at 100 ℃ for 24 hours to obtain a powder product. Soaking the product in anhydrous methanol at room temperature for three days, centrifuging to remove supernatant every day, adding methanol, treating the sample with acetone for 5 days, vacuum drying, and removing residual reactant in sample pores to obtain final product UiO-66- (COOH)2. 0.1g of UiO-66- (COOH)2And 0.446gEu (NO)3)36H2Adding O into a single-neck flask filled with 10mL of distilled water, heating at 60 ℃ for 24h, centrifugally washing after the reaction is finished to remove reactants in product pores, taking 6mg of sample after the washing is finished, adding 10mL of ethanol, and performing ultrasonic treatment to obtain high-concentration Eu3+@UiO-66-(COOH)2And (3) solution. Then adding ethanol to the Eu3+@UiO-66-(COOH)2Diluting the solution to 6mg/L to obtain Eu for detecting hydrogen sulfide in gasoline3+@UiO-66-(COOH)2The ethanol solution of (1).
Mixing the solution with transformer oil containing copper ions with different concentrations in a cuvette, fully shaking, performing ultrasonic treatment, and standing for five minutes. Under 305nm light excitation, Eu3+@UiO-66-(COOH)2The emission peak of the solution is mainly composed of two parts, one part is from the 393nm broadband emission of the ligand, and the other part is from Eu3+Characteristic emission peaks at 579, 592, 615, 651 and 700nm with Eu3+@UiO-66-(COOH)2The light emission ratio of (c). When Eu is used3+@UiO-66-(COOH)2After the solution extracts copper ions in the transformer oil, Eu3+@UiO-66-(COOH)2Is compounded with copper ions in the solution to inhibit ligand from being converted to Eu3+So that the ligand emits light strongly, and Eu3+The luminous intensity of (2) is significantly decreased. When the concentration of copper ions is 0-50 ppm, the fluorescence intensity and the ion concentration have a linear correlation relationship.
Example 5:
the method for detecting the concentration of iron ions in the transformer oil by using the DMASM @ ZIF-90 solution through an extraction method comprises the following specific synthetic route:
accurately weighing 0.1g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 8mL of DMF, adding 300 mu L of DMASM DMF solution with the concentration of 1mg/mL, stirring for 20 minutes, accurately weighing 0.25g of 2-formaldehyde imidazole, dissolving the 2-formaldehyde imidazole in 8mL of DMF, mixing the two solutions, stirring for 6 hours at room temperature, centrifugally collecting after the reaction is finished, and washing with DMF for three times. After the washing is finished, 6mg of sample is taken, 10mL of DMF is added, and the high-concentration DMASM @ ZIF-90 solution is obtained after ultrasonic treatment. And then, diluting the DMASM @ ZIF-90 solution to 6mg/L by using DMF to obtain the DMASM @ ZIF-90DMF solution for detecting iron ions in the transformer oil.
Mixing the solution with transformer oil containing iron ions with different concentrations in a cuvette, fully shaking, performing ultrasonic treatment, and standing for five minutes. Under the excitation of light of 380nm, the solution shows a fluorescence emission peak with the wavelength of 610 nm. In the range of 0-50 ppm of the iron ion concentration, the luminous peak intensity at 610nm increases with the increase of the iron ion concentration.
Example 6:
the method for detecting the concentration of iron ions in the transformer oil by using the UiO-67-bpydc aqueous solution comprises the following specific synthetic route:
2g of 4, 4' -bipyridine and 2.43g of zirconium tetrachloride were dispersed in 60mL of distilled water and 40mL of acetic acid with stirring at room temperature, and then heated at 100 ℃ for 24 hours to obtain a powder product. The product was soaked in anhydrous methanol for three days at room temperature, during which time the supernatant was centrifuged off each day and methanol was added, then the sample was treated with acetone for 5 days as well, dried under vacuum and the residual reaction in the pores of the sample was removed to give the final product UiO-67-bpydc. And preparing the UiO-67-bpydc powder deionized water into 6mg/L aqueous solution to obtain the aqueous solution for detecting iron ions in the transformer oil.
Mixing the solution with transformer oil containing iron ions with different concentrations in a cuvette, fully shaking, performing ultrasonic treatment, and standing for five minutes. Under 395nm light excitation, the UiO-67-bpydc solution emits fluorescence at 562 nm. After the UiO-67-bpydc solution extracts iron ions in the transformer oil, nitrogen atoms on the ligand can be combined with the iron ions, and the fluorescence of the ligand is inhibited. And the iron ions have certain fluorescence absorption capacity, so the fluorescence of the solution is quenched by the iron ions.
Claims (7)
1. A fluorescence detection method for concentration of ions to be detected in transformer oil is characterized in that ions in the transformer oil are transferred into a detection reagent through an extraction method, and then fluorescence intensity in the detection reagent is analyzed, so that the concentration of the ions to be detected in the transformer oil is obtained; the detection reagent is a solution prepared from a specific metal-organic framework material and a solvent, wherein the specific metal-organic framework material is a metal-organic framework material capable of generating specific fluorescent response to ions to be detected; the extraction method specifically comprises the following steps: and (3) dripping the transformer oil to be detected into the prepared detection reagent, fully oscillating and standing, wherein when the color of the transformer oil to be detected is light and the color of the detection reagent is dark, the extraction is finished, and the ions in the transformer oil are extracted into the detection reagent.
2. The fluorescence detection method for detecting the concentration of ions in transformer oil according to claim 1, wherein the specific metal-organic framework material has a size of nanometer level, and the detection reagent is a suspension formed by the specific metal-organic framework material and a solvent.
3. The fluorescence detection method for the concentration of ions to be detected in transformer oil according to claim 1, wherein the size of the specific metal-organic framework material is 1-500 nm.
4. The fluorescence detection method for detecting the concentration of ions in transformer oil according to claim 1, wherein the ions to be detected are hydrogen ions, hydroxide ions, sodium ions, magnesium ions, aluminum ions, sulfur ions, hydrogen sulfide ions, chloride ions, hypochlorite ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, tin ions, mercury ions, or lead ions.
5. The fluorescence detection method for the ion concentration to be detected in the transformer oil according to claim 1, wherein the solvent is selected from water, ethanol, methanol, N ' -dimethylformamide, N ' -dimethylacetamide, N ' -diethylformamide and acetonitrile.
6. The fluorescence detection method for the concentration of ions to be detected in transformer oil according to claim 1, wherein the specific metal-organic framework material is a metal-organic framework material which generates a specific fluorescence response to specific ions and is selected from the group consisting of MOF-525, R101@ ZIF-67, Eu3+@
UiO-66-(COOH)2，DMASM@ZIF-90，UiO-67-bpydc，Eu3+@ MIL-53-COOH (Al), or Eu3+/ Ag+@UiO-66-(COOH)2。
7. The fluorescence detection method for the concentration of ions to be detected in transformer oil according to claim 1, wherein the transformer oil is insulating oil used by each stage of transformer.
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