A device for regenerating transformer aged oil by light irradiation and a GC-MS differential spectrum detection method for color-causing substances in oil

Abstract

This invention belongs to the field of degraded oil regeneration technology, and specifically discloses a photoluminescence decolorization and regeneration device for transformer dismantling oil. The device includes a main body, a transparent processing container inside, a catalytic adsorption composite material at the bottom of the processing container, a sunshade outside the processing container, a lid on the top of the main body, and an ultraviolet lamp at the bottom of the lid. The ultraviolet lamp is inserted into the processing container and connected to a power source via wires and a plug. This invention has the advantages of simple structure and high-quality regeneration of dismantled oil. Furthermore, this invention discloses a GC-MS differential spectral detection method for coloring substances in transformer dismantling oil.

Description

Technical Field

[0001] This invention belongs to the field of deteriorated oil regeneration technology, and in particular discloses a device for photo-irradiation decolorization and regeneration of transformer dismantling oil and a GC-MS differential spectrum detection method for coloring substances in oil. Background Technology

[0002] While general recycled oil processes can meet the requirements of DL / T1419 for other indicators, the recently revised GB / T7595 standard requires that the color number of the treated oil be ≤2. New transformer oil is generally water-white, but the repair of old transformers generates a large amount of dark-colored waste oil. Traditional adsorption methods cannot completely decolorize the waste oil, resulting in dark-colored oil labels on repaired transformers, which affects their appearance and makes it difficult to sell the repaired transformer labels.

[0003] Current technology involves mixing new and waste oil in a specific ratio. However, the presence of unidentified small-molecule deterioration products can affect insulation, posing a high safety risk. Furthermore, the transformer's color darkens after a period of use. Since most transformer repair work involves oil treatment and replacement, failing to regenerate the replaced oil contradicts energy conservation and carbon reduction policies. Additionally, existing transformer oil decolorization and regeneration devices are relatively complex. Summary of the Invention

[0004] To address the aforementioned problems, the present invention aims to disclose a device for the photoluminescence decolorization and regeneration of transformer dismantling oil and a GC-MS differential spectral detection method for coloring substances in oil, which are achieved using the following technical solutions.

[0005] A transformer decolorization and regeneration device for dismantling old oil includes a main body of the regeneration device, a transparent processing container inside the main body of the regeneration device, a catalytic adsorption composite material at the bottom of the processing container, a sunshade outside the processing container, a cover on the top of the main body of the regeneration device, an ultraviolet lamp at the bottom of the cover, the ultraviolet lamp being inserted into the processing container, and the ultraviolet lamp being connected to a power source through wires and a plug.

[0006] The above-mentioned transformer dismantling oil light decolorization and regeneration device has a sunshade cover with a sunshade cloth attached to the inner wall.

[0007] The above-described transformer dismantling oil photoluminescence decolorization and regeneration device uses a prism-shaped ultraviolet lamp column. Multiple lamp beads are arranged along the prism direction on the side wall of the ultraviolet lamp column. The height of the uppermost lamp bead is lower than the height of the upper edge of the sun-proof cloth, and the height of the uppermost lamp bead is lower than the surface height of the transformer dismantling oil in the processing container.

[0008] The above-mentioned transformer dismantling oil light-emitting decolorization and regeneration device uses ultraviolet light emitted by lamp beads with a wavelength of 350-400nm.

[0009] The above-described transformer dismantling oil decolorization and regeneration device maintains the oil temperature at 20℃.

[0010] The above-described transformer dismantling oil photo-irradiation decolorization and regeneration device has a photocatalytic adsorption time of 24-30 hours.

[0011] The above-described transformer dismantling oil decolorization and regeneration device uses a catalytic adsorption composite material 4, which is a glucose-encapsulated attapulgite particle catalyst.

[0012] The above-mentioned transformer dismantling oil light-dyeing decolorization and regeneration device uses a catalytic adsorption composite material prepared according to the following raw material weight ratios: 25 parts of a strong acid solution with a mass percentage concentration of 2 mol / L, 23 parts of an aluminum sulfate solution with a mass percentage concentration of 6.9-7%, 23 parts of a sodium silicate solution with a mass percentage concentration of 6.0-6.1%, and 1.35 parts of ammonia water with a mass percentage concentration of 26%.

[0013] The preparation steps are as follows: 25 parts of 2 mol / L strong acid are poured into 23 parts of 6.95% aluminum sulfate solution and stirred evenly. Then, 23 parts of 6.02% sodium silicate solution are added and stirred evenly. Finally, 1.35 parts of 26% ammonia water are added. The mixture is then pumped into a reactor for aging at 90℃ for 8 hours. After aging, the mixture is washed with water in a cleaning tank and dried. It is then placed in an oven and dried at 120℃. After drying, it is soaked in phosphoric acid, washed with water, and then baked again at 135℃ for 24 hours to obtain the finished adsorbent.

[0014] The aforementioned transformer dismantling oil photo-decolorization and regeneration device uses a catalytic adsorption composite material 4 at a dosage of 1.5%-2% of the oil weight. This 1.5% catalytic adsorption composite material 4 can reduce the colored substances in the oil to zero, which is half the amount of traditional adsorbents, demonstrating significant photo-enhancing benefits. The adsorption catalysis cost is approximately 2000 yuan / ton, while the profit margin is 3000-4000 yuan / ton.

[0015] The above-described transformer dismantling oil light-dyeing and regeneration device also incorporates glucose zinc oxide or titanium dioxide nanoparticles in its catalytic adsorption composite material.

[0016] In the above-mentioned transformer dismantling oil light-dyeing and regeneration device, glucose zinc oxide and titanium dioxide nanoparticles account for 20-50% of the weight of the catalytic adsorption composite material.

[0017] The above-described GC-MS differential spectral method for detecting color-causing substances in transformer dismantling oil includes the following steps:

[0018] Step 01: Use a chromatograph to separate the substances in the recycled oil. Place the recycled oil in a column oven and increase the column temperature from 120°C to 325°C at a rate of 5°C / min to vaporize the substances in the recycled oil. At the same time, helium gas with a purity higher than 99.999% is introduced at a flow rate of 1.0 mL / min. After vaporization, the substances pass through the chromatographic column under the push of the helium gas and are separated and fixed by the stationary liquid in the chromatographic column.

[0019] Step 2: Use a mass spectrometer to identify the chromogenic substances. In the selected ion detection mode (SIM), the electron impact ion source (EI) is 230C and the electron energy is set to 70eV. The mass-to-charge ratio of each substance is obtained and compared with the database to determine the molecular formula of the corresponding substance.

[0020] Step 3: After the decolorized recycled oil is processed through steps 1 and 2, the changes in the peak areas of the old oil and the recycled oil can be compared to analyze the color-causing substances removed from the oil before and after decolorization.

[0021] This application has the following beneficial technical effects: good adsorption effect on impurities, the old oil after light adsorption can meet the requirements of GB7595 operating oil quality standard, good light transmittance, significantly reduced acid value, significantly reduced dielectric loss value, significantly increased breakdown voltage, and lower cost. Attached Figure Description

[0022] Figure 1 This is a three-dimensional structural schematic diagram of an embodiment of the present invention.

[0023] Figure 2 This is a schematic diagram of the internal structure of an embodiment of the present invention.

[0024] Figure 3 This is a TIC diagram of dismantled oil and recycled oil measured by GC-MS according to an embodiment of the present invention.

[0025] In the figure, the corresponding figures are: 1. Main body of regeneration device, 2. Cover, 21. Handle, 3. Wire and plug, 4. Catalytic adsorption composite material, 5. Ultraviolet lamp column, 6. Processing container, 7. Sunshade. Detailed Implementation

[0026] Example: Figures 1 to 2A transformer oil decolorization and regeneration device includes a transparent main body 1, a transparent processing container 6 inside the main body 1, a catalytic adsorption composite material 4 at the bottom of the processing container 6, a sunshade 7 outside the processing container 6, and a sunshade cloth on the inner wall of the sunshade 7. The top of the main body 1 is provided with a cover 2, and a quadrangular prism-shaped ultraviolet lamp column 5 is provided at the bottom of the cover 2. Multiple ultraviolet lamp beads that can emit ultraviolet rays are provided along the ridge direction on the side wall of the ultraviolet lamp column 5. The ultraviolet lamp column 5 is inserted into the processing container 6. The height of the uppermost lamp bead is lower than the height of the upper edge of the sunshade cloth and lower than the surface height of the transformer oil in the processing container 6. The lamp beads are connected to a power source through wires and plugs 3.

[0027] The above-mentioned transformer dismantling oil light-emitting decolorization and regeneration device uses ultraviolet light emitted by lamp beads with a wavelength of 350-400nm, and a typical value of 395nm.

[0028] The above-described transformer dismantling oil decolorization and regeneration device maintains the oil temperature at 20℃.

[0029] The above-described transformer dismantling oil photo-irradiation decolorization and regeneration device has a photocatalytic adsorption time of 24-30 hours.

[0030] The above-described transformer dismantling oil decolorization and regeneration device uses a catalytic adsorption composite material 4, which is a glucose-encapsulated attapulgite particle catalyst.

[0031] The above-mentioned transformer dismantling oil light-dyeing decolorization and regeneration device uses a catalytic adsorption composite material 4 prepared according to the following raw material weight ratios: 25 parts of a strong acid solution with a mass percentage concentration of 2 mol / L, 23 parts of an aluminum sulfate solution with a mass percentage concentration of 6.9-7%, 23 parts of a sodium silicate solution with a mass percentage concentration of 6.0-6.1%, and 1.35 parts of ammonia water with a mass percentage concentration of 26%.

[0032] The preparation steps are as follows: 25 parts of a 2 mol / L strong acid are poured into 23 parts of a 6.95% aluminum sulfate solution and stirred until homogeneous. Then, 23 parts of a 6.02% sodium silicate solution are added and stirred until homogeneous again. Finally, 1.35 parts of a 26% ammonia solution are added. The mixture is then pumped into a reactor for aging at 90℃ for 8 hours. After aging, the mixture is washed with water in a cleaning tank and dried. It is then placed in an oven and baked at 120℃. After drying, it is soaked in phosphoric acid, washed with water, and then baked again at 135℃ for 24 hours to obtain the finished adsorbent.

[0033] The aforementioned transformer dismantling oil photo-decolorization and regeneration device uses a catalytic adsorption composite material 4 at a dosage of 1.5%-2% of the oil weight. This 1.5% catalytic adsorption composite material 4 can reduce the colored substances in the oil to zero, which is half the amount of traditional adsorbents, demonstrating significant photo-enhancing benefits. The adsorption catalysis cost is approximately 2000 yuan / ton, while the profit margin is 3000-4000 yuan / ton.

[0034] The above-mentioned transformer dismantling oil light-dyeing and regeneration device also includes a catalytic adsorption composite material 4 doped with glucose zinc oxide or titanium dioxide nanoparticles, which account for 20-50% of the weight of the catalytic adsorption composite material 4.

[0035] To investigate the mechanism of photo-adsorption degradation of color-causing impurities in transformer dismantling oil, GC-MS tests were performed on the regenerated oil after photo-degradation of the transformer dismantling oil. The relative content of substances was determined based on the peak position and peak area. Technicians compared the changes in the types of some acidic substances in the oil before and after adsorption. Figure 3 As shown, at retention times of 6.17 min, 8.29 min, 15.87 min, 16.34 min, 17.14 min, 17.36 min, 17.82 min, 18.16 min, 18.25 min, 19.27 min, 21.25 min, 21.86 min, and 22.74 min, changes in the peak area of ​​substances were observed in both the old oil TIC peak and the regenerated oil. This indicates a halving or disappearance of the relative content of the substances. By comparing these changes, the changes in the substances in the oil before and after photocatalysis can be inferred.

[0036] Based on the GC-MS test results, the organic impurities degraded by photocatalysis were scientifically analyzed and summarized in Table 1. Some of the results identified by mass spectrometry include the easily discoloring antioxidant 2,6-di-tert-butyl-p-cresol, the deep yellow flame retardant 2-bromohexadecane, and the slightly yellow organic compounds 1,3,5-trimethyl-2-octadecylcyclohexane, 2-methyl-1-hexadecane, 2-methyleicosane, and 1-tetradecane.

[0037] Table 1

[0038] A GC-MS differential spectral method for detecting color-causing substances in transformer dismantling oil includes the following steps:

[0039] Step 01: Use a chromatograph to separate the substances in the recycled oil. Place the recycled oil in a column oven and increase the column temperature from 120°C to 325°C at a rate of 5°C / min to vaporize the substances in the recycled oil. At the same time, helium gas with a purity higher than 99.999% is introduced at a flow rate of 1.0 mL / min. After vaporization, the substances pass through the chromatographic column under the push of the helium gas and are separated and fixed by the stationary liquid in the chromatographic column.

[0040] Step 2: Use a mass spectrometer to identify the chromogenic substances. In the selected ion detection mode (SIM), the electron impact ion source (EI) is 230C and the electron energy is set to 70eV. The mass-to-charge ratio of each substance is obtained and compared with the database to determine the molecular formula of the corresponding substance.

[0041] Step 3: After the decolorized recycled oil is processed through steps 1 and 2, the changes in the peak areas of the old oil and the recycled oil can be compared to analyze the color-causing substances removed from the oil before and after decolorization.

[0042] The GC-MS chromatograph is an Agilent 5977b, manufactured by Agilent Technologies, USA; the Agilent 19091S-433 column (30m x 250μm x 0.25μm); the carrier gas is helium with a purity higher than 99.999%, and the flow rate is 1.0mL / min; the column oven has an operating temperature range of 30–300℃. The mass spectrometer is a quadrupole mass spectrometer with an electron impact ion source of 230°C (C is the unit of charge), a maximum of 250°C, and an electron energy of 70 eV. Operating in selected ion detection mode (SIM), it can measure the mass-to-charge ratio of various chromogenic substances, such as 2,6-di-tert-butyl-p-cresol (mass-to-charge ratios of 367.1 and 382 m / z); 1,3,5-trimethyl-2-octadecylcyclohexane (mass-to-charge ratios of 43.1, 57.1, 69.1, 83.1, 111.1, 125.1, and 192.1); and 2-methyl-1-hexadecanool (mass-to-charge ratios of 43.1, 57.1, 71.1, 85.1, and 97.1).

[0043] The applicant conducted three experiments:

[0044] Experiment 1: The used transformer oil was subjected to adsorption under three 200W UV lamps. Because transformer oil often contains the antioxidant 2,6-di-tert-butylcresol, it easily turns yellow under high temperatures. Furthermore, the used oil also contains a significant amount of corrosive sulfur and metal ions; these impurities can also cause the oil to turn yellow or even dark brown. When the used transformer oil was treated with the GLU-APT composite material under optimal conditions, its porous structure allowed for the removal of color-causing impurities through a physical adsorption process driven by van der Waals forces. This transformed the oil from dark yellow to a colorless and transparent state, free of sediment and suspended matter, meeting the quality standards for transformer oil. Table 2 shows that the decolorization rate of the regenerated oil reached 87.3%, the acid value decreased by 82.1%, the dielectric loss decreased by 97.8%, and the breakdown voltage increased by 40.6%. Therefore, this composite adsorption material can regenerate used transformer oil, improving its physicochemical and electrical properties.

[0045] Table 2 Comparison of Physicochemical and Electrical Properties of Old Oil Before and After Adsorption Treatment

[0046] Experiment 2: The experimental system was configured with a photocatalytic material and old oil mass ratio of 1:8, and 1.5 kg of catalytic adsorption composite material was used for photocatalysis; two 200W ultraviolet lamps (365nm) were used for irradiation for 24-72 hours, and the temperature was kept at room temperature.

[0047] After 24 hours, the oil color number was lower than that after 72 hours, and after further vacuum filtration, it reached color number 1. The deep yellow oil was regenerated and recycled, and a catalytic adsorption composite material was used to bring the oil color back to the level of new oil (GB / T7595 standard requirement, treated oil color number ≤2). The insulation resistance increased threefold after adsorption. After 96 hours of light adsorption, the oil color returned to color number 4.

[0048] The oil exposed to sunlight for 24 hours was vacuum filtered to obtain transformer regenerated oil with a color number of 1. This oil was then used on six transformers at Yunmeng Limin transformer depot. A follow-up analysis was conducted six months later, comparing the oil quality before and after the exposure, as shown in the table below:

[0049] Table 3: Summary of Oil Quality Tracking for Six Devices Listed Online for Six Months

[0050] Results: The color of the oil from the six transformers that were subjected to light adsorption was stable, and the moisture content, dielectric loss, breakdown voltage, and color all met the requirements of the GB7595 operating oil quality standard.

[0051] Experiment 3: Comparison of oil adsorption only and light adsorption

[0052] A comparative experiment was conducted focusing on photocatalytic adsorption and adsorption using only the catalytic adsorption composite material. The experimental systems were configured as follows: 1L of oil with 5g of the catalytic adsorption composite material (adsorption only); and 1L of oil with 80g of glucose-zinc oxide and 50g of the catalytic adsorption composite material (photo-adsorption). The experimental equipment included a 1L oil cup from Huansheng, a Shenzhen Ruislang 405nm / 200W UV lamp, a 100L Buchner filter flask, a Zijing Tianrui LD-4 centrifuge, and a Shanghai Optical Instrument Factory 721 spectroscope.

[0053] The experimental procedure was designed with two pathways: one was catalysis under UV light followed by adsorption using a catalytic adsorption composite material; the other was parallel XDK adsorption only. After treatment, the samples were washed with distilled water, and the transmittance was measured using a spectroscope. The results are shown in the table below:

[0054] This application has the following beneficial effects:

[0055] It has a good adsorption effect on impurities. The used oil after light adsorption can meet the requirements of GB7595 operating oil quality standard, with good light transmittance, significantly reduced acid value, significantly reduced dielectric loss value, significantly increased breakdown voltage, and lower cost.

[0056] The above embodiments are merely preferred technical solutions of the present invention and should not be considered as limitations on the present invention. The scope of protection of the present invention should be limited to the technical solutions described in the claims, including equivalent substitutions of the technical features described in the claims. That is, equivalent substitutions and improvements within this scope are also within the scope of protection of the present invention.

Claims

1. A transformer dismantling oil light-dyeing and regeneration device, comprising a main body of the regeneration device (1), characterized in that, The main body (1) of the regeneration device is equipped with a transparent processing container (6). The bottom of the processing container (6) is equipped with a catalytic adsorption composite material (4). The processing container (6) is equipped with a sunshade (7). The top of the main body (1) of the regeneration device is equipped with a cover (2). The bottom of the cover (2) is equipped with an ultraviolet lamp. The ultraviolet lamp is inserted into the processing container (6). The ultraviolet lamp is connected to the power supply through a wire and a plug (3).

2. The transformer dismantling oil light-dyeing and regeneration device according to claim 1, characterized in that, The inner wall of the sunshade (7) is covered with sunshade cloth.

3. The transformer dismantling oil light-dyeing and regeneration device according to claim 2, characterized in that, The ultraviolet lamp is a prism-shaped ultraviolet lamp column (5). Multiple lamp beads are provided on the side wall of the ultraviolet lamp column (5) along the prism direction. The height of the uppermost lamp bead is lower than the height of the upper edge of the sunshade cloth, and the height of the uppermost lamp bead is lower than the height of the old transformer oil in the processing container (6).

4. The transformer dismantling oil light-dyeing and regeneration device according to claim 3, characterized in that, The ultraviolet light emitted by the LED beads has a wavelength of 350-400nm.

5. The transformer dismantling oil light-dyeing and regeneration device according to claim 4, characterized in that, The catalytic adsorption composite material (4) is a glucose-encapsulated attapulgite particle catalyst.

6. The transformer dismantling oil light-blowing decolorization and regeneration device according to claim 4, characterized in that, The catalytic adsorption composite material (4) is prepared according to the weight ratio of the raw materials: 25 parts of strong acid solution with a mass percentage concentration of 2 mol / L, 23 parts of aluminum sulfate solution with a mass percentage concentration of 6.9-7%, 23 parts of sodium silicate solution with a mass percentage concentration of 6.0-6.1%, and 1.35 parts of ammonia water with a mass percentage concentration of 26%.

7. The transformer dismantling oil light-dyeing and regeneration device according to claim 5, characterized in that, The preparation steps of the catalytic adsorption composite material (4) are as follows: 25 parts of 2 mol / L strong acid are poured into 23 parts of aluminum sulfate solution with a mass percentage concentration of 6.95%, and stirred evenly. Then, 23 parts of sodium silicate solution with a mass percentage concentration of 6.02% are added and stirred evenly. Finally, 1.35 parts of ammonia water with a mass percentage concentration of 26% are added. The mixture is pumped into a reaction vessel for aging. The aging temperature is controlled at 90℃ and the aging time is 8 hours. After aging, the mixture is washed with water in a washing pool and dried. It is then placed in an oven for baking at a temperature controlled at 120℃. After drying, it is soaked in phosphoric acid and washed with water. Then it is placed in the oven for baking at a temperature controlled at 135℃ for 24 hours to obtain the finished adsorbent.

8. The transformer dismantling oil light-dyeing and regeneration device according to claim 7, characterized in that, The amount of catalytic adsorption composite material (4) used is 1.5%-2% of the oil weight.

9. A transformer dismantling oil light-blowing decolorization and regeneration device according to claim 8, characterized in that, The catalytic adsorption composite material (4) is also doped with glucose zinc oxide or titanium dioxide nanoparticles; the glucose zinc oxide and titanium dioxide nanoparticles account for 20-50% of the weight of the catalytic adsorption composite material.

10. A GC-MS differential spectral method for detecting coloring substances in transformer dismantling oil, employing the photo-irradiation decolorization and regeneration device for transformer dismantling oil as described in claim 9, characterized in that the detection method includes the following steps: Step 01: Use a chromatograph to separate the substances in the recycled oil. Place the recycled oil in a column oven and increase the column temperature from 120°C to 325°C at a rate of 5°C / min to vaporize the substances in the recycled oil. At the same time, helium gas with a purity higher than 99.999% is introduced at a flow rate of 1.0 mL / min. After vaporization, the substances pass through the chromatographic column under the push of the helium gas and are separated and fixed by the stationary liquid in the chromatographic column. Step 2: Use a mass spectrometer to identify the chromogenic substances. In the selected ion detection mode (SIM), the electron impact ion source (EI) is 230C and the electron energy is set to 70eV. The mass-to-charge ratio of each substance is obtained and compared with the database to determine the molecular formula of the corresponding substance. Step 3: After the decolorized recycled oil is processed through steps 1 and 2, the changes in the peak areas of the old oil and the recycled oil can be compared to analyze the color-causing substances removed from the oil before and after decolorization.

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