Macroporous polar adsorption resin for removing paint film in oil for electric power and preparation method of macroporous polar adsorption resin

Abstract

The invention discloses macroporous polar adsorption resin for removing a paint film in oil for electric power and a preparation method of the macroporous polar adsorption resin, and relates to the technical field of purification and regeneration treatment of the oil for electric power, the preparation method comprises the following steps: mixing macroporous adsorption resin and an organic solvent, heating, and continuously stirring in the heating process until the macroporous adsorption resin is fully swelled to obtain a swelled product; a functional monomer is added into the swelling product, heating is conducted, the stirring speed is kept, stirring is conducted, then a reaction is conducted, modified resin is obtained, and the functional monomer is an alkaline strong-polarity modifier; and filtering and washing the modified resin until the washing liquid is neutral and completely clear, and drying to obtain the macroporous polar adsorption resin. The macroporous adsorption resin is used as the precursor, so that the synthesis method is simple and good in stability, the functional monomer containing amino is used for modifying the precursor, the effect of removing the paint film in the degraded electric oil is better, the chromaticity of the oil can be reduced, and the service life of the oil can be effectively prolonged.

Description

Technical Field

[0001] The present invention relates to a macroporous polar adsorption resin for removing paint films in electric power oil and a preparation method thereof, belonging to the technical field of purification and regeneration treatment of electric power oil. Background Art

[0002] Electric power oil mainly includes transformer oil, turbine oil and fire-resistant oil, which are important insulating, lubricating, cooling and speed-regulating media for electric power equipment, and its quality directly affects the safe operation of electric power equipment.

[0003] However, during the use process, electric power oil is gradually oxidized and degraded under the action of oxygen, high temperature, metal impurities, etc., generating oxidation by-products such as acids, aldehydes, ketones and sludge. These oxidation products condense to form insoluble substances suspended in the oil, and finally polymerize to form a soft film substance, and the color of the oil becomes darker. The paint film in the oil will block the filter in the equipment, making the filtration "ineffective", causing poor lubrication of the equipment and equipment wear; the paint film adheres to the servo valve or directional valve, reducing the lubrication gap of the equipment, increasing friction, and seriously causing the valve core to stick and the operation to fail; the paint film deposited on the cooler will cause poor heat dissipation, then the oil temperature rises, the oxidation of the oil accelerates, and the remaining service life of the oil is reduced. Therefore, it is very important to remove the paint film in electric power oil in time to ensure the safe operation of the equipment.

[0004] At present, the paint film in electric power oil is detected according to ASTM D7843 Standard Test Method for Measuring Insoluble Color Bodies Formed by Lubricants in In-Service Turbine Oils by Film Patch Colorimetry. When the paint film propensity index MPC value ≤ 15, it indicates that there is less paint film in the oil; when 15 < MPC value ≤ 30, it indicates that the speed of paint film generation due to oil quality deterioration is relatively fast, and monitoring needs to be strengthened; when MPC > 30, it indicates that a large amount of paint film is generated in the oil and purification treatment is required.

[0005] Due to advantages such as simple operation and strong practicability, the adsorption method has become a commonly used method for the regeneration of electric power oil at present. The adsorbent is the key to determining a high-performance adsorption treatment process.

[0006] At present, the research and application of adsorbents in the field of deteriorated oil regeneration are mostly concentrated on white clay, activated carbon, silicon aluminum molecular sieve, and ion exchange resin, while there is less research on adsorption resin. For example, Liu Shuqiang, Li Zhongkai, Dai Jianqiang, Lin Jian and others disclosed an adsorbent for treating transformer waste oil and its production method (Announcement No.: CN105126748B). The adsorbent components prepared by the patent include nickel ferrite, ferroferric oxide, bentonite and zeolite molecular sieve, which have a large specific surface area and good adsorption effect, but the adsorbent is not easy to recover. Li Yefeng, Liu Yongluo, Wang Juan, Wang Xiaowei and others disclosed a microporous polarity induced adsorbent for regeneration of power oil and its preparation method (Announcement No.: CN103432983A). The patent adds silicon source, aluminum source and quaternary ammonium salt to ethanol aqueous solution, and the prepared mixed solution is transferred to a high-pressure reactor for hydrothermal reaction. The obtained white gel-like substance is subjected to a series of treatments to finally obtain a microporous polarity induced adsorbent. The adsorbent has micropore size, large specific surface area, high molecular polarity and activity, and greatly improves the adsorption capacity and adsorption rate of polar molecular compounds after oil deterioration. However, the adsorbent modification method is relatively complicated. Summary of the invention

[0007] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a macroporous polar adsorption resin for removing varnish in electric power oil and a preparation method thereof. The macroporous adsorption resin is used as a precursor, so that the synthesis method is simple and the stability is good. The precursor is modified by using amino-containing functional monomers, which has a better effect on removing varnish in deteriorated electric power oil, and can reduce the chromaticity of the oil, effectively extending the service life of the oil.

[0008] To achieve the above object, the present invention is implemented by adopting the following technical solutions: In a first aspect, the present invention provides a method for preparing a macroporous polar adsorption resin for removing varnish from electric power oil, comprising: The macroporous adsorption resin is mixed with an organic solvent, the temperature is raised to temperature a, and the mixture is continuously stirred during the heating process until the mixture is fully swollen, thereby obtaining a swollen product; Adding a functional monomer to the swollen product, heating to a temperature b, maintaining a stirring rate c, and stirring to obtain a modified resin, wherein the functional monomer is an alkaline strong polar modifier; The modified resin is filtered and washed until the washing liquid is neutral and completely clear, and then dried to obtain a macroporous polar adsorption resin.

[0009] Furthermore, the macroporous polar adsorption resin is one or more of polyacrylamide resin, polypropylene resin and polystyrene resin.

[0010] Furthermore, the organic solvent is one or more of dichloromethane, dimethylformamide, N-methylpyrrolidone, 1,2-dichloroethane and N,N-dimethylacetamide.

[0011] Furthermore, the mass ratio of the macroporous polar adsorption resin to the organic solvent is 0.05~1:1.

[0012] Furthermore, the temperature a ranges from 40 to 80° C.; and / or the swelling time is 12 to 24 hours.

[0013] Further, the functional monomer is one or more of diethylamine, 2,5-diaminobenzenesulfonic acid, 3,4-diaminobenzenesulfonic acid, 3,5-diaminobenzenesulfonic acid, and 2,4-diaminobenzenesulfonic acid; Furthermore, the mass ratio of the functional monomer to the macroporous polar adsorption resin is 0.2-5:1.

[0014] Furthermore, the temperature b is in the range of 60-120° C.; and / or the stirring rate c is in the range of 80-200 rpm; and / or the reaction time is in the range of 6-12 h.

[0015] Furthermore, the washing liquid is one or more of deionized water, ethanol or methanol; and / or the drying parameters include a drying temperature of 40-80° C. and a drying time of 8-20 hours.

[0016] In a second aspect, the present invention further provides a macroporous polar adsorption resin for removing varnish from electric power oil, which is prepared by any of the above-mentioned methods for preparing a macroporous polar adsorption resin for removing varnish from electric power oil.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses a macroporous adsorption resin as a precursor, so that the synthesis method is simple and the stability is good. The precursor is modified by using an amino-containing functional monomer, which has a better effect on removing the paint film in the deteriorated power oil, and can reduce the chromaticity of the oil, effectively extending the service life of the oil. The present invention has the advantages of high cost-effectiveness, high removal efficiency, no by-products and a wide range of applications, and is suitable for treating deteriorated power oil, and is of great significance to energy conservation and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a SEM schematic diagram of the macroporous polar adsorption resin PS-DEA-5 in Example 1 of the present invention. DETAILED DESCRIPTION

[0019] The present invention will be further described below in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and cannot be used to limit the protection scope of the present invention. Example 1

[0020] The embodiment of the present invention provides a method for preparing a macroporous polar adsorption resin for removing paint film in power oil, comprising the following steps: Take 5 g of polystyrene resin and 50 ml of N,N-dimethylformamide in a three-necked round-bottom flask, heat to 60 °C and maintain the same temperature, stir at 120 rpm, and fully swell for 24 hours; add 10.25 g of diethylamine, heat and heat to 70 °C, maintain a stirring speed of 120 rpm and react at the same temperature for 10 hours. After the reaction is completed, filter and wash with deionized water until the washing liquid is completely clear and neutral; finally, place it in a 60 °C vacuum oven and dry it for 12 hours to obtain a macroporous polar adsorption resin PS-DEA-5, such as Figure 1 shown. Example 2

[0021] The embodiment of the present invention provides a method for preparing a macroporous polar adsorption resin for removing paint film in power oil, comprising the following steps: Take 5 g of polystyrene resin and 50 ml of N,N-dimethylformamide in a three-necked round-bottom flask, heat to 60 °C and maintain the same temperature, stir at 120 rpm, and fully swell for 24 hours; add 10.25 g of 3,4-diaminobenzenesulfonic acid, heat and heat to 70 °C, maintain a stirring speed of 120 rpm and the same temperature for 10 hours. After the reaction is completed, filter and wash with deionized water until the washing liquid is completely clear and neutral; finally, place it in a 60 °C vacuum oven and dry it for 12 hours to obtain the macroporous polar adsorption resin PS-DBS-5. Example 3

[0022] The embodiment of the present invention provides a method for preparing a macroporous polar adsorption resin for removing paint film in power oil, comprising the following steps: Take 5 g of polystyrene resin and 50 ml of N,N-dimethylformamide in a three-necked round-bottom flask, heat to 60 °C and maintain the same temperature, stir at 120 rpm, and fully swell for 24 hours; add 10.25 g of 2,5-diaminobenzenesulfonic acid, heat and heat to 70 °C, maintain a stirring speed of 120 rpm and the same temperature for 10 hours. After the reaction is completed, filter and wash with deionized water until the washing liquid is completely clear and neutral; finally, place it in a 60 °C vacuum oven and dry it for 24 hours to obtain the macroporous polar adsorption resin PS-MPDSA-5. Example 4

[0023] The embodiment of the present invention provides a method for preparing a macroporous polar adsorption resin for removing paint film in power oil, comprising the following steps: Take 5 g of polystyrene resin and 50 ml of N,N-dimethylformamide in a three-necked round-bottom flask, heat to 60 °C and maintain the same temperature, stir at 120 rpm, and fully swell for 24 hours; add 2.05 g of diethylamine, heat and heat to 70 °C, maintain a stirring speed of 120 rpm and react at the same temperature for 10 hours. After the reaction is completed, filter and wash with deionized water until the washing liquid is completely clear and neutral; finally, place it in a 60 °C vacuum oven and dry it for 24 hours to obtain the macroporous polar adsorption resin PS-DEA-1. Example 5

[0024] The embodiment of the present invention provides a method for preparing a macroporous polar adsorption resin for removing paint film in power oil, comprising the following steps: Take 5 g of polystyrene resin and 50 ml of N,N-dimethylformamide in a three-necked round-bottom flask, heat to 60 °C and maintain the same temperature, stir at 120 rpm, and fully swell for 24 hours; add 6.15 g of diethylamine, heat and heat to 70 °C, maintain a stirring speed of 120 rpm and react at the same temperature for 10 hours. After the reaction is completed, filter and wash with deionized water until the washing liquid is completely clear and neutral; finally, place it in a 60 °C vacuum oven and dry it for 12 hours to obtain the macroporous polar adsorption resin PS-DEA-3. Example 6

[0025] The embodiment of the present invention provides a method for preparing a macroporous polar adsorption resin for removing paint film in power oil, comprising the following steps: Take 5 g of polystyrene resin and 50 ml of N,N-dimethylformamide in a three-necked round-bottom flask, heat to 60 °C and maintain the same temperature, stir at 120 rpm, and fully swell for 24 hours; add 14.35 g of diethylamine, heat and heat to 80 °C, maintain a stirring speed of 120 rpm and react at the same temperature for 10 hours. After the reaction is completed, filter and wash with deionized water until the washing liquid is completely clear and neutral; finally, place it in a 60 °C vacuum oven and dry it for 12 hours to obtain the macroporous polar adsorption resin PS-DEA-7.

[0026] The following is a test analysis of the macroporous polar adsorption resins prepared in Examples 1 to 6.

[0027] Test method: 50 mg of adsorption resin was placed in a 100 mL conical flask, 50 g of deteriorated power oil was added, and the flask was placed in a constant temperature oscillating water bath for adsorption at 55 °C with an oscillation frequency of 140 r / min. After 2 h of adsorption, the MPC value of the oil sample was detected according to ASTM D7843 "Standard Test Method for Measurement of Insoluble Color Bodies Generated by Lubricants in Used Turbine Oils by Membrane Patch Colorimetry".

[0028] For transformer oil, turbine oil and fire-resistant oil, the film tendency index MPC values ​​of the macroporous polar adsorption resins prepared in Examples 1 to 6 before and after regeneration are shown in Tables 1 to 3 respectively: Table 1: Comparison of the paint film tendency index MPC values ​​of transformer oil before and after regeneration of the macroporous polar adsorption resin prepared in Examples 1 to 6

[0029] Table 2: Comparison of the film tendency index MPC values ​​of the turbine oil before and after regeneration of the macroporous polar adsorption resin prepared in Examples 1 to 6

[0030] Table 3: Comparison of the paint film tendency index MPC values ​​of the fire-resistant oils before and after regeneration of the macroporous polar adsorption resins prepared in Examples 1 to 6

[0031] It can be seen from Table 1 to Table 3 that the macroporous polar adsorption resins prepared in Examples 1 to 6 are all capable of removing the varnish in deteriorated power oil, reducing the chromaticity of the oil, and effectively extending the service life of the oil.

[0032] It can be seen from a single table that the effect of removing the paint film when diethylamine is used as the functional monomer is better than when 2,5-diaminobenzenesulfonic acid is used as the functional monomer. Therefore, diethylamine is preferably used as the functional monomer.

[0033] Furthermore, as the mass ratio of functional monomer to macroporous polar adsorption resin gradually increases to 5:1, the paint film removal effect continues to improve until it reaches the best. However, when the mass ratio of functional monomer to macroporous polar adsorption resin gradually increases from 5:1 to 7:1, the paint film removal effect is getting worse. This effectively shows that the more functional monomer is added, the better. The optimal mass ratio of functional monomer to macroporous polar adsorption resin is 5:1.

[0034] The above is only a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the technical principle of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a macroporous polar adsorption resin for removing paint film from power oil, characterized in that: include: The macroporous adsorption resin is mixed with an organic solvent, the temperature is raised to temperature a, and the mixture is continuously stirred during the heating process until the mixture is fully swollen, thereby obtaining a swollen product; Adding a functional monomer to the swollen product, heating to a temperature b and stirring at a stirring rate c to obtain a modified resin, wherein the functional monomer is an alkaline strong polar modifier; The modified resin is filtered and washed until the washing liquid is neutral and completely clear, and then dried to obtain a macroporous polar adsorption resin.

2. The method for preparing the macroporous polar adsorption resin for removing varnish from power oil according to claim 1, characterized in that: The macroporous polar adsorption resin is one or more of polyacrylamide resin, polypropylene resin and polystyrene resin.

3. The method for preparing the macroporous polar adsorption resin for removing paint film in power oil according to claim 1, characterized in that: The organic solvent is one or more of dichloromethane, dimethylformamide, N-methylpyrrolidone, 1,2-dichloroethane and N,N-dimethylacetamide.

4. The method for preparing the macroporous polar adsorption resin for removing varnish from power oil according to claim 1, characterized in that: The mass ratio of the macroporous polar adsorption resin to the organic solvent is 0.05-1:

1.

5. The method for preparing the macroporous polar adsorption resin for removing paint film in power oil according to claim 1, characterized in that: The temperature a ranges from 40 to 80° C.; and / or the swelling time ranges from 12 to 24 hours.

6. The method for preparing the macroporous polar adsorption resin for removing varnish from power oil according to claim 1, characterized in that: The functional monomer is one or more of diethylamine, 2,5-diaminobenzenesulfonic acid, 3,4-diaminobenzenesulfonic acid, 3,5-diaminobenzenesulfonic acid and 2,4-diaminobenzenesulfonic acid.

7. The method for preparing the macroporous polar adsorption resin for removing varnish from power oil according to claim 1, characterized in that: The mass ratio of the functional monomer to the macroporous polar adsorption resin is 0.2-5:

1.

8. The method for preparing a macroporous polar adsorption resin for removing varnish from power oil according to claim 1, characterized in that: The temperature b is in the range of 60-120° C.; and / or, the stirring rate c is in the range of 80-200 rpm; and / or, the reaction time is in the range of 6-12 h.

9. The method for preparing a macroporous polar adsorption resin for removing paint film from power oil according to claim 1, characterized in that: The washing liquid is one or more of deionized water, ethanol or methanol; and / or the drying parameters include a drying temperature of 40-80° C. and a drying time of 8-20 hours.

10. A macroporous polar adsorption resin for removing paint film from power oil, characterized in that: The macroporous polar adsorption resin is prepared by the preparation method for removing varnish in power oil as described in any one of claims 1 to 9.

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