CN113201387B - Low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance and preparation method thereof - Google Patents

Low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance and preparation method thereof Download PDF

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CN113201387B
CN113201387B CN202110516740.0A CN202110516740A CN113201387B CN 113201387 B CN113201387 B CN 113201387B CN 202110516740 A CN202110516740 A CN 202110516740A CN 113201387 B CN113201387 B CN 113201387B
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oil
natural ester
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CN113201387A (en
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杨涛
姚德贵
王飞鹏
李剑
吕中宾
郑含博
寇晓适
黄正勇
姚伟
付刚
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Chongqing University
State Grid Corp of China SGCC
Guangxi University
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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State Grid Corp of China SGCC
Guangxi University
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/048Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/401Fatty vegetable or animal oils used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts

Abstract

The invention discloses low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance and a preparation method thereof, and the environment-friendly natural ester mixed insulating oil consists of an insulating oil mixture, zinc diamyl dithiocarbamate accounting for 1.3-1.5% of the weight of the oil, antimony dialkyl dithiocarbamate accounting for 1.1-1.3% of the weight of the oil, 4' -methylene-bis (2, 6-di-tert-butylphenol) accounting for 0.5-0.7% of the weight of the oil, polymethacrylate accounting for 0.8-1.0% of the weight of the oil and poly alpha olefin accounting for 12-15% of the weight of the oil, wherein the insulating oil mixture is prepared by mixing natural ester insulating oil, epoxidized insulating oil and high-oleic acid insulating oil according to the volume ratio of 4-5. The natural ester mixed insulating oil prepared by the invention has excellent oxidation resistance and low temperature resistance, good physical, chemical and electrical properties, can meet the use conditions at low temperature, and effectively expands the application range of the natural ester insulating oil.

Description

Low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance and preparation method thereof
Technical Field
The invention belongs to the technical field of insulating oil, and particularly relates to low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance and a preparation method thereof.
Background
The oil-immersed transformer has been used for more than 100 years by adopting mineral insulating oil as a cooling insulating medium, but the biodegradability of the mineral insulating oil is poor, leakage often occurs in the using process to pollute the environment, and particularly in areas such as agriculture, forestry, water sources and buildings, the difficult problem of recycling waste mineral insulating oil and the fire and large-area power failure accidents caused by overload of the mineral insulating oil transformer seriously affect the life of people. Compared with mineral insulating oil, the dielectric constants of the natural ester insulating oil and the insulating paper are closer, and the electric field distribution of the insulating oil and the insulating paper in an alternating current electric field in a natural ester oil paper insulating system is more uniform; the natural ester insulating oil can effectively delay the aging rate of insulating paper and prolong the insulating life of the paper, the service life of the insulating paper in the natural ester insulating oil transformer is 5-8 times that of the insulating paper in a mineral oil transformer, and the life cycle cost of the natural ester insulating oil transformer can be effectively reduced. Because the natural ester insulating oil has the characteristics of reproducibility, high ignition point, easy biodegradation, paper insulation aging delay and the like, the natural ester insulating oil is considered to be a good liquid dielectric medium for developing an energy-saving oil-immersed transformer with overload capacity. Therefore, with the increasing shortage of petroleum resources and the gradual enhancement of environmental awareness of people, the natural ester insulating oil as a green, environment-friendly and renewable resource is inevitably a future development direction in the field of insulating oil, and at present, more than 200 tens of thousands of natural ester insulating oil transformers are in net hanging operation globally.
The natural ester insulating oil has the following defects while having excellent performance: 1) Poor oxidation resistance, mainly caused by the large number of unsaturated double bonds in the fatty acid chains of the triglycerides and the glyceryl groups in the triglycerides; 2) The poor low temperature fluidity is mainly caused by the large molecular weight of triglycerides. It is generally considered that monounsaturated fatty acids have good oxidation stability and low-temperature fluidity, so that natural ester insulating oil needs to select natural ester having a high content of monounsaturated fatty acids as a raw material oil. The content of monounsaturated fatty acid in camellia oil and olive oil can reach more than 70 percent, but the production cost is high, the content of monounsaturated fatty acid in soybean oil is relatively high, the planting range is wide, and the production cost is low, so that the soybean oil is mostly adopted to process and produce natural ester insulating oil at home and abroad.
Modifications or additives may be used to improve the oxidation resistance and low temperature fluidity of natural ester insulating oils in general. However, the oxidation resistance and low-temperature fluidity of the natural ester insulating oil are improved by using the additive alone, and the obtained oxidation resistance and low-temperature fluidity cannot meet related performance requirements under normal conditions; the double bonds of triglyceride in the natural ester insulating oil can be eliminated by adopting an epoxidation modification mode, so that the natural ester insulating oil has better oxidation resistance, the tendency of forming oil sludge is obviously reduced, and the antioxidant also has very good sensitivity, but the saturation degree of the natural ester insulating oil is increased, and further the low-temperature fluidity is further deteriorated; hydrogenation can completely convert unsaturated fatty acids in the natural ester insulating oil into saturated fatty acids, but improves the oxidation resistance of the natural ester insulating oil and simultaneously reduces the low-temperature fluidity of the natural ester insulating oil.
To further improve the properties of natural ester insulating oils, there are currently a number of studies reporting the combination of modification and the use of additives. Chinese patent CN101538500A discloses a method for preparing insulating oil using vegetable oil as raw material, which comprises the steps of alkali neutralization, reduced pressure distillation, hydrogenation, deep refining, etc. of vegetable oil, and finally adding additives to prepare the insulating oil using vegetable oil as raw material. Chinese patent CN102682869A discloses a vegetable insulating oil and a preparation method thereof, wherein the vegetable insulating oil is prepared by carrying out ester exchange, reduced pressure distillation, decoloration, acid reduction, filtration, deep dehydration and other processes on refined vegetable oil, and finally adding an additive.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance and a preparation method thereof. The preparation method has the advantages of short period, environmental protection, economy and high efficiency, can obviously improve the oxidation resistance and low temperature resistance of the natural ester mixed insulating oil, and effectively enlarges the application range of the natural ester mixed insulating oil.
In order to achieve the purpose, the invention adopts the following technical scheme:
the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance is characterized by comprising an insulating oil mixture, zinc diamyldithiocarbamate accounting for 1.3-1.5% of the weight of the oil, antimony dialkyldithiocarbamate accounting for 1.1-1.3% of the weight of the oil, 4' -methylenebis (2, 6-di-tert-butylphenol) accounting for 0.5-0.7% of the weight of the oil, polymethacrylate accounting for 0.8-1.0% of the weight of the oil and poly alpha olefin accounting for 12-15% of the weight of the oil.
Further, the insulating oil mixture is composed of a natural ester insulating oil, an epoxidized insulating oil and a high oleic acid insulating oil, all of which are based on soybean oil.
Furthermore, the volume ratio of the natural ester insulating oil to the epoxidized insulating oil to the high oleic acid insulating oil is 4-5.
Furthermore, the high-oleic-acid insulating oil is refined from high-oleic-acid soybean oil or prepared by selectively hydrogenating and modifying soybean oil, and the oleic acid content in the obtained high-oleic-acid insulating oil is more than 70%.
Further, the preparation method of the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance comprises the following steps:
(1) Under the conditions of stirring and vacuum, heating natural ester insulating oil, epoxidized insulating oil and high oleic acid insulating oil respectively, then carrying out vacuum dehydration, then mixing according to corresponding proportion, carrying out short-time ultrasonic dispersion treatment, and continuously stirring for 15-18 min;
(2) And (2) sequentially adding zinc diamyldithiocarbamate, antimony dialkyldithiocarbamate, 4' -methylenebis (2, 6-di-tert-butylphenol), polymethacrylate and poly-alpha-olefin in corresponding mass proportion into the insulating oil mixture subjected to ultrasonic treatment in the step (1), performing short-time ultrasonic dispersion treatment again, continuously stirring for 25-30 min, and then cooling the natural ester mixed insulating oil to room temperature in vacuum to obtain the product of the invention.
Further, in the step (1), the stirring speed is 80-100 r/min, and the vacuum degree is 30-50 Pa; the heating temperature is 65-68 ℃.
Further, the short-time ultrasonic dispersion treatment conditions in the step (1) are as follows: the ultrasonic power is 120-160W, the ultrasonic frequency is 16-30 kHz, the ultrasonic treatment time is 8-10 min, and a circulation mode of ultrasonic dispersion for 90-120 s and stopping for 90-120 s is adopted.
Further, the short-time ultrasonic dispersion treatment conditions in the step (2) are as follows: the ultrasonic power is 100-120W, the ultrasonic frequency is 16-20 kHz, the ultrasonic treatment time is 8-10 min, and a circulation mode of ultrasonic dispersion for 60-90 s and stopping for 90-120 s is adopted.
The weight of the oil is the weight of the environment-friendly natural ester mixed insulating oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention improves the saturation degree of the natural ester mixed insulating oil to a certain extent by adding the quantitative epoxidized insulating oil, and effectively improves the oxidation resistance and the sensitivity to the antioxidant of the natural ester mixed insulating oil; on the basis, the antioxidant synergistic performance of the antioxidants is perfectly combined, the antioxidant performance of the natural ester mixed insulating oil is greatly improved, the tendency of forming oil sludge is reduced, and the problem of poor low-temperature fluidity caused by excessive addition of the epoxidized insulating oil is effectively avoided.
(2) The addition of the high-oleic-acid insulating oil improves the content of monounsaturated fatty acid in the natural ester mixed insulating oil, effectively improves the oxidation resistance and low-temperature fluidity of the natural ester mixed insulating oil, combines the excellent low-temperature characteristic and oxidation stability of the poly-alpha-olefin, and can effectively improve the low-temperature performance of the natural ester mixed insulating oil by being compounded with the pour point depressant.
(3) The strong vibration and stirring action generated by the secondary effect of the ultrasonic wave can effectively improve the uniform dispersion degree of each component in the natural ester mixed insulating oil, and is more favorable for improving the oxidation resistance and low-temperature fluidity of the natural ester mixed insulating oil; by accurately controlling the ultrasonic dispersion power, frequency and time, the problems of additive failure caused by excessive ultrasonic dispersion energy and C produced by cracking of natural ester insulating oil can be effectively avoided 2 H 6 、C 2 H 2 And the like, and polar substances such as aldehyde, ketone and the like.
(4) The natural ester mixed insulating oil obtained by the preparation method has excellent oxidation resistance and low temperature resistance, the pour point is less than-27.5 ℃, the total acid value after 48h oxidation stability test is less than 0.31mgKOH/g, the dielectric loss factor (90 ℃) is less than 8.1 percent, the performance stability is good, the technical advantage is obvious, and the application range of the natural ester insulating oil is effectively expanded.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited to the scope of the examples. These examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance consists of an insulating oil mixture, zinc diamyl dithiocarbamate accounting for 1.3 percent of the weight of the oil, antimony dialkyl dithiocarbamate accounting for 1.3 percent of the weight of the oil, 4' -methylene-bis (2, 6-di-tert-butylphenol) accounting for 0.7 percent of the weight of the oil, polymethacrylate accounting for 1.0 percent of the weight of the oil and poly-alpha-olefin accounting for 13 percent of the weight of the oil, wherein the insulating oil mixture consists of natural ester insulating oil, epoxidized insulating oil and high-oleic acid insulating oil which all use soybean oil as base oil according to a volume ratio of 5.
The preparation method of the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance comprises the following steps:
(1) Respectively heating natural ester insulating oil, epoxidized insulating oil and high oleic acid insulating oil to 68 ℃ under the conditions of 100r/min and 50Pa, then performing vacuum dehydration, then mixing according to a volume ratio of 5.5;
(2) Adding zinc diamyldithiocarbamate, antimony dialkyldithiocarbamate, 4' -methylenebis (2, 6-di-tert-butylphenol), polymethacrylate and poly-alpha-olefin in corresponding weight ratio into the insulating oil mixture subjected to ultrasonic treatment in the step (1) in sequence, performing short-time ultrasonic dispersion treatment again in a circulation mode of ultrasonic dispersion for 60s and stopping for 90s, wherein the ultrasonic power is 100W, the ultrasonic frequency is 20kHz, the ultrasonic treatment is performed for 10min, continuously stirring for 30min after the ultrasonic treatment is finished, and performing vacuum cooling to room temperature to obtain the product, namely the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance.
Example 2
The low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance is composed of an insulating oil mixture, zinc diamyldithiocarbamate accounting for 1.5 percent of the weight of the oil, antimony dialkyldithiocarbamate accounting for 1.2 percent of the weight of the oil, 4' -methylenebis (2, 6-di-tert-butylphenol) accounting for 0.5 percent of the weight of the oil, polymethacrylate accounting for 0.8 percent of the weight of the oil and poly alpha olefin accounting for 15 percent of the weight of the oil, wherein the insulating oil mixture is composed of natural ester insulating oil, epoxidized insulating oil and high-oleic acid insulating oil which all use soybean oil as base oil according to a volume ratio of 4.
The preparation method of the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance comprises the following steps:
(1) Heating natural ester insulating oil, epoxidized insulating oil and high oleic acid insulating oil to 65 ℃ under the conditions of 80r/min and 35Pa respectively, then performing vacuum dehydration, mixing according to a volume ratio of 4;
(2) And (2) sequentially adding zinc diamyldithiocarbamate, antimony dialkyldithiocarbamate, 4' -methylenebis (2, 6-di-tert-butylphenol), polymethacrylate and poly-alpha-olefin in corresponding weight ratios into the insulating oil mixture subjected to ultrasonic treatment in the step (1), performing short-time ultrasonic dispersion treatment again in a circulation mode of ultrasonic dispersion for 90s and stopping for 120s, performing ultrasonic treatment for 8min at an ultrasonic power of 120W and an ultrasonic frequency of 16kHz, continuously stirring for 25min after the ultrasonic treatment is finished, and performing vacuum cooling to room temperature to obtain the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance.
Example 3
The low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance consists of an insulating oil mixture, zinc diamyl dithiocarbamate accounting for 1.5 percent of the weight of the oil, antimony dialkyl dithiocarbamate accounting for 1.1 percent of the weight of the oil, 4' -methylene-bis (2, 6-di-tert-butylphenol) accounting for 0.7 percent of the weight of the oil, polymethacrylate accounting for 0.85 percent of the weight of the oil and poly-alpha-olefin accounting for 15 percent of the weight of the oil, wherein the insulating oil mixture consists of natural ester insulating oil, epoxidized insulating oil and high-oleic acid insulating oil which all use soybean oil as base oil according to a volume ratio of 4.5.
The preparation method of the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance comprises the following steps:
(1) Heating natural ester insulating oil, epoxidized insulating oil and high oleic acid insulating oil to 66 ℃ under the conditions of 100r/min and 30Pa, performing vacuum dehydration, then mixing according to a volume ratio of 4.5;
(2) And (2) sequentially adding zinc diamyldithiocarbamate, antimony dialkyldithiocarbamate, 4' -methylenebis (2, 6-di-tert-butylphenol), polymethacrylate and poly-alpha-olefin in corresponding weight ratios into the insulating oil mixture subjected to ultrasonic treatment in the step (1), performing short-time ultrasonic dispersion treatment again in a circulation mode of ultrasonic dispersion for 75s and stopping for 90s, wherein the ultrasonic power is 120W, the ultrasonic frequency is 18kHz, the ultrasonic treatment is performed for 8min, continuously stirring for 30min after the ultrasonic treatment is finished, and performing vacuum cooling to room temperature to obtain the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance.
Comparative example 1
A natural ester-based mixed insulating oil, which is prepared by removing epoxidized insulating oil from the components, and other components and preparation method are the same as example 1.
Comparative example 2
A natural ester mixed insulating oil, wherein the volume ratio of the natural ester insulating oil to the epoxidized insulating oil to the high oleic acid insulating oil in the insulating oil mixture is 3.5.
Comparative example 3
The natural ester mixed insulating oil is prepared by removing high oleic acid insulating oil from the components, and other components and the preparation method are the same as example 2.
Comparative example 4
A natural ester-based mixed insulating oil was prepared in the same manner as in example 3 except that short-time ultrasonic dispersion treatment was not performed in steps (1) and (2).
The main performance parameters of the natural ester-based hybrid insulating oils prepared in examples 1 to 3 of the present invention and comparative examples 1 to 4 are shown in tables 1 and 2.
As can be seen from the comparison of the data in tables 1 and 2, the oxidation resistance of the natural ester-based hybrid insulating oil is significantly reduced compared to that of example 1 after the epoxidized insulating oil component in the insulating oil mixture is removed in comparative example 1; comparative example 2 the proportion of the epoxidized insulating oil in the insulating oil mixture was increased to 35%, and although the natural ester-based mixed insulating oil had good oxidation resistance, its low temperature performance was deteriorated and its pour point could only reach-23.5 ℃; comparative example 3 after the high oleic acid insulating oil component in the insulating oil mixture was removed, the monounsaturated fatty acid content in the natural ester-based mixed insulating oil was reduced, and both the low temperature fluidity and the oxidation resistance were reduced; comparative example 4 short-time ultrasonic dispersion treatment was not used in the preparation process, which affects the degree of uniform dispersion of each component in the natural ester-based mixed insulating oil, and is not favorable for improving the oxidation resistance and low-temperature fluidity of the natural ester-based mixed insulating oil.
Table 1 main performance parameters of natural ester-based hybrid insulating oils prepared in examples 1-3
Figure BDA0003061794370000101
Table 2 main performance parameters of natural ester-based hybrid insulating oils prepared in comparative examples 1 to 4
Figure BDA0003061794370000111
In conclusion, the comprehensive performance of the natural ester mixed insulating oil prepared in the embodiments 1 to 3 of the present invention is superior to that of the comparative examples 1 to 4, which shows that the composition of the component proportions of the natural ester mixed insulating oil and the preparation process parameters thereof directly affect the performance of the product, and the oxidation resistance and the low temperature fluidity of the natural ester mixed insulating oil are greatly improved by the precise blending of the component proportions and the precise control of the preparation parameters.
It should be noted that the above-mentioned embodiments are only detailed descriptions of the present invention, and are not intended to limit the protection scope of the present invention. Modifications and equivalents of the present invention may be made without departing from the spirit and scope of the invention and are intended to be covered by the appended claims.

Claims (2)

1. The low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance is characterized by comprising an insulating oil mixture, zinc diamyldithiocarbamate accounting for 1.3-1.5 percent of the weight of the oil, antimony dialkyldithiocarbamate accounting for 1.1-1.3 percent of the weight of the oil, 4' -methylenebis (2, 6-di-tert-butylphenol) accounting for 0.5-0.7 percent of the weight of the oil, polymethacrylate accounting for 0.8-1.0 percent of the weight of the oil and poly alpha olefin accounting for 12-15 percent of the weight of the oil; the insulating oil mixture consists of natural ester insulating oil, epoxidized insulating oil and high oleic acid insulating oil which all take soybean oil as base oil; the volume ratio of the natural ester insulating oil to the epoxidized insulating oil to the high oleic acid insulating oil is 4-5; the high-oleic-acid insulating oil is refined from high-oleic-acid soybean oil or prepared by selective hydrogenation modification of soybean oil, and the oleic acid content in the obtained high-oleic-acid insulating oil is more than 70%; the preparation method of the low-temperature-resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance comprises the following steps: (1) Respectively heating natural ester insulating oil, epoxidized insulating oil and high oleic acid insulating oil under stirring and vacuum conditions, then performing vacuum dehydration, then mixing according to corresponding proportions, performing short-time ultrasonic dispersion treatment, and continuously stirring for 15-18 min, wherein the short-time ultrasonic dispersion treatment conditions are as follows: the ultrasonic power is 120-160W, the ultrasonic frequency is 16-30 kHz, the ultrasonic treatment time is 8-10 min, and a circulation mode of ultrasonic dispersion for 90-120 s and stopping for 90-120 s is adopted; (2) Adding zinc diamyldithiocarbamate, antimony dialkyldithiocarbamate, 4' -methylenebis (2, 6-di-tert-butylphenol), polymethacrylate and poly alpha olefin in corresponding mass proportion into the ultrasonically treated insulating oil mixture in the step (1) in sequence, and performing short-time ultrasonic dispersion treatment again, wherein the short-time ultrasonic dispersion treatment conditions are as follows: the ultrasonic power is 100-120W, the ultrasonic frequency is 16-20 kHz, the ultrasonic treatment time is 8-10 min, the circulation mode of ultrasonic dispersion is 60-90 s and stopping 90-120 s is adopted, the natural ester mixed insulating oil is cooled to the room temperature in vacuum after being continuously stirred for 25-30 min, and the natural ester mixed insulating oil is obtained.
2. The low temperature resistant environment-friendly natural ester mixed insulating oil with good oxidation resistance as claimed in claim 1, wherein in the step (1), the stirring speed is 80-100 r/min, and the vacuum degree is 30-50 Pa; the heating temperature is 65-68 ℃.
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