CN101538505B - Environment-friendly insulating oil taking vegetable oil as raw material - Google Patents
Environment-friendly insulating oil taking vegetable oil as raw material Download PDFInfo
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- CN101538505B CN101538505B CN2009101037093A CN200910103709A CN101538505B CN 101538505 B CN101538505 B CN 101538505B CN 2009101037093 A CN2009101037093 A CN 2009101037093A CN 200910103709 A CN200910103709 A CN 200910103709A CN 101538505 B CN101538505 B CN 101538505B
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Abstract
The invention provides environment-friendly insulating oil which takes vegetable oil as the raw material, and has high flash point and anti-oxidation stability, consists essentially of triglyceride and antioxidant, and also contains a metal deactivator in the further technical proposal. The environment-friendly insulating oil is prepared by refinement by taking vegetable oil as the raw material, does not contain toxic substances, dose not cause damage to environment and human body, and can be rapidly and thoroughly biodegraded, is environment-friendly insulating liquid, and can be applied in places with requirement of high fireproof performance as the flash point and the fire point thereof are both higher than 300 DEG C; the risk of fire and explosion is far lower than that of the traditional transformer oil; and all other performance indexes fully conform to the national standard GB 2536-90 of mineral transformer oil.
Description
Technical field
The present invention relates to the vegetables oil is the environmental protection transformer oil of raw material.
Background technology
Transformer oil is important liquid insulating medium, in electrical equipments such as X-former, uses in a large number.Because mineral insulating oil is with low cost, insulating property and cooling performance are good, in the electrical equipment manufacturing, are used widely.But the biodegradable of mineral insulating oil is poor, in case serious leakage will cause severe contamination to soil, water source and even public community on every side; And the burning-point of mineral insulating oil is low, and is high temperature resistant and fire resistance is poor, is not suitable in the mine, mine, military installations, Highrise buildings etc. are to using in the high place of fire-fighting safety requirements; The reserves of natural oil are limited simultaneously, estimate serious oil shortage will occur in the middle of this century.
In order to satisfy the demand to high burning-point liquid insulating material, the work of seeking high-temperature behavior good insulation performance oil is the direction that people study always.Not fuel oil of Askarel has been invented by nineteen twenty-nine Britain Si Wang company, and its staple is polychlorinated biphenyl (PCB).PCB has very high chemicalstability and electric insulation intensity, and is poisonous but late 1960s it is found that PCB, and various countries all prohibite and use and sell afterwards.Substituting in the oily process of searching PCB, number of research projects has been done by various countries manufacturer.The 1950's, silicone oil was invented by the U.S., but just came out up to first transformer silicon oil in 1974.Britain GEC company had made first X-former with the synthetic ester of the Midel7131 of difficult combustion in 1977.The beginning of the eighties, Britain developed not fuel oil of Formel, and nineteen eighty-three, first X-former put into operation.U.S. DSI company has developed the petroleum-type fire resistant oil in recent years successively, has wherein that α oil, β are oily, a polyalphaolefin etc.
Fuel oil and fire resistant oil do not grow up because of transformer oil fire resistance difference; The seventies is in the process that substitutes oil product of seeking X-former; People require with being not less than 300 ℃ with the burning-point that has, and this index table doubles above than transformer oil and is widely accepted.All more than 300 ℃, each item performance and transformer oil are suitable for the burning-point of these composite insulations, but cost is too high, therefore are very limited in the use.
Publication number is that the Chinese invention patent Shen Qing Publication specification sheets of CN101230304A discloses a kind of environment-friendly type transformer oil and preparation method thereof; With vegetables oil and tankage thereof is raw material, through alkali refining, dehydration, esterification alcoholysis, stop neutralization, washing exquisiteness, underpressure distillation, decolorization filtering and 0.1-5.0wt% oxidation inhibitor is gone in blending, the 0.1-5.0wt% pour point depressant makes.But publication number be the flash-point of environment-friendly type transformer oil of CN101230304A about 215 ℃, can not reach requirement as difficult burning-point oil, limited its application in high fire resistance place.Secondly, the antioxidative stabilizer of this environment-friendly type transformer oil is still waiting further raising.
Summary of the invention
In view of this, in order to address the above problem, it is the environmental protection transformer oil of raw material with the vegetables oil that the present invention provides a kind of, and flash-point is high, and antioxidative stabilizer is strong.
The objective of the invention is to realize like this, is the environmental protection transformer oil of raw material with the vegetables oil, comprises component A and inhibitor like general formula (1), wherein R
1, R
2, R
3For carbonatoms 12～22 alkane or alkene; Said component A and B component are that raw material makes with the vegetables oil;
Further, said vegetables oil is one or more in rapeseed oil, VT 18, sweet oil, sunflower seed oil, peanut oil, camellia seed oil and the Oleum Gossypii semen;
Further, said inhibitor is a DBPC 2,6 ditertiary butyl p cresol, 4, one or more in 4-methylene-bis (2,6 di t butyl phenol), certain herbaceous plants with big flowers base phenyl alpha-naphthylamine (korenyl alpha-naphthylamine), tertiarybutylhydroquinone, tea-polyphenol and the Rosmarinus officinalis;
Further, said is that the environmental protection transformer oil of raw material also comprises metal passivator with the vegetables oil;
Further, said metal passivator is one or more in Methylbenzotriazole verivate, liquid triazole verivate or the triazole tetrahydrobenzene, and said is that the mass percent of metal passivator is 0.1%～0.5% in the environmental protection transformer oil of raw material with the vegetables oil;
Further, said with the vegetables oil be the mass percent of component A in the environmental protection transformer oil of raw material greater than 95%, the mass percent of inhibitor is 0.2%～0.5%;
Further, said is that the mass percent of component A, inhibitor and metal passivator is respectively 99%, 0.5%, 0.5% in the environmental protection transformer oil of raw material with the vegetables oil.
Further, said is that the environmental protection insulating oil flash point of raw material is 315～328 ℃ with the vegetables oil;
Further, said is that the frequency breakdown voltage of the environmental protection transformer oil of raw material is 73～95kV with the vegetables oil;
Further, said is that the dielectric loss tangent value of the environmental protection transformer oil of raw material is 0.5%～0.8% with the vegetables oil.
Compared with prior art, the present invention has following advantage:
(1) the present invention is that the environmental protection transformer oil of raw material is obtained through refining by vegetables oil with the vegetables oil, does not contain Toxic matter, can not damage environment and human body, and biological degradation fast and up hill and dale, be a kind of environment-friendly type insulated liquid;
(2) the present invention is that the environmental protection transformer oil of raw material is a kind of flame retardant resistance transformer oil with the vegetables oil, and its flash-point and burning-point all are higher than 300 ℃, can be applied to the place that high fire resistance requires, and the risk of presence of fire and blast is all far below traditional transformer oil;
(3) the present invention is that the environmental protection transformer oil of raw material has good physics and chemistry and dielectric properties with the vegetables oil; Acid number is lower than 0.03mg KOH/g; Condensation point is lower than-18 ℃, and frequency breakdown voltage surpasses 70kV, and 90 ℃ of Jie's damage value tg δ are lower than 0.0075; Volume specific resistance is higher than 7 * 1010 Ω m, and specific inductivity is 2.93.The performance constant can reach or be higher than the standard as insulating liquid in the electricinstallation; Other performance index also meet the standard GB 2536-90 of mineral transformer oil fully.
Other advantages of the present invention, target; To in specification sheets subsequently, set forth to a certain extent with characteristic; And to a certain extent,, perhaps can from practice of the present invention, obtain instruction based on being conspicuous to those skilled in the art to investigating of hereinafter.Target of the present invention and other advantages can be passed through following specification sheets, claims, and the structure that is particularly pointed out in the accompanying drawing realizes and obtains.
Embodiment
Below will carry out detailed description to the preferred embodiments of the present invention.
Of the present invention is that the environmental protection transformer oil of raw material can be through the preparation of following method with the vegetables oil:
1) vegetable oil material is carried out the alkali neutralization:
11) in 5～10min, the NaOH solution that accounts for vegetable oil material weight 1%～4% of adding and oily equality of temperature carries out the alkali neutralization; Behind the 30min, carry out vegetable oil material is washed with the zero(ppm) water of equality of temperature, then standing demix; Separation of fatty acids and sodium hydroxide neutralized reaction product sodium soap leave standstill more than the 30min then, with vacuum distillation apparatus oil sample are distilled 30min again; Stop heating, remove vacuum;
12) in alkali with after vegetable oil material add the discoloring agent account for vegetable oil material weight 2.0～5.0%; Decompression and heating, residual voltage 20～50mmHg in the container, 90～95 ℃ of oil temperature, bleaching time 20～30min after decolouring finishes, is cooled to 70 ℃, removes vacuum;
13) repeating step 11) and 12), until the vegetable oil material clear, and acid number≤0.03mgKOHg
-1
2) in the alkali with after vegetable oil material carry out underpressure distillation: keeping the container residual voltage is 20～50mmHg, and 95 ℃ of oil temperature are distilled and removed moisture, elimination impurity in 3 hours;
3) vegetable oil material after the underpressure distillation is carried out hydrogenation: add the catalyzer that accounts for vegetable oil material weight 0.4%～0.5%, under sealing, nitrogen environment, heat up by 5～10 ℃/min; Keep 180～200 ℃ of temperature, pressure 0.15～0.2MPa, stir speed (S.S.) 300～700rmin
-1, in vegetable oil material, feed hydrogen, hydrogenation 130min～180min;
4) vegetable oil material after the hydrogenation is carried out dark refining: dark purified purpose is to remove the trace copper of enzymatic oxidation effect with Hydrocerol A; Add the Hydrocerol A that accounts for vegetable oil material weight 0.3-1.0% in the vegetable oil material after hydrogenation; Underpressure distillation 1-2 hour, pressure 20-50mmHg, temperature 80-90 ℃; Add the bentonite that accounts for vegetable oil material weight 0.1-0.3%, underpressure distillation 1-2 hour, pressure 20-50mmHg, temperature 80-90 ℃ again;
5) vegetable oil material after the dark refining is carried out underpressure distillation once more: keeping the container residual voltage is 20～50mmHg, and the oil temperature is distilled and removed moisture suction filtration then, impurity such as elimination catalyzer in 3 hours at 95 ℃;
6) add inhibitor and metal passivator in the vegetable oil material after underpressure distillation once more.
Embodiment 1
With the rapeseed oil is raw material; Preparation as stated above in the step 6), adds certain herbaceous plants with big flowers base phenyl alpha-naphthylamine (korenyl alpha-naphthylamine) as inhibitor; Add IRGAMET 39 as metal passivator; What make is in the environmental protection transformer oil of raw material with the vegetables oil, and effective constituent is component A, inhibitor and the metal passivator of general formula shown in (1) formula, and the mass percent of the component A of its formula of shown in (1) formula is 95%; The mass percent of inhibitor is 0.2%, and the mass percent of metal passivator is 0.1%;
Embodiment 2
With the Oleum Gossypii semen is raw material, and preparation as stated above is in the step 6); Add Rosmarinus officinalis as oxygenant, add IRGAMET 39 as metal passivator, what make is in the environmental protection transformer oil of raw material with the vegetables oil; Effective constituent is component A, inhibitor and the metal passivator of general formula shown in (1) formula; The mass percent of the component A of general formula shown in (1) formula is 96%, and the mass percent of inhibitor is 0.1%, and the mass percent of metal passivator is 0.5%;
Embodiment 3
Mixture with sweet oil, camellia seed oil and Oleum Gossypii semen is a raw material, and preparation as stated above is in the step 6); Add 4,4-methylene-bis (2,6 di t butyl phenol) is as inhibitor; Add IRGAMET 30 as metal passivator; What make is in the environmental protection transformer oil of raw material with the vegetables oil, and effective constituent is component A, inhibitor and the metal passivator of general formula shown in (1) formula, and the mass percent of the component A of general formula shown in (1) formula is 98%; The mass percent of inhibitor is 0.5%, and the mass percent of metal passivator is 0.3%;
Embodiment 4
Mixture with sunflower seed oil, peanut oil is a raw material, and preparation as stated above is in the step 6); Add 2; 6-ditertbutylparacresol and tertiarybutylhydroquinone add IRGAMET 30 as metal passivator as inhibitor, and what make is in the environmental protection transformer oil of raw material with the vegetables oil; Effective constituent is component A, inhibitor and the metal passivator of general formula shown in (1) formula; The mass percent of the component A of general formula shown in (1) formula is 99%, and the mass percent of inhibitor is 0.5%, and the mass percent of metal passivator is 0.5%;
The leading indicator of the vegetable insulating oil of the present invention's preparation is following:
| Parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Transformer oil (GB 2536-90) |
| Outward appearance | Faint yellow, transparent | Faint yellow, transparent | Faint yellow, transparent | Faint yellow, transparent | Transparent, inclusion-free |
| Flash-point/℃ | 315 | 320 | 328 | 325 | ≥135 |
| Acid number/mgKOHg -1 | 0.02 | 0.02 | 0.02 | 0.02 | ≤0.03 |
| Water soluble acid/pH | 5.6 | 5.6 | 5.6 | 5.6 | - |
| Frequency breakdown voltage/kV | 95 | 89 | 82 | 73 | ≥35 |
| Dielectric loss tangent value tg δ (90 ℃)/% | 0.8 | 0.65 | 0.6 | 0.75 | ≤0.5 |
| Volume specific resistance (90 ℃)/Ω m | 7×10 10 | 7×10 10 | 7×10 10 | 7×10 10 | ≥6×10 10 |
| Relative permittivity (90 ℃) | 2.89 | 2.90 | 2.91 | 2.93 | - |
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and obviously, those skilled in the art can carry out various changes and modification and not break away from the spirit and scope of the present invention the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (6)
1. with the vegetables oil of the application of raw material combination thing as transformer oil; It is characterized in that: said composition comprises component A and the inhibitor like general formula (1); Said component A is that raw material makes with the vegetables oil, and the mass percent of component A is greater than 95% in the said compsn, and the mass percent of inhibitor is 0.2%～0.5%; Said compsn also comprises metal passivator; Said metal passivator is the triazole tetrahydrobenzene, and the mass percent of metal passivator is 0.1%～0.5% in the said compsn, wherein R
1, R
2, R
3For carbonatoms 12～22 alkane or alkene;
Said vegetables oil is one or more in rapeseed oil, the camellia seed oil.
2. application according to claim 1 is characterized in that: said inhibitor is one or more in DBPC 2,6 ditertiary butyl p cresol, tertiarybutylhydroquinone, bitter edible plant polyphenol and the Rosmarinus officinalis.
3. application according to claim 1 is characterized in that: in the said compsn, the mass percent of component A, inhibitor and metal passivator is respectively 99%, 0.5%, 0.5%.
4. application according to claim 1 is characterized in that: the flash-point of said compsn is 315～328 ℃.
5. application according to claim 1 is characterized in that: the frequency breakdown voltage of said compsn is 73～95kV.
6. application according to claim 1 is characterized in that: the dielectric loss tangent value of said compsn is 0.5%～0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101037093A CN101538505B (en) | 2009-04-28 | 2009-04-28 | Environment-friendly insulating oil taking vegetable oil as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101037093A CN101538505B (en) | 2009-04-28 | 2009-04-28 | Environment-friendly insulating oil taking vegetable oil as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101538505A CN101538505A (en) | 2009-09-23 |
| CN101538505B true CN101538505B (en) | 2012-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101037093A Expired - Fee Related CN101538505B (en) | 2009-04-28 | 2009-04-28 | Environment-friendly insulating oil taking vegetable oil as raw material |
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260574A (en) * | 2010-06-07 | 2011-11-30 | 江苏双江石化制品有限公司 | Processing technology for improving oxidation stability of transformer oil |
| CN102543262A (en) * | 2010-12-31 | 2012-07-04 | 西安卓源电力科技有限公司 | Vegetable insulating oil and preparation method thereof |
| CN102222537A (en) * | 2011-03-31 | 2011-10-19 | 国网电力科学研究院武汉南瑞有限责任公司 | Plant insulating oil for transformer and preparation method thereof |
| CN102533402A (en) * | 2011-12-15 | 2012-07-04 | 重庆大学 | vegetable insulating oil additive combination and preparation method thereof |
| EP2770512B1 (en) * | 2013-02-21 | 2015-09-16 | ABB Technology Ltd | Renewable hydrocarbon based insulating fluid |
| CN104134519B (en) * | 2014-07-15 | 2016-08-24 | 国家电网公司 | A kind of environment-friendly type oil immersion-type distribution transformer based on high burning-point vegetable oil |
| CN105623784A (en) * | 2014-10-27 | 2016-06-01 | 国家电网公司 | Environmental protection nanometer heat conduction transformer oil and preparation method thereof |
| CN105047257A (en) * | 2015-07-06 | 2015-11-11 | 重庆大学 | Method for preparing compounds containing modified fullerene nanoparticles and plant insulating oil |
| CN105296110B (en) * | 2015-10-29 | 2017-12-01 | 上海中孚特种油品有限公司 | A kind of environmental-friendly plant transformer oil and preparation method thereof |
| CN106350148A (en) * | 2016-07-29 | 2017-01-25 | 广东卓原新材料科技有限公司 | Vegetable insulating oil based on shinyleaf yellowhorn oil and application of vegetable insulating oil |
| CN106190431A (en) * | 2016-07-29 | 2016-12-07 | 广东卓原新材料科技有限公司 | A kind of vegetable insulating oil based on almond oil and application thereof |
| CN106479621B (en) * | 2016-08-26 | 2019-10-18 | 重庆大学 | A kind of preparation method of mixed plant insulating oil |
| CN106520259A (en) * | 2016-10-09 | 2017-03-22 | 安徽四新电子有限责任公司 | Insulating oil for explosion-proof capacitor |
| CN109054948B (en) * | 2018-08-03 | 2021-07-20 | 国网重庆市电力公司电力科学研究院 | Low-cost antioxidant nano mixed oil and preparation method thereof |
| CN110747037A (en) * | 2019-10-30 | 2020-02-04 | 凉山德农生物能源股份有限公司 | Jatropha curcas insulating oil and preparation method thereof |
| CN111704953A (en) * | 2020-06-18 | 2020-09-25 | 中国石油化工股份有限公司 | Biodegradable high-ignition-point insulating oil and preparation method thereof |
| CN111892981A (en) * | 2020-08-18 | 2020-11-06 | 江苏双江能源科技股份有限公司 | Vegetable oil-based synthetic ester insulating oil and preparation method thereof |
| CN116731773B (en) * | 2023-06-13 | 2023-12-12 | 上海江天高分子材料有限公司 | Degradable soybean-based natural ester insulating oil and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218497A (en) * | 1996-05-15 | 1999-06-02 | 更新润滑油公司 | Biodegradable lubricant composition from triglycerides and oil-soluble copper |
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| CN101538505A (en) | 2009-09-23 |
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