CN101230304B - Environment-friendly type transformer oil and preparation method thereof - Google Patents
Environment-friendly type transformer oil and preparation method thereof Download PDFInfo
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- CN101230304B CN101230304B CN200710010169A CN200710010169A CN101230304B CN 101230304 B CN101230304 B CN 101230304B CN 200710010169 A CN200710010169 A CN 200710010169A CN 200710010169 A CN200710010169 A CN 200710010169A CN 101230304 B CN101230304 B CN 101230304B
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Abstract
The invention provides a kind of environment-friendly transformer oil and the preparation method. The invention takes vegetable oil and the leftovers thereof as the materials, and is prepared after alkali refining, dehydration, esterifying alcoholysis, stopping neutralization, washing and refining, decompression and distillation, decolorization filtration; and after mixing 0.1-5.0 wt percent antioxidant and 0.1-5.0 wt percent pour inhibitor in. The high-grade fatty acid monoester content is 5-95 wt percent; the mono-substituted disubstituted, trisubstituted high-grade fatty acid glyceride contents are 5-95 percent. The appearance of the environment-friendly transformer oil is light-yellow transparent liquid, the kinematic viscosity at 50 DEG C is 2-8mm2/s, the breakdown tension is 40-90KV/2.5mm, and the specific inductive capacity is 2.3-3.2. The environment-friendly transformer oil does not contain sulfur, is innoxious, has high natural decomposability, and can reduce environmental pollution.
Description
Technical field
The present invention relates to environment-friendly type transformer oil and preparation method thereof, relating to vegetables oil and tankage thereof specifically is environment-friendly type transformer oil of raw material and preparation method thereof.
Background technology
Now, the lubricant that the whole world is used, except that the mechanical normal consumption of a part fall and partially recycled utilization, all the other all directly flow into environment, only the European Community just has 600,000 tons of lubricants to flow in the environment every year.Flow into lubricant severe contamination landing field, rivers and the lake of environment, both caused the loss of natural resources, again the influence ecological environment and the eubiosis.
And along with the increasingly stringent of environmental requirement of shortage gradually of petroleum resources, people pay attention to the Application and Development of animal-plant oil as lubricant again, and wish to improve its thermal oxidation stability and low-temperature performance by chemical process, can become the important lubricant of following proxy-mineral lubricating oil.
The effect of transformer oil in transformer mainly is insulation and heat radiation.Mineral base transformer oil is very complicated various hydrocarbon polymers-a be called mixture of " hydro carbons " that contains.In addition, also contain elements such as sulphur, nitrogen, oxygen.As the raw material of mineral lubricating oils, generally to take from the cut that the oil mid-boiling point is higher than 300 ℃ or 350 ℃, or be equivalent in the hydrocarbon molecules, main carbonatoms is about 20～40 various hydro carbons.In the manufacturing of transformer and use inevitably leakage phenomenon can appear, these can not natural degradation and toxic action be extremely serious to the pollution of environment.The environment-friendly type transformer oil that we developed under above-mentioned prerequisite, realizes that for better the strategy of sustainable development contributes from resource and two aspects of environment just.
Green lubricating oil is different with the physicochemical property of traditional mineral oil, the conventional lubrication oil additive all designs at mineral oil, and green lubricating oil and mineral oil have very big-difference on the susceptibility of additive, and the mechanism of action of base oil and additive is also different.Green lubricating oil requires additive hypotoxicity, low pollution, biodegradable, and the design of traditional additive molecule is main from satisfying the use properties angle of lubricating oil, seldom considers factors such as environmental protection and health.The adding of additive can influence to some extent to the biodegradability of base oil itself, especially can damaging effect be arranged to living microorganism in the base oil degradation process or enzyme, thereby influences the biological degradation rate of base oil.So it is the important preceding topic that realizes green lubricating oil practical application that development is applicable to green lubricated oil additives, and this work is worldwide also at the early-stage.Germany's " Blue Angel " tissue has been made following provisions to the lubricated oil additives of green: no carcinogens, nothing cause gene mutagenesis, aberrant; Not chloride and nitrite; Containing metal (deliming outer) not; The maximum additive with potential biodegradable (the OECD302B method is measured, biological degradation rate＞20%) that allows use 7%; Also can add 2% not biodegradable additive, but must be hypotoxic; To biodegradable additive then unrestricted (according to OECD301A-E).
The technical performance index of environmental type transformer oil is compared with mineral base transformer oil, improves to some extent in the following aspects:
1. specific inductivity improves 30%, and breakdown voltage improves 15% approximately;
2. viscosity reduces by 30%, and heat transfer efficiencies improves 20% approximately;
3. sulfur-bearing not is pollution-free, natural decomposition performance height;
4. point of ignition is more than 200 ℃, and is safe in utilization.
Other performance index meet the standard GB 2536-90 of mineral transformer oil fully.
Summary of the invention
The object of the invention provides a kind of plant oil based environment-friendly type transformer oil and preparation method thereof, this transformer oil is compared with traditional mineral oil based transformer oil, remove the breakdown voltage height, dielectric properties are good, and viscosity is low, outside the heat transfer efficiencies height, also have not sulfur-bearing, pollution-free, natural decomposition performance height, point of ignition is more than 200 ℃, characteristics safe in utilization.
Technical solution of the present invention comprises that with vegetables oil the pressed oil of Viscotrol C, Oleum Cocois, Oleum Gossypii semen, brown tung oil, palm-kernel oil, soybean oil, linseed oil, vegetable seed wet goods, the tankage (oil foot, soap stock) that leach oil and grease processing industry and carbonatoms are that 2～5 lower alcohol is the raw material production environment-friendly type transformer oil.It contains high-grade aliphatic ester and oxidation inhibitor, pour point depressant, it is characterized in that containing in the said high-grade aliphatic ester component A of general formula (I) and the component B of general formula (II),
ROO-R
0 (I)
Wherein R is that carbonatoms is 12～23 alkane or alkene, R
0Be that carbonatoms is 2～5 alkyl,
Wherein R is that carbonatoms is 12～22 alkane or alkene, can be identical group, also can be different groups.The content of component A is 5～95wt%, and the content of component B is 5～95wt%.The add-on of oxidation inhibitor is 0.1～5.0wt% of environment-friendly type transformer oil gross weight, and the add-on of pour point depressant is 0.1～5.0wt% of environment-friendly type transformer oil gross weight.The environment-friendly type transformer oil outward appearance is a light yellow transparent liquid, and kinematic viscosity is 2～8mm in the time of 40 ℃
2/ s, voltage breakdown is 40～90KV/2.5mm, specific inductivity is 2.8～3.2, and sulfur-bearing not, toxicological harmless, natural decomposition height.
The preparation method of environment-friendly type transformer oil of the present invention comprises alkali refining, dehydration, esterification alcoholysis, stops neutralization, washing is refining, underpressure distillation, decolorization filtering and allocate oxidation inhibitor, pour point depressant into.Vegetables oil is through alkali refining, free fatty acids and the moisture content of dehydration in the removal of oil and grease, to reduce in the esterification alcoholysis reaction process influence to katalysis, control acid number≤0.002mgKOH/g, water content≤0.01%.Esterification alcoholysis processing condition are: oleyl alcohol mol ratio 1: 3～9, reaction pressure are normal pressure, and temperature of reaction is 60～150 ℃, and the reaction times is 1～8 hour.The chemical equation of esterification alcoholysis is as follows:
Wherein R is that carbonatoms is 12～22 alkane or alkene, can be identical group, also can be different groups, R
0Be that carbonatoms is 2～5 alkyl.Esterification alcoholysis catalyst for reaction and consumption are sodium methylate or NaOH or KOH, and consumption is 0.1～5.0wt% of grease weight; Solid super base, consumption are 1～25wt% of grease weight; Inorganic heteropolyacid, consumption are 1～25wt% of grease weight.Refining, the vacuum distillation process separating by-products glycerine of washing reclaims excessive low-carbon alcohol, removes moisture content and low molecular weight volatile thing, and the employing packing tower carries out vacuum distilling, and absolute pressure is 0.5～10mmHg during vacuum distilling, temperature to 150 ℃.The used discoloring agent of decolorization filtering is atlapulgite, Calcium Chloride Powder Anhydrous, molecular sieve, gac, and consumption is 10～80wt% of grease weight, 30～150 ℃ of bleaching temperatures, bleaching time 10～120 minutes.Add oxidation inhibitor in the products therefrom, pour point depressant is concocted, and makes environment-friendly type transformer oil of the present invention.
The solid super basic catalyst that uses in the esterification alcoholysis reaction process of the present invention is hydrotalcite, houghite and calcined material thereof, and composition is { Mg
6(CO
3) [Al (OH)
6]
2(OH)
44H
2O}.
The inorganic heteropolyacid catalyst that uses in the esterification alcoholysis reaction process of the present invention is SO
4 2-/ WO
3-TiO
2Or S
2O
8 2-/ TiO
2/ MCM-41.
The oxidation inhibitor that adds in the environment-friendly type transformer oil of the present invention is tertiary butyl hydroxyl phenylmethylether (HBA), 2,6 ditertiary butyl p cresol (BHT), 3,4,5-Propylgallate (Tenox PG PG), Tert. Butyl Hydroquinone (TBHQ).
The pour point depressant that adds in the environment-friendly type transformer oil of the present invention is alpha-olefin copolymer, poly-alpha olefins.
Compared with the prior art the preparation process of environment-friendly type transformer oil of the present invention has that technology is simple, easy to operate, constant product quality, production process is pollution-free, can obtain good economic benefit, can reduce the advantage of environmental pollution again.Environment had both been protected in the use of environmental type transformer oil, reduced and polluted, and reduced electric energy loss again, drove peripheral development of rural economy simultaneously, improved peasant's income, comprehensive obvious social benefit.
Embodiment
Now the present invention is described in further detail in conjunction with example:
Example 1
Raw material is that vegetables oil comprises Viscotrol C, Oleum Cocois, Oleum Gossypii semen, plam oil, palm-kernel oil, soybean oil, linseed oil, the pressed oil of vegetable seed wet goods, leach the tankage (oil foot of oil and grease processing industry, soap stock) through alkali refining, processed, detect acid number≤0.002mgKOH/g, water content≤0.01%, with carbonatoms be that 2～5 lower alcohol drops into reactor in following ratio, back flow reaction is 1～8 hour under 60～150 ℃ of temperature, stop neutralization, vacuum distilling is carried out with packing tower in the refining back of washing, absolute pressure is 0.5～4mmHg during vacuum distilling, temperature to 150 ℃, separating by-products glycerine, reclaiming excessive low-carbon alcohol reuses, remove moisture content and low molecular weight volatile thing, use the atlapulgite of grease weight 10～80wt% at last, Calcium Chloride Powder Anhydrous, molecular sieve, the composite discoloring agent of gac, under 30～150 ℃ of temperature condition, stirring decolouring in 10～120 minutes handles, use the pressure filter filtered while hot, the oxidation inhibitor of products therefrom and its weight 0.1～5.0wt% and the pour point depressant of its weight 0.1～5.0wt% are mixed, make environment-friendly type transformer oil of the present invention.
Vegetables oil: 100 parts
Low-carbon alcohol: 20～100 parts
Sodium methylate or NaOH or KOH:0.1～5.0 part
Above-mentioned all shares are weight quota.
Example 2
Raw material is that vegetables oil comprises Viscotrol C, Oleum Cocois, Oleum Gossypii semen, plam oil, palm-kernel oil, soybean oil, linseed oil, the pressed oil of vegetable seed wet goods, leach the tankage (oil foot of oil and grease processing industry, soap stock) through alkali refining, processed, detect acid number≤0.002mgKOH/g, water content≤0.01%, with carbonatoms be that 2～5 lower alcohol drops into reactor in following ratio, back flow reaction is 1～8 hour under 60～150 ℃ of temperature, stop neutralization, vacuum distilling is carried out with packing tower in the refining back of washing, absolute pressure is 0.5～4mmHg during vacuum distilling, temperature to 150 ℃, separating by-products glycerine, reclaiming excessive low-carbon alcohol reuses, remove moisture content and low molecular weight volatile thing, use the atlapulgite of grease weight 10～80wt% at last, Calcium Chloride Powder Anhydrous, molecular sieve, the composite discoloring agent of gac, under 30～150 ℃ of temperature condition, stirring decolouring in 10～120 minutes handles, use the pressure filter filtered while hot, the oxidation inhibitor of products therefrom and its weight 0.1～5.0wt% and the pour point depressant of its weight 0.1～5.0wt% are mixed, make environment-friendly type transformer oil of the present invention.
Vegetables oil: 100 parts
Low-carbon alcohol: 20～100 parts
Solid super base: 1～25 part
Above-mentioned all shares are weight quota.
Example 3
Raw material is that vegetables oil comprises Viscotrol C, Oleum Cocois, Oleum Gossypii semen, plam oil, palm-kernel oil, soybean oil, linseed oil, the pressed oil of vegetable seed wet goods, leach the tankage (oil foot of oil and grease processing industry, soap stock) through alkali refining, processed, detect acid number≤0.002mgKOH/g, water content≤0.01%, with carbonatoms be that 2～5 lower alcohol drops into reactor in following ratio, back flow reaction is 1～8 hour under 60～150 ℃ of temperature, stop neutralization, vacuum distilling is carried out with packing tower in the refining back of washing, absolute pressure is 0.5～4mmHg during vacuum distilling, temperature to 150 ℃, separating by-products glycerine, reclaiming excessive low-carbon alcohol reuses, remove moisture content and low molecular weight volatile thing, use the atlapulgite of grease weight 10～80wt% at last, Calcium Chloride Powder Anhydrous, molecular sieve, the composite discoloring agent of gac, under 30～150 ℃ of temperature condition, stirring decolouring in 10～120 minutes handles, use the pressure filter filtered while hot, the oxidation inhibitor of products therefrom and its weight 0.1～5.0wt% and the pour point depressant of its weight 0.1～5.0wt% are mixed, make environment-friendly type transformer oil of the present invention.
Vegetables oil: 100 parts
Low-carbon alcohol: 20～100 parts
Inorganic heteropolyacid: 1～25 part
Above-mentioned all shares are weight quota.
Adopt the environment-friendly type transformer oil of the present invention's preparation, every index after testing, with 20
#The mineral oil based transformer oil is very nearly the same, alternative its use fully.
Attached: the environment-friendly type transformer oil leading indicator of the present invention's preparation is as follows:
| Project | The environment-friendly type transformer | GB2536-90(DB-25) | Test method |
| Outward appearance | Light yellow transparent liquid | Transparent, nothing precipitates and suspended substance | GB511-77 |
| 40 ℃ of kinematic viscosity, mm 2/s≤ | 8.5 | 9.6 | GB265-75 |
| Condensation point, ℃≤ | -25 | -25 | GB510-77 |
| Flash-point, ℃ 〉= | 215 | 140 | GB261-77 |
| Acid number, mgKOH/g≤ | 0.01 | 0.03 | GB264-77 |
| Water soluble acid or alkali | Do not have | Do not have | GB259-77 |
| Oxidation stability: oxidation postprecipitation thing, acid number after %≤oxidation, mgKOH/g≤ | 0.03 0.1 | 0.05 0.2 | SY2670-76 GB264-77 |
| 90 ℃ of dielectric loss tangents, %≤ | 0.4 | 0.5 | SY2654-76 |
| Voltage breakdown, KV/2.5mm 〉= | 56 | 35 | GB507-77 |
Claims (10)
1. environment-friendly type transformer oil, it comprises that pressed oil with vegetables oil, the tankage that leach oil and grease processing industry and carbonatoms are that 2～5 lower alcohol is high-grade aliphatic ester, oxidation inhibitor and the pour point depressant of raw material production, it is characterized in that containing in the said high-grade aliphatic ester component A of general formula (I) and the component B of general formula (II)
ROO-R
0 (I)
Wherein R is that carbonatoms is 12～23 alkane or alkene, R
0Be that carbonatoms is 2～5 alkyl,
Wherein R is that carbonatoms is 12～22 alkane or alkene, the content of component A accounts for 5～95wt% of high-grade aliphatic ester, the content of component B accounts for 5～95wt% of high-grade aliphatic ester, the add-on of oxidation inhibitor is 0.1～5.0wt% of environment-friendly type transformer oil gross weight, the add-on of pour point depressant is 0.1～5.0wt% of environment-friendly type transformer oil gross weight, and surplus is a high-grade aliphatic ester.
2. according to the described environment-friendly type transformer oil of claim 1, it is characterized in that: said vegetables oil is one or more in Viscotrol C, Oleum Cocois, Oleum Gossypii semen, plam oil, palm-kernel oil, soybean oil, linseed oil, the rapeseed oil.
3. according to the described environment-friendly type transformer oil of claim 1, it is characterized in that: said pour point depressant is alpha-olefin copolymer or poly-alpha olefins.
4. according to the described environment-friendly type transformer oil of claim 1, it is characterized in that: said oxidation inhibitor is tertiary butyl hydroxyl phenylmethylether, 2,6 ditertiary butyl p cresol, 3,4, any in 5-Propylgallate, the Tert. Butyl Hydroquinone.
5. the method for preparing the described environment-friendly type transformer oil of claim 1, it is characterized in that: it is characterized in that with vegetables oil and tankage thereof be raw material, through alkali refining, dehydration back and carbonatoms is that 2～5 lower alcohol carries out the esterification alcoholysis, termination neutralization, washing are carried out underpressure distillation, decolorization filtering after making with extra care again, add oxidation inhibitor, pour point depressant at last.Esterifying alcohol solves processing condition: oleyl alcohol mol ratio 1: 3～9, reaction pressure are normal pressure, and temperature of reaction is 60～150 ℃, and the reaction times is 1～8 hour.
6. according to the described preparation environment-friendly type transformer oil of claim 5 method, it is characterized in that: the esterification alcoholysis catalysts is sodium methylate or NaOH or KOH, and catalyst levels is 0.1～5.0wt% of grease weight.
7. according to the described preparation environment-friendly type transformer oil of claim 5 method, it is characterized in that: the esterification alcoholysis catalysts is a solid super base, and catalyst levels is 1～25wt% of grease weight.
8. according to the described preparation environment-friendly type transformer oil of claim 5 method, it is characterized in that: the esterification alcoholysis catalysts is inorganic heteropolyacid, and catalyst levels is 1～25wt% of grease weight.
9. according to the described preparation environment-friendly type transformer oil of claim 5 method, it is characterized in that: the used discoloring agent of decolorization filtering is two or more in atlapulgite, Calcium Chloride Powder Anhydrous, molecular sieve, the gac, consumption is 10～80wt% of grease weight, 30～150 ℃ of bleaching temperatures, bleaching time 10～120 minutes.
10. according to the described preparation environment-friendly type transformer oil of claim 5 method, it is characterized in that: underpressure distillation adopts packing tower to carry out vacuum distilling, and absolute pressure is 0.5～4mmHg during vacuum distilling, temperature to 150 ℃.
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|---|---|---|---|
| CN200710010169A CN101230304B (en) | 2007-01-25 | 2007-01-25 | Environment-friendly type transformer oil and preparation method thereof |
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| CN101230304B true CN101230304B (en) | 2010-05-19 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538500B (en) * | 2009-04-28 | 2012-07-04 | 重庆大学 | Preparation method of insulating oil taking vegetable oil as raw material |
| 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 |
| CN102507467A (en) * | 2011-10-20 | 2012-06-20 | 湖南省电力公司科学研究院 | Test method of oxidation stability of transformer oil |
| CN102682869B (en) * | 2012-04-11 | 2015-01-07 | 中国电力科学研究院 | Preparation method of vegetable insulating oil |
| CN102827675B (en) * | 2012-09-21 | 2013-09-04 | 西安卓源电力科技有限公司 | Method for preparing environment-friendly insulating oil by taking plant oil or recovered oil as raw materials |
| 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 |
| CN104450037B (en) * | 2014-11-04 | 2017-02-15 | 云南电网公司电力科学研究院 | Novel transformer anti-aging mixed insulating oil and preparation method thereof |
| CN104987914B (en) * | 2015-07-21 | 2018-04-20 | 武汉南瑞电力工程技术装备有限公司 | A kind of low pour point mix insulation oil and preparation method thereof |
| CN105273819A (en) * | 2015-11-11 | 2016-01-27 | 国网山东郯城县供电公司 | Environment-friendly insulation oil for transformer and preparing method of environment-friendly insulation oil |
| CN106046806A (en) * | 2016-07-26 | 2016-10-26 | 潘明华 | High-heat-radiativity insulating power transformer oil and preparation process thereof |
| CN106318593A (en) * | 2016-08-25 | 2017-01-11 | 刘雁 | Recycled lubricating oil regeneration technology |
| PL3352177T3 (en) | 2017-01-24 | 2021-12-20 | Avantherm Ab | Biogenic low viscosity insulating oil |
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