JP5047271B2 - Manufacturing method of vegetable insulating oil and vegetable insulating oil manufactured by the manufacturing method - Google Patents
Manufacturing method of vegetable insulating oil and vegetable insulating oil manufactured by the manufacturing method Download PDFInfo
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- JP5047271B2 JP5047271B2 JP2009507572A JP2009507572A JP5047271B2 JP 5047271 B2 JP5047271 B2 JP 5047271B2 JP 2009507572 A JP2009507572 A JP 2009507572A JP 2009507572 A JP2009507572 A JP 2009507572A JP 5047271 B2 JP5047271 B2 JP 5047271B2
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- 235000013311 vegetables Nutrition 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003921 oil Substances 0.000 claims description 34
- 235000019198 oils Nutrition 0.000 claims description 34
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 30
- 239000008158 vegetable oil Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000003549 soybean oil Substances 0.000 claims description 19
- 235000012424 soybean oil Nutrition 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 241000196324 Embryophyta Species 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000010735 electrical insulating oil Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 239000002480 mineral oil Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 10
- 235000010446 mineral oil Nutrition 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000994 depressogenic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- -1 ester compound Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 231100000209 biodegradability test Toxicity 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating 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
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Fats And Perfumes (AREA)
- Lubricants (AREA)
- Catalysts (AREA)
Description
本発明は、電気絶縁油に関するもので、より詳細には、植物油を利用して酸化安定性が優秀で、使用後自然生態系で容易に分解される生分解性を有する植物性電気絶縁油に関するものである。 The present invention relates to an electrical insulating oil, and more particularly to a vegetable electrical insulating oil having excellent oxidative stability using a vegetable oil and having biodegradability that is easily degraded in a natural ecosystem after use. Is.
産業革命以後、機械の発達と共に油の需要が急激に増加し、潤滑剤の使用条件が過酷になるにつれ、より優秀な油の性質が要求され始めた。 Since the industrial revolution, the demand for oil has increased rapidly with the development of machinery, and as the conditions of use of lubricants have become harsh, better oil properties have begun to be required.
これによって、鉱油系列の油がいろいろな産業分野で広範囲に使用されているが、鉱油は生分解性が劣り、使用中の漏洩や使用後の廃棄時に提起される根本的な環境問題を有している。 As a result, mineral oils are widely used in various industrial fields, but mineral oils are inferior in biodegradability and have fundamental environmental problems raised during use and disposal after use. ing.
電気絶縁油は、各種電気機器が高電圧化及び大容量化する傾向に伴い、それに対応する性能が要求されており、その要求によって主に鉱油を基本にして各種の添加物が添加され、その要求条件に相応する絶縁油として開発使用されてきた。 As electrical insulation oil tends to have higher voltages and larger capacities of various electrical equipment, performance corresponding to it is required, and various additives are mainly added based on mineral oil according to the demand. It has been developed and used as an insulating oil that meets the requirements.
その例として、大韓民国特許公報公告番号特１９９４−０００３８０３号公報は、鉱油系絶縁油に二重結合を有する直鎖状炭化水素化合物、菜種油、エステル化合物の中から選択された化合物を添加して、絶縁破壊電圧特性が優秀な絶縁油を公開しており、日本国特公昭６３−４２８６号公報では、鉱油系絶縁油にフッ素系有機化合物を添加して、絶縁破壊電圧特性を向上させる技術を公開しており、同特開昭６９−８４７１４号公報では、鉱油に燐酸エステルの界面活性剤を添加する技術を公開している。 As an example, Korean Patent Gazette Publication No. 1994-0003803 adds a compound selected from a linear hydrocarbon compound having a double bond, a rapeseed oil and an ester compound to a mineral oil-based insulating oil, Insulating oil with excellent dielectric breakdown voltage characteristics is disclosed. Japanese Patent Publication No. 63-4286 discloses a technique for improving dielectric breakdown voltage characteristics by adding a fluorinated organic compound to mineral oil-based insulating oil. JP-A-69-84714 discloses a technique for adding a phosphate ester surfactant to mineral oil.
前述したように、鉱油を主原料とし、各種の添加剤を添加して絶縁破壊電圧特性などを向上させる技術の開発によって、鉱油系電気絶縁油の電気的特性に多くの発展がなされ、電気絶縁油の寿命延長などに多くの寄与があったが、電気絶縁油の場合、十分な使用後には変圧器などから劣化された電気絶縁油を回収し、回収された電気絶縁油を精製及び再生処理して新しい絶縁油と混用して使用したり廃棄しなければならない。 As described above, the development of technology that uses mineral oil as the main raw material and adds various additives to improve the dielectric breakdown voltage characteristics, etc., has led to many developments in the electrical characteristics of mineral oil-based electrical insulating oils. Although many contributions were made to extending the life of oil, in the case of electrical insulation oil, after sufficient use, the deteriorated electrical insulation oil is recovered from transformers, etc., and the recovered electrical insulation oil is purified and regenerated. It must be mixed with new insulating oil and discarded.
再生が不可能で廃棄される電気絶縁油の場合、添加剤として添加される抗酸化剤などのため容易に燃焼されず、また燃焼させる場合、ダイオキシンなどの公害物質が発生して環境汚染を起こすという問題があった。 In the case of electrical insulating oil that cannot be regenerated and discarded, it is not easily combusted due to antioxidants added as additives, and when it is combusted, pollutants such as dioxins are generated, causing environmental pollution There was a problem.
従って、近来は環境に親しい電気絶縁油の開発が要求されているのが実情であり、そのような要求に従い、米国特許第５，９５８，８５１号では、オレイン酸を含有する大豆油を主原料とし、これを水素化またはメチルエステル化して酸化防止剤を添加し、トランス油として用いる技術を公開している。 Therefore, in recent years, there is a demand for the development of environmentally friendly electrical insulating oils. In accordance with such demands, US Pat. No. 5,958,851 uses soybean oil containing oleic acid as the main raw material. And a technique for hydrogenating or methylesterifying it, adding an antioxidant and using it as a trans oil.
しかし、大豆油は、酸化安定性が低いという問題点と、低温で結晶が形成され、高温で固化が生じるという問題点を内包しており、実用的な適用が難しい点があるということを共に公開しているが、この発明は、大豆油などの植物油が電気絶縁油として代替可能であることを示してくれた効果があると言えるだろう。 However, soybean oil has both the problem of low oxidative stability and the problem that crystals are formed at low temperature and solidification occurs at high temperature. Although disclosed, it can be said that this invention has the effect of showing that vegetable oils such as soybean oil can be substituted as electrical insulating oils.
また、米国特許第５，９４９，０１７号では、７５％以上のオレイン酸トリグリセリドと炭素水１６ないし２２の不飽和脂肪酸、炭素水１６ないし２２の飽和脂肪酸及び抗酸化剤で構成される植物油を鉱油などと混合してトランス油として使用することを公開しており、このようなオレイン酸を含有する植物油としてひまわり油、オリーブ油、紅花油などを例に挙げている。 In US Pat. No. 5,949,017, vegetable oil composed of 75% or more oleic acid triglyceride, unsaturated fatty acid of carbon water 16-22, saturated fatty acid of carbon water 16-22 and antioxidant is used as mineral oil. As a vegetable oil containing oleic acid, sunflower oil, olive oil, safflower oil and the like are given as examples.
前記米国特許第５，９４９，０１７号で公知された絶縁油は、オレイン酸トリグリセリドのようなエステル化合物を含有しており、高温で水と接触する場合は、加水分解に対する安定性が落ちるという問題点を内包しており、価格が高いという問題があるが、植物油を鉱油などと混合して生分解性を向上させたという効果がある。 The insulating oil known in US Pat. No. 5,949,017 contains an ester compound such as oleic acid triglyceride, and has a problem that the stability to hydrolysis decreases when it comes into contact with water at a high temperature. Although it has a problem that it contains a point and is expensive, it has the effect of improving biodegradability by mixing vegetable oil with mineral oil.
しかし、高電圧の電気絶縁油については、まだ植物油だけで使用されていないのが現実で、植物油が電気絶縁油として高電圧に耐えるために、酸化安定性と低い流動点が確保される必要がある。 However, high-voltage electrical insulating oil is not yet used only with vegetable oil, and in order for vegetable oil to withstand high voltage as an electrical insulating oil, it is necessary to ensure oxidation stability and a low pour point. is there.
本発明は、電気絶縁油として使用されることのできる植物油の配合と化学反応によって、高い酸化安定性、高い絶縁破壊電圧と低い流動点を有する植物性絶縁油を製造して、親環境的な電気絶縁油を供給することを目的とする。 The present invention produces a vegetable insulating oil having a high oxidation stability, a high dielectric breakdown voltage and a low pour point by blending and chemical reaction of a vegetable oil that can be used as an electric insulating oil. The purpose is to supply electrical insulating oil.
前記の目的を達成するための本発明は、大豆油４０重量部ないし５０重量部と菜種油６０重量部ないし５０重量部でなった混合植物油を、アルミノケイ酸塩触媒存在下でエチルアルコールと反応させてエステル化させることを特徴とする植物性絶縁油の製造方法を提供することで達成されることができる。 In order to achieve the above object, the present invention comprises a reaction of a mixed vegetable oil comprising 40 to 50 parts by weight of soybean oil and 60 to 50 parts by weight of rapeseed oil with ethyl alcohol in the presence of an aluminosilicate catalyst. This can be achieved by providing a method for producing a vegetable insulating oil characterized by esterification.
前記で大豆油と菜種油を混合する理由は、大豆油だけを使用する場合、低温で結晶が生成される問題があり、高温では固化が生じるという問題があるだけでなく、酸化安定性にも問題があり、菜種油を混合することによって、低いヨード価と低い全酸価、低い流動点及び金属との相互安定性が優秀で、温度変化による粘度の変化を減らすことができるという利点があり、この時菜種油の含量を６０重量％以上にする場合は、安定性が落ちて容易に加水分解されて酸化され、非鉄金属を腐食させる原因となり、５０重量部以下で使用する場合は、流動点の上昇をもたらし、冬場の使用に問題があるだけでなく、流動点を低めるために流動点降下剤などを添加することになり、流動点降下剤の添加は、生分解性の低下につながるという問題があるので、混合植物油の配合比率は、大豆油４０重量部ないし５０重量部と菜種油６０重量部ないし５０重量部にするのが好ましい。 The reason why soybean oil and rapeseed oil are mixed as described above is that when only soybean oil is used, there is a problem that crystals are generated at a low temperature, and there is a problem that solidification occurs at a high temperature. By mixing rapeseed oil, there is the advantage that low iodine number and low total acid number, low pour point and mutual stability with metal are excellent, and change in viscosity due to temperature change can be reduced. When the rapeseed oil content is 60% by weight or more, the stability is lowered and it is easily hydrolyzed and oxidized, causing corrosion of non-ferrous metals. When used at 50 parts by weight or less, the pour point is increased. In addition to the problem of use in winter, pour point depressant is added to lower the pour point, and the addition of pour point depressant leads to a decrease in biodegradability. is there In, mixing ratio of the mixed vegetable oil, preferably soybean oil 40 parts by weight to 50 parts by weight of rapeseed oil 60 parts by weight to 50 parts by weight.
前記エステル化反応時に使用可能な触媒として、アルカリ触媒及びアルミノケイ酸塩系触媒が使用されることができ、好ましくは、ゼオライト触媒が使用される。 As a catalyst that can be used during the esterification reaction, an alkali catalyst and an aluminosilicate catalyst can be used, and a zeolite catalyst is preferably used.
前記でエステル化反応時の反応温度は、１４０℃ないし１７０℃にするのが好ましく、反応時間は３時間ないし５時間が良い。 The reaction temperature during the esterification reaction is preferably 140 ° C. to 170 ° C., and the reaction time is preferably 3 hours to 5 hours.
エチルアルコールとのエステル化反応で反応温度を１４０℃以下に進行する場合は、エステル化反応が完全に行われず、残留溶剤が植物油と混合された状態で存在することになるという問題が発生し、１７０℃を超過する温度でエステル化反応を進行させると、高温による製造物の色及び劣化による製造物の性状低下を起こすという問題を発生させることになるので、反応温度を１４０℃ないし１７０℃にするのが好ましい。 When the reaction temperature proceeds to 140 ° C. or lower in the esterification reaction with ethyl alcohol, the esterification reaction is not performed completely, and there is a problem that the residual solvent is present in a state mixed with vegetable oil. If the esterification reaction proceeds at a temperature exceeding 170 ° C, the color of the product due to high temperature and the problem of deterioration of the properties of the product due to deterioration may occur, so the reaction temperature is increased to 140 ° C to 170 ° C. It is preferable to do this.
また、このような温度条件下で反応時間を３時間以下で終了する場合は、低いエステル化によって反応が完全に行われず、流動点及び酸化安定性に問題があり、５時間を超過して反応させると、長時間の高温反応によって色及び製造物の性状低下を起こし、原価上昇の一要因として作用するので、３時間ないし５時間の範囲内で反応を終了させるのが好ましい。 In addition, when the reaction time is completed in 3 hours or less under such temperature conditions, the reaction is not completely performed due to low esterification, and there is a problem in the pour point and oxidation stability. In this case, the color and product properties are lowered by the high-temperature reaction for a long time, which acts as a factor of the cost increase. Therefore, the reaction is preferably terminated within the range of 3 hours to 5 hours.
通常のエステル化反応には、硫酸、塩酸などの酸触媒、または、水酸化ナトリウム、ナトリウムメトキシド、水酸化カリウムなどのアルカリ触媒が多く使用されているが、酸触媒の場合は、層分離現象を起こすことになり、界面で反応が起きることになるので、反応速度が遅く、反応を促進させるために激烈な攪拌と界外に水を除去しなければならないという煩わしさが伴い、アルカリ触媒を使用する場合は、比較的高い収率で得ることができ、安定して反応を進行させることができるが、植物油のアルカリによる鹸化のため、注意を傾けないと収率が低くなるという問題がある。 In ordinary esterification reactions, an acid catalyst such as sulfuric acid or hydrochloric acid, or an alkali catalyst such as sodium hydroxide, sodium methoxide, or potassium hydroxide is often used. Because the reaction occurs at the interface, the reaction rate is slow, and the use of an alkali catalyst is accompanied by intense stirring and the trouble of removing water outside the field to promote the reaction. In this case, a relatively high yield can be obtained and the reaction can proceed stably. However, because of the saponification of the vegetable oil with an alkali, there is a problem that the yield decreases unless care is taken.
しかし、本発明で使用されるアルミノケイ酸塩系触媒の場合は、層分離現象及び鹸化などが起こらないため、高い収率による反応物を得られるという長所と共に、反応後生成物から触媒の除去が容易になるという長所があり、このような系統の化合物として、ゼオライト、ベントナイトなどを使用することができる。 However, in the case of the aluminosilicate catalyst used in the present invention, since the layer separation phenomenon and saponification do not occur, the catalyst can be removed from the product after the reaction, with the advantage that the reaction product can be obtained in a high yield. There is an advantage that it becomes easy, and zeolite, bentonite and the like can be used as compounds of such a system.
植物油とエステルを形成するために多様な種類のアルコールを使用することができるが、粘度流動点、全酸価などを鑑みると、エチルアルコールを使用するのが好ましい。 Various types of alcohol can be used to form an ester with the vegetable oil, but it is preferable to use ethyl alcohol in view of viscosity pour point, total acid value, and the like.
＜実施例１＞ <Example 1>
大豆油と菜種油を表１に示すように混合し、混合植物油に対する粘度（KS M 2014による）、流動点（KS M 2016による）、引火点（KS M 2010による）を測定し、表１に示した。
前記表１から、大豆油と菜種油の混合比率で、菜種油の重量比を相対的に高く設定する場合は、粘度は上昇しているが、流動点と引火点が低くなり、菜種油の重量比を低く設定する場合は、反対に粘度は低くなり、流動点と引火点は上昇していることを確認することができる。 From Table 1 above, when the weight ratio of rapeseed oil is set relatively high in the mixing ratio of soybean oil and rapeseed oil, the viscosity is increased, but the pour point and flash point are lowered, and the weight ratio of rapeseed oil is On the other hand, when it is set low, the viscosity becomes low, and it can be confirmed that the pour point and the flash point are increased.
混合植物油の流動点の上昇は、エステル化反応後、流動点の上昇を加速化させることになり、冬場の使用の問題、流動点を低めるための降下剤の添加及び流動点降下剤の添加による生分解性の低下の問題が発生する可能性が高く、また、引火点を考慮するなら、混合比率を大豆油４０重量部ないし５０重量部と菜種油６０重量部ないし５０重量部の配合比に設定するのが好ましいことが分かる。
＜実施例２＞
The rise of the pour point of mixed vegetable oil will accelerate the rise of the pour point after the esterification reaction, which is due to the problems of use in winter, the addition of a depressant to lower the pour point and the addition of the pour point depressant. There is a high possibility that the problem of biodegradability will decrease, and if the flash point is taken into consideration, the mixing ratio is set to 40 to 50 parts by weight of soybean oil and 60 to 50 parts by weight of rapeseed oil It can be seen that this is preferable.
<Example 2>
実施例１から得られたデータを根拠に、最も良い結果をもたらす大豆油４０重量部と菜種油６０重量部で混合された混合植物油１００重量部に対して、ゼオライト触媒０．４重量部を添加し、アルコールを表２のような条件で反応容器に入れ、１７０℃で４００ｒｐｍの速度で攪拌しながら５時間にわたってエステル化反応させた後、実施例１と同一な方法で粘度と流動点を測定し、下記の方法で全酸価をKS M 2004に従い測定し、その結果を表２に示した。
前記表２から確認されるように、エステル化反応の結果、エチルアルコールの場合が最も低い粘度と流動点と全酸価を示していることを確認することができ、アルコールの使用量に関連しても、エチルアルコールの場合が粘度、流動点及び全酸価で安定的な結果を示していることを確認することができる。
＜実施例３＞
As can be seen from Table 2 above, as a result of the esterification reaction, it can be confirmed that ethyl alcohol shows the lowest viscosity, pour point and total acid value, and is related to the amount of alcohol used. However, it can be confirmed that ethyl alcohol shows stable results in terms of viscosity, pour point and total acid number.
<Example 3>
前記実施例１及び実施例２の結果に基づいて、大豆油と菜種油の混合比率及び触媒を表３のようにし、エチルアルコールを混合植物油１００重量部に対して１０重量部添加し、１７０℃で５時間の間反応させて製造された絶縁油に対して、流動点、引火点及び全酸価を実施例１及び実施例２での方法と同一な方法で測定し、その結果を表３に示した。
前記表３から確認されるように、触媒量の増加によって流動点が低くなり、引火点が高くなり、全酸価が減るという点を発見することができて、触媒の添加がエステル化反応に相当なる影響を及ぼしていることを確認することができ、無添加である場合は、全酸価が０．１０２mgKOH/g、０．１１０mgKOH/g及び０．１１５mgKOH/gと相当高く現れており、このような高い全酸価は、変圧器の投入使用時、早期にスラッジを生成させ、電気絶縁油の抵抗率の低下と共に変圧器の損傷が生じる原因となり、電気絶縁油の生命である絶縁能力の低下問題を発生させるので、触媒の存在下に反応させるのが好ましいということが確認できる。
＜実施例４＞
As can be seen from Table 3, it can be found that increasing the amount of catalyst lowers the pour point, raises the flash point, and reduces the total acid value. It can be confirmed that it has a considerable influence, and when it is not added, the total acid value appears to be quite high as 0.102 mgKOH / g, 0.110 mgKOH / g and 0.115 mgKOH / g, Such a high total acid value generates sludge early when the transformer is used, causing damage to the transformer along with a decrease in the resistivity of the electrical insulating oil, and the insulation capacity that is the life of the electrical insulating oil It can be confirmed that the reaction is preferably performed in the presence of a catalyst.
<Example 4>
大豆油４０重量部と菜種油６０重量部でなった混合植物油に、ゼオライト触媒を混合植物油１００重量部に対して０．４重量部とになるように添加し、添加されるエチルアルコールの量を表４のように変化させながら、１７０℃で５時間にわたってエステル化反応を進行させた後、引火点、流動点及び全酸価を前述した実施例のような方法で測定し、その結果を表４に示した。
前記表４から確認されるように、エチルアルコールの添加量が３重量部未満である場合、引火点については問題がないが、高い流動点による添加剤投入量過多による生分解性の低下が発生し、また、全酸価も上昇し、電気絶縁油の生命である絶縁能力が低下するという問題を起こす可能性があるので、５重量部以上添加するのが好ましいが、１５重量部以上添加する場合は、引火点、流動点及び全酸価に大きな変化がないので、しいて過量に添加する必要はなく、かえって未反応のエチルアルコールを除去しなければならないという不便が伴うことになる。
＜実施例５＞
As can be seen from Table 4 above, when the amount of ethyl alcohol added is less than 3 parts by weight, there is no problem with the flash point, but the biodegradability decreases due to the excessive amount of additive added due to the high pour point. In addition, since the total acid value also rises and there is a possibility that the insulation ability that is the life of the electrical insulating oil is lowered, it is preferable to add 5 parts by weight or more, but 15 parts by weight or more is added. In this case, there is no significant change in the flash point, pour point and total acid value, so there is no need to add an excessive amount, but there is an inconvenience that unreacted ethyl alcohol must be removed.
<Example 5>
大豆油４５重量部と菜種油５５重量部でなった混合植物油１００重量部に対して、ゼオライト触媒０．４重量部とエチルアルコールの添加量と反応温度を下記の表５のように変化させながら、５時間の間エステル化反応を進行させた後、引火点、流動点及び全酸価を前述した実施例のような方法で測定し、その結果を表５に示した。
表５で確認されるように、反応温度が１３０℃である場合は、引火点が著しく低く、流動点と全酸価が高くあらわれた点から、十分な反応が行われなかったことを確認することができ、反応温度が１８０℃である場合は、全酸価が０．０８３mgKOH/g、０．０８９mgKOH/gに上昇することを確認することができ、全酸価の上昇は、絶縁能力の低下と直接的な関連を有することになるので、本発明の範囲である１４０℃ないし１７０℃にエステル反応温度を設定するのが好ましい。 As confirmed in Table 5, when the reaction temperature is 130 ° C., the flash point is remarkably low, and from the point that the pour point and the total acid value appear high, it is confirmed that sufficient reaction has not been performed. When the reaction temperature is 180 ° C., it can be confirmed that the total acid number increases to 0.083 mg KOH / g and 0.089 mg KOH / g. It is preferable to set the ester reaction temperature to 140 ° C. to 170 ° C., which is the range of the present invention, since it has a direct relationship with the decrease.
前記実施例１ないし実施例５の結果から確認されるように、大豆油と菜種油の配合比率は４０ないし５０重量部：６０ないし５０重量部の比率で混合されるのが好ましいことが分かり、植物油の混合物とエステル化反応に使用されるアルコールとしては、エチルアルコールが混合植物油１００重量部に対して５重量部ないし２０重量部の範囲で使用されるのが好ましく、エステル化反応触媒としては、アルミノケイ酸塩系の触媒であるゼオライトが混合植物油１００重量部に対して０．２重量部ないし０．６重量部使用されるのが好ましく、反応温度においては、１４０℃ないし１７０℃が適当なものであることを確認することができた。 As confirmed from the results of Examples 1 to 5, it was found that the blending ratio of soybean oil and rapeseed oil is preferably 40 to 50 parts by weight: 60 to 50 parts by weight. As the alcohol used in the esterification reaction with a mixture of the above, ethyl alcohol is preferably used in the range of 5 to 20 parts by weight with respect to 100 parts by weight of the mixed vegetable oil. It is preferable to use 0.2 to 0.6 parts by weight of zeolite which is an acid-based catalyst with respect to 100 parts by weight of mixed vegetable oil, and a reaction temperature of 140 to 170 ° C. is appropriate. I was able to confirm that there was.
前記で確認されたように、本発明による電気絶縁油は、混合植物油をエステル化して製造されたもので、電気絶縁油として高い引火点と低い全酸価を維持しているだけでなく、適当な粘度を維持でき、変圧器などの電気絶縁油として効果的に使用できるが、一般的に、植物油は、酸化安定性が鉱油に比べて劣るので、電気絶縁油に添加されるブチル化ヒドロキシトルエン（Buthylated hydroxytoluene;BHT）、ターシャリーブチルヒドロキノン（Tertiary Buthylhydroquinone;TBHQ）などの酸化安定剤を通常的に添加される量添加すれば、酸化安定性が補強され、電気絶縁油としてより長期間使用することもできる。
＜実験例＞ 絶縁破壊電圧
As confirmed above, the electrical insulating oil according to the present invention is produced by esterifying a mixed vegetable oil, which not only maintains a high flash point and a low total acid number as an electrical insulating oil, but is also suitable. However, vegetable oil is generally inferior to mineral oil in terms of oxidation stability, so that butylated hydroxytoluene added to the electrical insulating oil can be maintained. (Buthylated hydroxytoluene; BHT), Tertiary Buthylhydroquinone (TBHQ) and other oxidation stabilizers can be added to increase oxidation stability and use for longer periods as electrical insulating oil You can also.
<Experimental example> Dielectric breakdown voltage
大豆油４０重量部と菜種油６０重量部でなった混合植物油１００重量部に対して、ゼオライト触媒０．４重量部とエチルアルコールの添加量を１０重量部にし、最適の反応温度である１４０℃から１７０℃まで変化させながら、５時間の間エステル化反応を進行させた後、KS C ISO 60156に基づき絶縁破壊電圧を測定し、その結果を表６に示した。
前記表６から確認されるように、本発明の方法によって製造された植物性絶縁油の絶縁破壊電圧は、７３KVないし８０KVを示しており、これは韓国工業規格で定めている鉱油系電気絶縁油規格である１種２号、１種４号絶縁油の絶縁破壊電圧である３０KV、４０KVを遥かに上回っていることが分かる。
＜実験例＞ 生分解性試験
As can be seen from Table 6, the dielectric breakdown voltage of the plant insulating oil produced by the method of the present invention is 73 KV to 80 KV, which is a mineral oil-based electric insulating oil defined by Korean Industrial Standards. It can be seen that it is far higher than the standard breakdown voltage 30 KV and 40 KV of Type 1 No. 2 and Type 1 No. 4 insulating oil.
<Experimental example> Biodegradability test
植物性絶縁油の生分解性試験は、アメリカの環境庁試験法（EPA OPPTS 835.3100）で提示した装置と方法を利用して実施した。
まず三つのフラスコに各々絶縁油の生分解性実験のために接種液１００MLにテスト試薬１、テスト試薬２及びテスト試薬３を各々１MLずつ含有する脱イオン水（deionized water）９００MLを混合して製造された試験培養液を入れて１Lに調節し、１４日間放置した後、ここに試験資料として実施例５から得た結果を土台に、大豆油４５重量部と菜種油５５重量部でなった混合植物油１００重量部に対して、ゼオライト触媒０．４重量部とエチルアルコールの１０重量部を添加し、１７０℃で５時間の間エステル化反応を進行させて製造した植物性絶縁油を使用した。
The biodegradability test of the vegetable insulating oil was carried out by using the apparatus and method presented in the American Environmental Agency test method (EPA OPPTS 835.3100).
First, in order to test the biodegradability of insulating oil in each of three flasks, inoculum 100ML is mixed with 900ml of deionized water (deionized water) containing 1ml each of test reagent 1, test reagent 2 and test reagent 3. The test culture broth was added, adjusted to 1 L, allowed to stand for 14 days, and then mixed vegetable oil consisting of 45 parts by weight soybean oil and 55 parts by weight rapeseed oil based on the results obtained from Example 5 as test data. A vegetable insulating oil produced by adding 0.4 parts by weight of a zeolite catalyst and 10 parts by weight of ethyl alcohol to 100 parts by weight and allowing the esterification reaction to proceed at 170 ° C. for 5 hours was used.
生分解性試験では、０．２ノルマル濃度の水酸化バリウム溶液１０ccを入れた中間容器を設置した三角フラスコを使用したが、三つのフラスコに前記試験培養液を入れた後、これらに植物性絶縁油１５３MLを投入したもの（試験区）と、クエン酸ナトリウム３５．８mg添加したもの（対照区）及び何も添加していないもの（無添加区）に各々製造した。 In the biodegradability test, an Erlenmeyer flask equipped with an intermediate container containing 10 cc of a 0.2 normal concentration barium hydroxide solution was used. After the test culture solution was put into three flasks, plant insulation was added thereto. Oil 153ML was added (test group), sodium citrate added 35.8 mg (control group) and nothing added (non-added group).
各フラスコにCO２を含有しない空気（CO２ free air）でパージ（Purge）して密封処理した後、攪拌器に入れて２５℃、１２５RPMで攪拌しながら３０日から４５日間生分解されるようにした。 Each flask was purged with CO2 free air (CO2 free air) and sealed, and then placed in a stirrer and allowed to biodegrade for 30 to 45 days with stirring at 25 ° C and 125 RPM. .
生分解期間中一定時間間隔に各フラスコの中間容器に入っている水酸化バリウム溶液１０MLを採取した後、ここに脱イオン水１０MLとフェノールフタレイン０．２MLを添加した後、０．１N HCIに滴定し、下記の数学式を利用して発生されたCO２量を算出し、表７に示した。
After collecting 10 ml of barium hydroxide solution contained in the intermediate container of each flask at a certain time interval during the biodegradation period, 10 ml of deionized water and 0.2 ml of phenolphthalein were added thereto, and then 0.1N HCI was added. Titration was performed, and the amount of CO 2 generated was calculated using the following mathematical formula.
前記数学式１で、TFは試験区または対照区のBa（OH）２の滴定に使用された０．１N HCIのMLを意味し、CFは無添加区のBa（OH）２の滴定に使用された０．１N HCIのMLを意味する。
前記表７で時間の流れによってCO２の発生量が増加して３０日が経過した場合は、製造された植物性絶縁油を入れた試験区から、理論的CO２発生量の９６．４％が発生されるのが確認されたが、標準試料であるクエン酸ナトリウムから発生された６４．８％より遥かに多い量で、製造された植物性絶縁油の生分解性が優秀であることを見せている。 In Table 7, when 30 days have passed since the amount of CO2 generated increased with the passage of time, 96.4% of the theoretical amount of CO2 generated was generated from the test plot containing the plant insulation oil produced. It was confirmed that the biodegradability of the plant insulating oil produced was much better than 64.8% generated from the standard sample sodium citrate. Yes.
ここで、生分解性実験に使用された各種溶液は、次のような方法によって製造されたものである。
＜接種液の製造＞
Here, the various solutions used for the biodegradability experiment were manufactured by the following methods.
<Manufacture of inoculum>
下水終末処理場から入手した活性汚泥液２５MLと京畿道ヨジュ市野山、江原道平沢市野山及び安山市半月公団で地表面から２０cmの深さに存在する土壌を採取して均等に混合した後、直径５mmのふるいにかけ、その中１gを取って脱イオン水１Lと混合してろ過したろ過液を三角フラスコに入れ、上部入口を塞いだ状態で２５℃で１４日間順応期間を経た後使用した。
＜テスト試薬の製造＞
After collecting and mixing evenly the soil that is present at a depth of 20cm from the ground surface at 25ml of activated sludge obtained from the sewage sewage treatment plant and Nosan, Yeosu City, Gangwon Province The filtrate was filtered through a sieve with a diameter of 5 mm, 1 g of which was mixed with 1 L of deionized water, put into an Erlenmeyer flask, and used after passing through an acclimatization period at 25 ° C. for 14 days with the upper inlet closed. .
<Manufacture of test reagents>
テスト試薬１の製造；NH４Cl ３５g、KNO３ １５g、K２HPO４３H２O ７５g、NaH２PO４H２O ２５gを蒸留水に入れて１Lにする。 Preparation of test reagent 1: NH4Cl 35g, KNO3 15g, K2HPO43H2O 75g, NaH2PO4H2O 25g are put into distilled water to make 1L.
テスト試薬２の製造；KCｌ １０g、MgSO４ ２０g、FeSO４７H２O １gを蒸留水に入れて１Lにする。 Preparation of test reagent 2: KCl 10g, MgSO4 20g, FeSO47H2O 1g are put in distilled water to 1L.
テスト試薬３の製造；CaCl２ ５g、ZnCl２ ０.０５g、MnCl２４H２O ０.５g、CuCl２ ０.０５g、CoCl２ ０.００１g、H３BO３ ０.００１g、MoO３ ０.００４gを蒸留水に入れて１Lにする。 Preparation of test reagent 3: CaCl2 5g, ZnCl2 0.05g, MnCl24H2O 0.5g, CuCl2 0.05g, CoCl2 0.001g, H3BO3 0.001g, MoO3 0.004g are made up to 1L.
前記で見たように、本発明の方法によって製造された電気絶縁油は、自然状態で自然界に存在する微生物によって容易に分解されることができるので、漏出または廃棄時微生物による分解が容易で、絶縁破壊電圧、引火点、酸化安定性などが優秀で電気的劣化にも優秀な結果を示しており、変圧器などの電気絶縁油として優秀な発明だといえる。 As seen above, the electrical insulating oil produced by the method of the present invention can be easily decomposed by microorganisms existing in nature in the natural state, so that it is easily decomposed by microorganisms at the time of leakage or disposal, The dielectric breakdown voltage, flash point, oxidation stability, etc. are excellent, and it shows excellent results in electrical degradation. It can be said that this is an excellent invention as an electrical insulating oil for transformers.
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| KR10-2006-0040064 | 2006-05-03 | ||
| KR1020060040064A KR100705296B1 (en) | 2006-05-03 | 2006-05-03 | Manufacturing method of insulating oil used vegetable oil and the isolating oil by the method |
| PCT/KR2007/001142 WO2007126207A1 (en) | 2006-05-03 | 2007-03-08 | Vegetable-based electric insulation oil and preparation thereof |
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| EP2042588A1 (en) * | 2007-09-21 | 2009-04-01 | Universita'degli Studi Di Milano | Process for the esterification and transesterification of fats |
| KR101384267B1 (en) | 2007-11-26 | 2014-04-11 | 에스케이종합화학 주식회사 | Vegetable insulating oil composition |
| JP5532562B2 (en) * | 2008-09-02 | 2014-06-25 | 株式会社明電舎 | Insulating polymer material composition |
| KR101451289B1 (en) * | 2012-05-03 | 2014-10-17 | 한국생산기술연구원 | Enviromentally affinitive vegetable insulating oil composition |
| 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 |
| KR101411026B1 (en) * | 2012-12-12 | 2014-06-25 | 주식회사 지코스 | Vegetable oil based insulation oil |
| JP6166092B2 (en) * | 2013-04-19 | 2017-07-19 | 愛知電機株式会社 | Degradation diagnosis method for vegetable insulating oil |
| KR101636742B1 (en) * | 2014-04-30 | 2016-07-07 | 한국생산기술연구원 | Vegetable dialectic fluid, method therof and electric power machine comprising the same |
| CN113671326B (en) * | 2021-08-23 | 2023-11-28 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Insulation oil low-temperature breakdown test method for oil immersed current transformer |
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| JPH06313188A (en) * | 1993-04-28 | 1994-11-08 | Kao Corp | Production of fatty acid ester |
| US6398986B1 (en) * | 1995-12-21 | 2002-06-04 | Cooper Industries, Inc | Food grade vegetable oil based dielectric fluid and methods of using same |
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| JP3145301B2 (en) * | 1996-03-21 | 2001-03-12 | 株式会社関西テック | Electrical insulating oil and method for producing the same |
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