菜籽绝缘油的精炼及其水解动力学特性的研究
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摘要
矿物油具有良好的冷却性能、电气绝缘以及低廉的成本,在油浸绝缘高电压设备中已经有一个多世纪的应用历史,但是其燃点、闪点低,不能满足高防火性能的要求,并且难以生物降解,一旦泄漏就会造成污染。因此,研究耐高温、高介电常数、可生物降解且成本适中的植物绝缘油成为国内外关注的热点课题;植物油的闪点普遍高于300℃,满足难燃油的要求,生物降解率大于97%,即使发生泄漏也不会对水源、居住环境等造成污染,在兼顾成本、生物降解性和原料来源等方面都占有优势,因此在利用基因技术研究高产、高品质植物油料作物取得突破和石油枯竭的新形势下,它将很有潜力成为矿物油的绿色替代品。
本文在对国内外植物绝缘油研究现状总结分析的基础上,探索了将菜籽油提炼为绝缘油的精炼工艺和方法,通过试验研究了精炼后菜籽绝缘油的各项理化、电气性能及其用作绝缘油的优缺点;系统测定了在不同温度、时间和水油比条件下的水解动力学数据,使用Arrhenius公式作为表征总反应实验速率系数与反应温度关系的经验定律;并进一步测试了菜籽绝缘油在不同水解程度下的工频击穿电压、介频电谱及体积电阻率等介电性能,以考核它能否作为液体绝缘材料,为菜籽油用作基础油的液体绝缘介质的开发奠定了基础,填补了国内在植物绝缘油研究上的空白。
研究发现,在选择基础油时,从植物油的化学组成和分子结构出发,以油酸含量高的菜籽油为最佳。通过对菜籽油精炼步骤中主要试验条件的控制,可将菜籽油的酸值控制在0.03mgKOH·g-1以下,击穿电压达到60kV以上,其理化及电气性能均达到GB2536-90《变压器油》的要求。实验数据显示,在10-2～106Hz的试验频率范围内,在不同水解程度下精炼后的菜籽绝缘油的介电常数、介质损耗、体积电阻率均随频率的升高而降低,其电气性能均发生了规律性的变化,对绝缘性能产生了不同程度的影响,本文从分子结构和电场作用的角度分析了在水解过程中其各项介电性能变化的机理,为进一步探讨植物绝缘油在变压器运行中的老化问题提供基本依据。
Mineral insulating oil has excellent high coolant capability and electric insulating property and low cost,it has played important roles in oil-immersed high voltage equipment more than a century. But its burning and flash points are too low to satisfy the requirement of fireproofing. At the same time,it is poorly biodegradable and may contaminate soil and resident conditions when serious oil leakage occurs. Therefore research of the environment-friendly vegetable insulating oil with high flash point and high biodegradable percent has become a pop project;Flash point of vegetable insulating oil is higher than 300℃, it is a fire resistant oil;its biodegradable percent is larger than 97%,it will not pollute the water and inhabited area. Nowadays,the output and quality of oil corps are improved by using gene techniques,and the reserves of mineral oil become decreased,so vegetable insulating oil could be the green substitute as mineral oil.
In this paper, the domestic and overseas research situation of vegetable insulating oil was summarized and analyzed; explored the methods how to refine the vegetable oil to dielectric liquid;based on the test researching results,the advantage and disadvantage of rape-seed oil for using as insulating oil was also researched. The hydrolysis dynamic of rape-seed insulation oil was systematically studied at different temperatures,reaction times and water-oil ratio,The variation between the hydrolysis degree of insulating oil and reaction temperature was determined using the Arrhenius Empirical equation;and the series dielectric properties of vegetable insulating oil under different hydrolysis degree was tested : AC-breakdown voltage , relative permittivity and dielectric dissipation. This paper is the groundwork of using rape-seed oil as dielectric liquid and filled up the blank of vegetable insulating oil studies in domestic study.
The investigation shows,according to the chemical composition and molecular structure of vegetable oil,rape-seed oil high in oleic acid is the best choice as base oil. Controlling the dominating testing conditions in vegetable oil refined processes, and using repeated refined method, the acid value of vegetable oil can be limited under 0.03mgKOH·g-1,the AC-breakdown voltage has reached more than 60kV,and the physical,chemical and electrical properties of vegetable oil met the requirements of standard GB2536-90.From the experiment data,the electrical properties of refined insulating oil changed regularly under different hydrolysis degree,insulating properties were influenced inordinately. According to the chemical molecular structure and the influence of electric field,the mechanism of the change of electrical properties are analyzed,and they provide experiment basis for the ageing problems of vegetable insulating oil in transformer operation.
本文在对国内外植物绝缘油研究现状总结分析的基础上,探索了将菜籽油提炼为绝缘油的精炼工艺和方法,通过试验研究了精炼后菜籽绝缘油的各项理化、电气性能及其用作绝缘油的优缺点;系统测定了在不同温度、时间和水油比条件下的水解动力学数据,使用Arrhenius公式作为表征总反应实验速率系数与反应温度关系的经验定律;并进一步测试了菜籽绝缘油在不同水解程度下的工频击穿电压、介频电谱及体积电阻率等介电性能,以考核它能否作为液体绝缘材料,为菜籽油用作基础油的液体绝缘介质的开发奠定了基础,填补了国内在植物绝缘油研究上的空白。
研究发现,在选择基础油时,从植物油的化学组成和分子结构出发,以油酸含量高的菜籽油为最佳。通过对菜籽油精炼步骤中主要试验条件的控制,可将菜籽油的酸值控制在0.03mgKOH·g-1以下,击穿电压达到60kV以上,其理化及电气性能均达到GB2536-90《变压器油》的要求。实验数据显示,在10-2～106Hz的试验频率范围内,在不同水解程度下精炼后的菜籽绝缘油的介电常数、介质损耗、体积电阻率均随频率的升高而降低,其电气性能均发生了规律性的变化,对绝缘性能产生了不同程度的影响,本文从分子结构和电场作用的角度分析了在水解过程中其各项介电性能变化的机理,为进一步探讨植物绝缘油在变压器运行中的老化问题提供基本依据。
Mineral insulating oil has excellent high coolant capability and electric insulating property and low cost,it has played important roles in oil-immersed high voltage equipment more than a century. But its burning and flash points are too low to satisfy the requirement of fireproofing. At the same time,it is poorly biodegradable and may contaminate soil and resident conditions when serious oil leakage occurs. Therefore research of the environment-friendly vegetable insulating oil with high flash point and high biodegradable percent has become a pop project;Flash point of vegetable insulating oil is higher than 300℃, it is a fire resistant oil;its biodegradable percent is larger than 97%,it will not pollute the water and inhabited area. Nowadays,the output and quality of oil corps are improved by using gene techniques,and the reserves of mineral oil become decreased,so vegetable insulating oil could be the green substitute as mineral oil.
In this paper, the domestic and overseas research situation of vegetable insulating oil was summarized and analyzed; explored the methods how to refine the vegetable oil to dielectric liquid;based on the test researching results,the advantage and disadvantage of rape-seed oil for using as insulating oil was also researched. The hydrolysis dynamic of rape-seed insulation oil was systematically studied at different temperatures,reaction times and water-oil ratio,The variation between the hydrolysis degree of insulating oil and reaction temperature was determined using the Arrhenius Empirical equation;and the series dielectric properties of vegetable insulating oil under different hydrolysis degree was tested : AC-breakdown voltage , relative permittivity and dielectric dissipation. This paper is the groundwork of using rape-seed oil as dielectric liquid and filled up the blank of vegetable insulating oil studies in domestic study.
The investigation shows,according to the chemical composition and molecular structure of vegetable oil,rape-seed oil high in oleic acid is the best choice as base oil. Controlling the dominating testing conditions in vegetable oil refined processes, and using repeated refined method, the acid value of vegetable oil can be limited under 0.03mgKOH·g-1,the AC-breakdown voltage has reached more than 60kV,and the physical,chemical and electrical properties of vegetable oil met the requirements of standard GB2536-90
引文
[1]李新森.电力用油[M].北京:中国石化出版社, 1988, pp5-8.
[2]王继龙,衣家文.变压器油的选择[J].变压器. 2005, Vol.42, No.4,pp 27-28.
[3] IEC296-1991(修订版) [S].英国BS148-1998规格标准,变压器油标准.
[4]贺以燕,郭振岩,赵良云.不燃油与难燃油及其变压器的发展[J].变压器. 2000, No.08.
[5]李晓峰.一种新型高燃点绝缘液体-R-TEMP油[J].变压器. 1995, No.02.
[6]田雷,白云玲,钟建江.微生物降解有机污染物的研究进展[J].工业微生物. 2000, Vol.30, No.2, pp46-50.
[7] T.V. Oommen, C.C. Claiborne, J.T.Mullen. Biodegradable electrical insulation fluids [J]. Proceedings of Electrical Insulation Conference, Sep 1997, pp465-468.
[8] T.V. Oommen. Vegetable oils for liquid filled transformers [J]. IEEE Electrical Insulation Magazine, 2002, Vol18, No.1 pp6-11.
[9] C. P McShane. Natural and synthetic ester dielectric fluid: their relative environ -mental, fire safety, and electrical performance [J]. Industrial and Commercial Power Systems Technical Conference, May 1999, pp1-8.
[10] [日]速水敏幸.电力设备的绝缘诊断[M].北京:科学出版社, 2003, pp155-161.
[11] C. P McShane. Relative properties of the new combustion resistant vegetable oil based dielectric coolants [J]. IEEE Transactions on Industry Applications, 2002, Vol37, No.4, pp1132-1139.
[12]王树森.变压器绝缘材料[J].变压器. 2005, Vol.42, No.4pp31-32.
[13] Bertrand Y, Hoang L.C. Vegetal oils as substitute for mineral oils [J]. Proceedings of the 7th International Conference on Properties and Applications of Dielectric Materials, June 2003, Vol.2, pp491 - 494 vol.2.
[14] Mcshane C P. Relative properties of the new combustion resistant vegetable oil based dielectric coolants [J].2000.
[15]贺以燕,郭振岩,赵良云.不燃油与难燃油及其变压器的发展[J].变压器. 2000, Vol37, No.8, pp4-7.
[16]刘玉兰.植物油脂生产与综合利用[M].北京:中国轻工业出版社, 1999.
[17] P.Boss, T.V. Oommen. New insulating fluids for transformers based on biodegradable high oleic vegetable oil and ester fluid [J]. IEE Colloquium on Insulating Liquids. May 1999, Vol.7, pp1-10.
[18] Oommen T V. Vegetable oils for liquid-filled transformers [J]. Electrical Insulation Magazine,IEEE Electrical Insulation Magazine, IEEE. 2002, Vol.18, No.1: pp6-11.
[19] Oommen T V, Claiborne C C, Walsh E J etal. A new vegetable oil based transformer fluid: development and verification [J]. 2000, Vol.1,pp308-312.
[20] Mcshane C P, Corkran J L, Rapp K J etal. Aging of paper insulation retrofilled with natural ester dielectric fluid [J]. 2003.
[21]日本开发出用植物油做绝缘油的变压器[J].东北电力技术. 2002,No.8, pp13.
[22] United States Patent. Electrical transformers containing electrical insulation fluids comprising high oleic acid oil compositions [J]. Patent Number: 5949017, Sep 1999.
[23] United States Patent. Soybean based transformer oil and transmission line fluid [J]. Patent Number: 5958851, Sep 1999.
[24] Mcshane C P, Rapp K J, Corkran J L etal. Aging of paper insulation in natural ester dielectric fluid [J]. 2001.
[25] Mcshane C P, Rapp K J, Corkran J L etal. Aging of Kraft paper in natural ester dielectric fluid [J]. 2002.
[26] Mcshane C P. Relative properties of the new combustion-resist egetable-oil-based dielectric coolants for distribution and power ransformers [J]. Industry Applications, IEEE Transactions on Industry Applications, IEEE Transactions on. 2001, Vol.37, No.4: pp1132-1139.
[27] Badent R, Hemmer M, Schwab A J. Inhibited rape-seed oil as substitute for mineral oils [J]. 2002
[28] Badent R, Hemmer M, Konekamp U etal. Streamer inception field strengths in rape-seed oils [J]. 2000.
[29] Badent R, Kist K, Schwab A J. Rape-seed oil-a substitute for mineral oil? [J]. 1999.
[34]毕艳兰.油脂化学[M].北京:化学工业出版社, 2005, pp22.
[35]陈洁.油脂化学[M].北京:化学工业出版社, 2004, pp17.
[36]伍越寰,李伟昶,沈晓明.有机化学[M].安徽:中国科学技术大学出版社. 2002,pp623-626.
[37] [美]斯沃恩,秦洪万译.贝雷油脂化学与工艺学[M].北京:中国轻工业出版社,1989.
[38]倪培德.油脂加工技术[M].北京:化学工业出版社, 2003.
[39]何东平.油脂精炼与加工工艺学[M].北京:化学工业出版社, 2005, pp40-67.
[40]马传国.油脂加工工艺与设备[M].北京:化学工业出版社, 2004, pp25-36.
[41]彭阳生.植物油脂加工实用技术[M].北京:金盾出版社, 2003, pp280-293.
[42] GB5530-1998《动植物油脂酸价和酸度测定》[S].
[43]宋华,陈颖.化工分离工程[M].哈尔滨:哈尔滨工业大学出版, 2003, pp201-217.
[44] [苏]H.C.阿鲁楚尼亚恩.油脂加工工艺[M].北京:化学工业出版社, 1990.
[45] [美]R.W.约翰逊, E.弗里兹编,陆用海,胡征宇主译.工业脂肪酸及其应用[M].北京:中国轻工业出版社, 1992.
[46]汪德生,张洪林,蒋林时等.高效活性白土制备和工艺改进[J].非金属矿. 2004, No.04.
[47]吕宪俊,崔学奇,刘晓东.高效活性白土的制备及其活化机理研究[J].中国非金属矿工业导刊. 2003, No.04.
[48]曹明礼,张凌燕,荣葵一.膨润土制备高效活性白土的研究[J].化工矿物与加工. 2000, No.02.
[49]杨虎,刘琼荪,钟波.数理统计[M].北京:高等教育出版社, 2004, pp168-178.
[50]刘玉兰.植物油脂生产与综合利用[M].北京:中国轻工业出版社, 1999.
[51]兰州大学复旦大学化学系有机教研室.有机化学实验[M].北京:高等教育出版社,1999.
[52]刘炳尧.电气设备绝缘试验[J].北京:水利电力出版社, 1993.
[53] GB5525《植物油脂检验透明度、色泽、气味、滋味鉴定法》[S].
[54] DL420-91《电气绝缘液体的折射率和比色散试验方法》[S].
[55] DL420.3-91《水溶性酸测定法》[S].
[56]孙辉,吕秀阳,陈良.不同植物油脂在近临界水中水解反应动力学的比较[J].化工学报.2007, No.04.
[57] Holliday RL,King JW,List GR. Hydrolysis of vegetable oils in sub-and supercritical water [J]. Industrial Engineering Chemical Research 1997; 36 (3): 932- 935.
[58] Mcshane CP. Relative properties of the new combustion-resistant vegetable-oil-based dielectric coolants for distribution and power transformers [J]. IEEE Transactions on Industry Applications 2001; 37 (4):1132-1139.
[59] Moore HR. Requirements and expectations of natural ester fluids for application in power transformers [J]. IEEE Transmission and distribution conference and exhibition 2005/2006 PES May 21-24, 2006:3-24.
[60] Moquin PHL,Temelli F. Kinetic modeling of hydrolysis of canola oil in supercritical media [J]. Journal of Supercritical Fluids 2008;45(1):94-101.
[61] McShane CP. Vegetable-Oil-Based Dielectric Coolants [J]. IEEE Industry Applications Magazine 2002:34-41.
[62] Hopkinson P, Dix L, McShane CP, Moore HR, Moore, S, Murphy J, Prevost T, Beaster B. Progress report on natural esters for distribution and power transformers [J]. IEEE Power and Energy Society General Meeting-PESGM 2009,VOLS 1-8 :2473-2475.
[2]王继龙,衣家文.变压器油的选择[J].变压器. 2005, Vol.42, No.4,pp 27-28.
[3] IEC296-1991(修订版) [S].英国BS148-1998规格标准,变压器油标准.
[4]贺以燕,郭振岩,赵良云.不燃油与难燃油及其变压器的发展[J].变压器. 2000, No.08.
[5]李晓峰.一种新型高燃点绝缘液体-R-TEMP油[J].变压器. 1995, No.02.
[6]田雷,白云玲,钟建江.微生物降解有机污染物的研究进展[J].工业微生物. 2000, Vol.30, No.2, pp46-50.
[7] T.V. Oommen, C.C. Claiborne, J.T.Mullen. Biodegradable electrical insulation fluids [J]. Proceedings of Electrical Insulation Conference, Sep 1997, pp465-468.
[8] T.V. Oommen. Vegetable oils for liquid filled transformers [J]. IEEE Electrical Insulation Magazine, 2002, Vol18, No.1 pp6-11.
[9] C. P McShane. Natural and synthetic ester dielectric fluid: their relative environ -mental, fire safety, and electrical performance [J]. Industrial and Commercial Power Systems Technical Conference, May 1999, pp1-8.
[10] [日]速水敏幸.电力设备的绝缘诊断[M].北京:科学出版社, 2003, pp155-161.
[11] C. P McShane. Relative properties of the new combustion resistant vegetable oil based dielectric coolants [J]. IEEE Transactions on Industry Applications, 2002, Vol37, No.4, pp1132-1139.
[12]王树森.变压器绝缘材料[J].变压器. 2005, Vol.42, No.4pp31-32.
[13] Bertrand Y, Hoang L.C. Vegetal oils as substitute for mineral oils [J]. Proceedings of the 7th International Conference on Properties and Applications of Dielectric Materials, June 2003, Vol.2, pp491 - 494 vol.2.
[14] Mcshane C P. Relative properties of the new combustion resistant vegetable oil based dielectric coolants [J].2000.
[15]贺以燕,郭振岩,赵良云.不燃油与难燃油及其变压器的发展[J].变压器. 2000, Vol37, No.8, pp4-7.
[16]刘玉兰.植物油脂生产与综合利用[M].北京:中国轻工业出版社, 1999.
[17] P.Boss, T.V. Oommen. New insulating fluids for transformers based on biodegradable high oleic vegetable oil and ester fluid [J]. IEE Colloquium on Insulating Liquids. May 1999, Vol.7, pp1-10.
[18] Oommen T V. Vegetable oils for liquid-filled transformers [J]. Electrical Insulation Magazine,IEEE Electrical Insulation Magazine, IEEE. 2002, Vol.18, No.1: pp6-11.
[19] Oommen T V, Claiborne C C, Walsh E J etal. A new vegetable oil based transformer fluid: development and verification [J]. 2000, Vol.1,pp308-312.
[20] Mcshane C P, Corkran J L, Rapp K J etal. Aging of paper insulation retrofilled with natural ester dielectric fluid [J]. 2003.
[21]日本开发出用植物油做绝缘油的变压器[J].东北电力技术. 2002,No.8, pp13.
[22] United States Patent. Electrical transformers containing electrical insulation fluids comprising high oleic acid oil compositions [J]. Patent Number: 5949017, Sep 1999.
[23] United States Patent. Soybean based transformer oil and transmission line fluid [J]. Patent Number: 5958851, Sep 1999.
[24] Mcshane C P, Rapp K J, Corkran J L etal. Aging of paper insulation in natural ester dielectric fluid [J]. 2001.
[25] Mcshane C P, Rapp K J, Corkran J L etal. Aging of Kraft paper in natural ester dielectric fluid [J]. 2002.
[26] Mcshane C P. Relative properties of the new combustion-resist egetable-oil-based dielectric coolants for distribution and power ransformers [J]. Industry Applications, IEEE Transactions on Industry Applications, IEEE Transactions on. 2001, Vol.37, No.4: pp1132-1139.
[27] Badent R, Hemmer M, Schwab A J. Inhibited rape-seed oil as substitute for mineral oils [J]. 2002
[28] Badent R, Hemmer M, Konekamp U etal. Streamer inception field strengths in rape-seed oils [J]. 2000.
[29] Badent R, Kist K, Schwab A J. Rape-seed oil-a substitute for mineral oil? [J]. 1999.
[34]毕艳兰.油脂化学[M].北京:化学工业出版社, 2005, pp22.
[35]陈洁.油脂化学[M].北京:化学工业出版社, 2004, pp17.
[36]伍越寰,李伟昶,沈晓明.有机化学[M].安徽:中国科学技术大学出版社. 2002,pp623-626.
[37] [美]斯沃恩,秦洪万译.贝雷油脂化学与工艺学[M].北京:中国轻工业出版社,1989.
[38]倪培德.油脂加工技术[M].北京:化学工业出版社, 2003.
[39]何东平.油脂精炼与加工工艺学[M].北京:化学工业出版社, 2005, pp40-67.
[40]马传国.油脂加工工艺与设备[M].北京:化学工业出版社, 2004, pp25-36.
[41]彭阳生.植物油脂加工实用技术[M].北京:金盾出版社, 2003, pp280-293.
[42] GB5530-1998《动植物油脂酸价和酸度测定》[S].
[43]宋华,陈颖.化工分离工程[M].哈尔滨:哈尔滨工业大学出版, 2003, pp201-217.
[44] [苏]H.C.阿鲁楚尼亚恩.油脂加工工艺[M].北京:化学工业出版社, 1990.
[45] [美]R.W.约翰逊, E.弗里兹编,陆用海,胡征宇主译.工业脂肪酸及其应用[M].北京:中国轻工业出版社, 1992.
[46]汪德生,张洪林,蒋林时等.高效活性白土制备和工艺改进[J].非金属矿. 2004, No.04.
[47]吕宪俊,崔学奇,刘晓东.高效活性白土的制备及其活化机理研究[J].中国非金属矿工业导刊. 2003, No.04.
[48]曹明礼,张凌燕,荣葵一.膨润土制备高效活性白土的研究[J].化工矿物与加工. 2000, No.02.
[49]杨虎,刘琼荪,钟波.数理统计[M].北京:高等教育出版社, 2004, pp168-178.
[50]刘玉兰.植物油脂生产与综合利用[M].北京:中国轻工业出版社, 1999.
[51]兰州大学复旦大学化学系有机教研室.有机化学实验[M].北京:高等教育出版社,1999.
[52]刘炳尧.电气设备绝缘试验[J].北京:水利电力出版社, 1993.
[53] GB5525《植物油脂检验透明度、色泽、气味、滋味鉴定法》[S].
[54] DL420-91《电气绝缘液体的折射率和比色散试验方法》[S].
[55] DL420.3-91《水溶性酸测定法》[S].
[56]孙辉,吕秀阳,陈良.不同植物油脂在近临界水中水解反应动力学的比较[J].化工学报.2007, No.04.
[57] Holliday RL,King JW,List GR. Hydrolysis of vegetable oils in sub-and supercritical water [J]. Industrial Engineering Chemical Research 1997; 36 (3): 932- 935.
[58] Mcshane CP. Relative properties of the new combustion-resistant vegetable-oil-based dielectric coolants for distribution and power transformers [J]. IEEE Transactions on Industry Applications 2001; 37 (4):1132-1139.
[59] Moore HR. Requirements and expectations of natural ester fluids for application in power transformers [J]. IEEE Transmission and distribution conference and exhibition 2005/2006 PES May 21-24, 2006:3-24.
[60] Moquin PHL,Temelli F. Kinetic modeling of hydrolysis of canola oil in supercritical media [J]. Journal of Supercritical Fluids 2008;45(1):94-101.
[61] McShane CP. Vegetable-Oil-Based Dielectric Coolants [J]. IEEE Industry Applications Magazine 2002:34-41.
[62] Hopkinson P, Dix L, McShane CP, Moore HR, Moore, S, Murphy J, Prevost T, Beaster B. Progress report on natural esters for distribution and power transformers [J]. IEEE Power and Energy Society General Meeting-PESGM 2009,VOLS 1-8 :2473-2475.