三羟甲基丙烷复合酯热氧化规律及氧化动力学研究
|
摘要
对三羟甲基丙烷复合酯分别进行不同温度与时间下的恒温氧化,检测其氧化后的黏度、黏度指数和酸值,并通过函数拟合得出它们随氧化温度与时间的变化规律;使用PDSC测试被氧化样品的起始氧化温度,并计算活化能、氧化速率常数和氧化半衰期,得到氧化温度与时间对油品后续氧化安定性的影响规律。结果表明:油品黏度与酸值的变化规律均近似logistic函数曲线,即起初增长缓慢,随后迅速增长并达到最快速率,最终速率逐渐下降;黏度与酸值函数的拟合参数与氧化温度密切相关,可用于评价与预测油品的氧化行为;三羟甲基丙烷复合酯经历不同条件的高温氧化后始终具有较高的黏度指数,并且起始氧化温度和活化能均未发生显著变化,表明其氧化后仍有着优异的黏温性能和氧化安定性。
The trimethylolpropane complex esters were oxidized by the oven at different temperatures and time.The kinematic viscosities,viscosity indexes and acid values of oxidized esters were tested respectively,and their change rules with oxidation temperature and time were obtained by fitting function.By testing the initial oxidation temperatures of the oxidized samples with the pressurized differential scanning calorimetry,calculating the activation energy,oxidation rate constant and half-life period,the effects of oxidation temperature and time on the oxidation stability of the oxidized samples were investigated.The results show that the variation trends of kinematic viscosity and acid value are close to logistic function curve,that is,they increase slowly at the initial stage,then grow rapidly and reach the fastest rate,and finally the rate is gradually decreased.The fitting parameters of viscosity and acidity function are closely related to oxidation temperature,which can be used to evaluate and predict the oxidation behaviors of oxidized esters.The trimethylolpropane complex esters keep high viscosity index after high temperature oxidation under different conditions,and their initial oxidation temperature and activation energy have not changed significantly,indicating that the trimethylolpropane complex esters still have excellent viscosity-temperature properties and oxidation stability after oxidation.
The trimethylolpropane complex esters were oxidized by the oven at different temperatures and time.The kinematic viscosities,viscosity indexes and acid values of oxidized esters were tested respectively,and their change rules with oxidation temperature and time were obtained by fitting function.By testing the initial oxidation temperatures of the oxidized samples with the pressurized differential scanning calorimetry,calculating the activation energy,oxidation rate constant and half-life period,the effects of oxidation temperature and time on the oxidation stability of the oxidized samples were investigated.The results show that the variation trends of kinematic viscosity and acid value are close to logistic function curve,that is,they increase slowly at the initial stage,then grow rapidly and reach the fastest rate,and finally the rate is gradually decreased.The fitting parameters of viscosity and acidity function are closely related to oxidation temperature,which can be used to evaluate and predict the oxidation behaviors of oxidized esters.The trimethylolpropane complex esters keep high viscosity index after high temperature oxidation under different conditions,and their initial oxidation temperature and activation energy have not changed significantly,indicating that the trimethylolpropane complex esters still have excellent viscosity-temperature properties and oxidation stability after oxidation.
引文
[1]刘维民,许俊,冯大鹏,等.合成润滑油的研究现状及发展趋势[J].摩擦学学报,2013,33(1):91-104.LIU W M,XU J,FENG D P,et al.The research status and prospect of synthetic lubricating oils[J].Tribology,2013,33(1):91-104.
[2]叶斌,陶德华.环境友好润滑剂的特点及发展[J].润滑与密封,2002,27(5):73-76.YE B,TAO D H.Development and characteristics of environmentally friendly lubricants[J].Lubrication Engineering,2002,27(5):73-76.
[3]陈国需,方建华,王泽爱,等.润滑油性质及应用[M].北京:中国石化出版社,2016:29-131.
[4]PONNEKANTI N,SAVITA K.Development of ecofriendly/biodegradable lubricants:an overview[J].Renewable and Sustainable Energy Reviews,2012,16(1):764-774.
[5]LESLIE R R,RONALD L S.Synthetic lubricants and high-performance functional fluids[M].北京:中国石化出版社,2006:53-81.
[6]李雁秋,王鹏,张宜涛,等.R22型空调压缩机专用冷冻机油的研制[J].石油商技,2012,30(4):28-31.LI Y Q,WANG P,ZHANG Y T,et al.The research of refrigerator oil used in R22 air condition compressor[J].Omnibraring Use of Oil,2012,30(4):28-31.
[7]费建奇,赵伟.多元醇酯类冷冻机机用基础油的合成及其性能[J].润滑油,2009,24(4):22-25.FEI J Q,ZHAO W.Synthesis of polyol ester used as basestock of refrigerator oil and its performance[J].Lubricating Oil,2009,24(4):22-25.
[8]陈毓暑.新型R290制冷系统用酯类冷冻机油的合成与性能研究[D].深圳:中国科学院深圳先进技术研究院,2014.
[9]李雁秋,康茵,王鹏,等.冷冻机油对R600a型冰箱压缩机制冷性能的影响[J].石油炼制与化工,2011,42(1):80-83.LI Y Q,KANG Y,WANG P,et al.Impact of refrigerator oil on the refrigeration effect of compressor using R600a refrigerant[J].Petroleum Processing and Petrochemicals,2011,42(1):80-83.
[10]金永亮,钱绪政,贾丹,等.三羟甲基丙烷油酸酯基础油高温氧化的拉曼光谱分析[J].润滑与密封,2015,40(10):19-22.JIN Y L,QIAN X Z,JIA D,et al.Raman spectral analysis of trimethylolpropane trioleate base oil in high temperature oxidation process[J].Lubrication Engineering,2015,40(10):19-22.
[11]程冰雪,贾丹,钱绪政,等.基于拉曼光谱的TMPTO热氧化特性研究[J].摩擦学学报,2016,36(1):7-12.CHENG B X,JIA D,QIAN X Z,et al.Thermal oxidation characteristic of TMPTO based on Raman spectroscopy[J].Tribology,2016,36(1):7-12.
[12]姚俊兵.利用扫描量热法评价润滑油的高温抗氧化性能[J].润滑与密封,2000,25(2):35-37.YAO J B.Evaluation of high temperature antioxidation performances for lubricants by differential scanning calorimetry(DSC)[J].Lubrication Engineering,2000,25(2):35-37.
[13]QIU C,HAN S,CHENG X G,et al.Determining the antioxidant activities of organic sulfides by rotary bomb oxidation test and pressurized differential scanning calorimetry[J].Thermochimica Acta,2006,447:36-40.
[14]张梅,李久盛,李建群.利用PDSC考察环境友好润滑油基础油氧化安定性的研究[J].润滑与密封,2006,31(12):152-154.ZHANG M,LI J S,LI J Q.Study on the oxidative stability of base oil for biodegradable lubricants using pressure differential scanning calorimetry method[J].Lubrication Engineering,2006,31(12):152-154.
[15]陈立波,郭绍辉.酯类合成油的热氧化及其状态监控技术研究进展[J].合成润滑材料,2001,28(2):19-23.CHEN L B,GUO S H.The development of research on thermal oxidation and condition monitoring of ester lubricants[J].Synthetic Lubricants,2001,28(2):19-23.
[16]MANNEKOTE J K,KAILAS S V.The effect of oxidation on tribological performance of few vegetable oils[J].Journal of Materials Research and Technology,2012,1(2):91-95.
[17]金永亮,钱绪政,向亚玲,等.三羟甲基丙烷油酸酯基础油热氧化规律研究[J].润滑与密封,2014,39(12):39-42.JIN Y L,QIAN X Z,XIANG Y L,et al.Thermal oxidation research of trimethylolpropane trioleate synthetic lubricant[J].Lubrication Engineering,2014,39(12):39-42.
[18]刘建芳,金永亮,向亚玲,等.酯类基础油的热氧化与水解稳定性能研究[J].润滑与密封,2014,39(5):56-61.LIU J F,JIN Y L,XIANG Y L,et al.Thermal oxidative and hydrolytic stability of the synthetic ester base oils[J].Lubrication Engineering,2014,39(5):56-61.
[19]郑哲,方建华,王建华,等.合成酯类油结构对水解安定性的影响[J].后勤工程学报,2016,32(1):29-34.ZHENG Z,FANG J H,WANG J H,et al.The effects of structure of synthetic ester base oils on hydrolytic stability[J].Journal of Logistics Engineering.2016,32(1):29-34.
[20]唐友云,李剑群,徐美娟,等.基于PDSC程序升温法的抗氧剂抗氧化能力评价[J].润滑与密封,2015,40(8):128-132.TANG Y Y,LI J Q,XU M J,et al.Evaluation on anti-oxidation ability of antioxidant based on programmed ramp method of PDSC[J].Lubrication Engineering,2015,40(8):128-132.
[21]YAN S C,LU Y F,LIU G Q,et al.The kinetics analysis of formation behavior for the MgB2phase[J].Journal of Alloys and compounds,2007,443(1):161-165.
[22]钱绪政,向亚玲,金永亮,等.动力学方法研究合成酯类油的抗氧化性能[J].材料保护,2014,47(2):85-87.QIAN X Z,XIANG Y L,JIN Y L,et al.Study on the oxidation resistance of synthetic ester oil by kinetic analysis method[J].Materials Protection,2014,47(2):85-87.
[23]卞森,费逸伟,姚婷,等.利用PDSC法监测酯类航空润滑油基础油的高温氧化安定性[J].河南师范大学学报(自然科学版),2016,44(5):65-69.BIAN S,FEI Y W,YAO T,et al.Monitoring the high-temperature oxidation stability of ester aviation lubricating base oil using high-press differential scanning calorimetry[J].Journal of Henan Normal University(Nation Science Edition),2016,44(5):65-69.
[24]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].2版.北京:科学出版社,2008.
[2]叶斌,陶德华.环境友好润滑剂的特点及发展[J].润滑与密封,2002,27(5):73-76.YE B,TAO D H.Development and characteristics of environmentally friendly lubricants[J].Lubrication Engineering,2002,27(5):73-76.
[3]陈国需,方建华,王泽爱,等.润滑油性质及应用[M].北京:中国石化出版社,2016:29-131.
[4]PONNEKANTI N,SAVITA K.Development of ecofriendly/biodegradable lubricants:an overview[J].Renewable and Sustainable Energy Reviews,2012,16(1):764-774.
[5]LESLIE R R,RONALD L S.Synthetic lubricants and high-performance functional fluids[M].北京:中国石化出版社,2006:53-81.
[6]李雁秋,王鹏,张宜涛,等.R22型空调压缩机专用冷冻机油的研制[J].石油商技,2012,30(4):28-31.LI Y Q,WANG P,ZHANG Y T,et al.The research of refrigerator oil used in R22 air condition compressor[J].Omnibraring Use of Oil,2012,30(4):28-31.
[7]费建奇,赵伟.多元醇酯类冷冻机机用基础油的合成及其性能[J].润滑油,2009,24(4):22-25.FEI J Q,ZHAO W.Synthesis of polyol ester used as basestock of refrigerator oil and its performance[J].Lubricating Oil,2009,24(4):22-25.
[8]陈毓暑.新型R290制冷系统用酯类冷冻机油的合成与性能研究[D].深圳:中国科学院深圳先进技术研究院,2014.
[9]李雁秋,康茵,王鹏,等.冷冻机油对R600a型冰箱压缩机制冷性能的影响[J].石油炼制与化工,2011,42(1):80-83.LI Y Q,KANG Y,WANG P,et al.Impact of refrigerator oil on the refrigeration effect of compressor using R600a refrigerant[J].Petroleum Processing and Petrochemicals,2011,42(1):80-83.
[10]金永亮,钱绪政,贾丹,等.三羟甲基丙烷油酸酯基础油高温氧化的拉曼光谱分析[J].润滑与密封,2015,40(10):19-22.JIN Y L,QIAN X Z,JIA D,et al.Raman spectral analysis of trimethylolpropane trioleate base oil in high temperature oxidation process[J].Lubrication Engineering,2015,40(10):19-22.
[11]程冰雪,贾丹,钱绪政,等.基于拉曼光谱的TMPTO热氧化特性研究[J].摩擦学学报,2016,36(1):7-12.CHENG B X,JIA D,QIAN X Z,et al.Thermal oxidation characteristic of TMPTO based on Raman spectroscopy[J].Tribology,2016,36(1):7-12.
[12]姚俊兵.利用扫描量热法评价润滑油的高温抗氧化性能[J].润滑与密封,2000,25(2):35-37.YAO J B.Evaluation of high temperature antioxidation performances for lubricants by differential scanning calorimetry(DSC)[J].Lubrication Engineering,2000,25(2):35-37.
[13]QIU C,HAN S,CHENG X G,et al.Determining the antioxidant activities of organic sulfides by rotary bomb oxidation test and pressurized differential scanning calorimetry[J].Thermochimica Acta,2006,447:36-40.
[14]张梅,李久盛,李建群.利用PDSC考察环境友好润滑油基础油氧化安定性的研究[J].润滑与密封,2006,31(12):152-154.ZHANG M,LI J S,LI J Q.Study on the oxidative stability of base oil for biodegradable lubricants using pressure differential scanning calorimetry method[J].Lubrication Engineering,2006,31(12):152-154.
[15]陈立波,郭绍辉.酯类合成油的热氧化及其状态监控技术研究进展[J].合成润滑材料,2001,28(2):19-23.CHEN L B,GUO S H.The development of research on thermal oxidation and condition monitoring of ester lubricants[J].Synthetic Lubricants,2001,28(2):19-23.
[16]MANNEKOTE J K,KAILAS S V.The effect of oxidation on tribological performance of few vegetable oils[J].Journal of Materials Research and Technology,2012,1(2):91-95.
[17]金永亮,钱绪政,向亚玲,等.三羟甲基丙烷油酸酯基础油热氧化规律研究[J].润滑与密封,2014,39(12):39-42.JIN Y L,QIAN X Z,XIANG Y L,et al.Thermal oxidation research of trimethylolpropane trioleate synthetic lubricant[J].Lubrication Engineering,2014,39(12):39-42.
[18]刘建芳,金永亮,向亚玲,等.酯类基础油的热氧化与水解稳定性能研究[J].润滑与密封,2014,39(5):56-61.LIU J F,JIN Y L,XIANG Y L,et al.Thermal oxidative and hydrolytic stability of the synthetic ester base oils[J].Lubrication Engineering,2014,39(5):56-61.
[19]郑哲,方建华,王建华,等.合成酯类油结构对水解安定性的影响[J].后勤工程学报,2016,32(1):29-34.ZHENG Z,FANG J H,WANG J H,et al.The effects of structure of synthetic ester base oils on hydrolytic stability[J].Journal of Logistics Engineering.2016,32(1):29-34.
[20]唐友云,李剑群,徐美娟,等.基于PDSC程序升温法的抗氧剂抗氧化能力评价[J].润滑与密封,2015,40(8):128-132.TANG Y Y,LI J Q,XU M J,et al.Evaluation on anti-oxidation ability of antioxidant based on programmed ramp method of PDSC[J].Lubrication Engineering,2015,40(8):128-132.
[21]YAN S C,LU Y F,LIU G Q,et al.The kinetics analysis of formation behavior for the MgB2phase[J].Journal of Alloys and compounds,2007,443(1):161-165.
[22]钱绪政,向亚玲,金永亮,等.动力学方法研究合成酯类油的抗氧化性能[J].材料保护,2014,47(2):85-87.QIAN X Z,XIANG Y L,JIN Y L,et al.Study on the oxidation resistance of synthetic ester oil by kinetic analysis method[J].Materials Protection,2014,47(2):85-87.
[23]卞森,费逸伟,姚婷,等.利用PDSC法监测酯类航空润滑油基础油的高温氧化安定性[J].河南师范大学学报(自然科学版),2016,44(5):65-69.BIAN S,FEI Y W,YAO T,et al.Monitoring the high-temperature oxidation stability of ester aviation lubricating base oil using high-press differential scanning calorimetry[J].Journal of Henan Normal University(Nation Science Edition),2016,44(5):65-69.
[24]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].2版.北京:科学出版社,2008.