异辛醇硝化制备硝酸异辛酯合成工艺热危险性的初步研究
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摘要
向硝硫混酸中滴加异辛醇硝化制备硝酸异辛酯(EHN)的过程具有较大的热危险性,国内类似工艺曾经发生两起爆炸事故,有必要对此工艺过程的热危险性开展系统分析、测试、评估和安全控制方向的研究。
本文主要通过实验室全自动反应量热仪(RCle)测试了这一半间歇硝化反应的热力学数据,同时利用差示扫描量热仪(DSC)以及用加速度量热仪(ARC)研究了产物的二次分解特性,从而对反应的热危险性进行评估分级。首先采用DSC对反应体系及产物在动态升温过程下的热分解特性进行了研究和分析；再采用RCle研究不同的反应温度、加料速率等参数对反应放热特性的影响,计算出间歇式反应失控条件下的绝热温升(△Tad)、反应所能达到的最高温度(MTSR)等参数；用ARC对反应产物体系在绝热状态下的热分解特性进行了研究,得出诱导期与温度的关系曲线,同时得到诱导期为24h所对应的温度TD24等参数；最后结合ARC数据和RCle数据,根据热失控危险等级分类标准进行热失控危险等级划分。
结果表明：对硝酸异辛酯(EHN)与混酸的混合物,混酸含量越大,EHN的起始分解温度越低；对合成EHN反应的工艺条件条件严格控制,尤其是反应温度,当温度超过20℃时,反应的热失控危险等级为第5级,非常危险；另外,通过对不同反应条件下的产物浓度测试得到温度较低时,产率也较低。因此应在保证生产安全的基础上对反应的工艺条件进行进一步的优化,使其经济效益达到最佳。
The nitrification process of producing 2-Ethylhexyl nitrate(EHN)by dosing isooctyl alcohol to nitric-sulfuric acid mixture is with greater risk of heat, and domestic similar process has been two explosions occurred.So,about the thermal hazard of this process, it is necessary to carry out the systems analysis, testing, evaluation and investigation on the direction of security control.
In this paper, Reaction Calorimeter(RCle) was used to measure the thermodynamics parameters of this nitration in semi-batch reactor, additionally, Differential Scanning Calorimeter(DSC) and Accelerating Rate Calorimeter (ARC) were used to study the secondary decomposition characterizations of the product, thereby, evaluating the thermal runaway criticality of the reaction. First of all,the thermodynamics behaviors of products and reaction system under non-isothermal mode were studied by DSC.Then a series of experiments were carried out with RCle to study the influence of several parameter, such as reaction temperature and dosing time on the exothermic character of the reaction; Some parameters such as adiabatic temperature increase of batch reaction(△Tad),maximum temperature of synthetic reaction(MTSR) were obtained here. After that, ARC was used to study the thermal decomposition of the product, the relation curve of the induction period and temperature can be fitted. Also the temperature when the explosion happened on 24h(TD24) were analyzed. Finally, combining the datum from ARC and RCle, the risk class of thermal runaway criticality is studied.
The results indicate that about the mixture of the mix acid and the 2-Ethylhexyl nitrate, the more the content of the mix acid was, the lower was the onset of the secondary decomposition of 2-Ethylhexyl nitrate. The process conditions of the synthetic reaction should be severely controlled, especially the reaction temperature. When the temperature is above 20℃,its risk class of thermal runaway reaction is class 5,which is very dangerous. Through the purity test of several reaction products under different conditions, it is found that the rate of production is lower if the reaction temperature blew 30℃.So, further optimizing the processing condition on assuring the security of the process of producting should be developed, to reach the best economic benefit.
本文主要通过实验室全自动反应量热仪(RCle)测试了这一半间歇硝化反应的热力学数据,同时利用差示扫描量热仪(DSC)以及用加速度量热仪(ARC)研究了产物的二次分解特性,从而对反应的热危险性进行评估分级。首先采用DSC对反应体系及产物在动态升温过程下的热分解特性进行了研究和分析；再采用RCle研究不同的反应温度、加料速率等参数对反应放热特性的影响,计算出间歇式反应失控条件下的绝热温升(△Tad)、反应所能达到的最高温度(MTSR)等参数；用ARC对反应产物体系在绝热状态下的热分解特性进行了研究,得出诱导期与温度的关系曲线,同时得到诱导期为24h所对应的温度TD24等参数；最后结合ARC数据和RCle数据,根据热失控危险等级分类标准进行热失控危险等级划分。
结果表明：对硝酸异辛酯(EHN)与混酸的混合物,混酸含量越大,EHN的起始分解温度越低；对合成EHN反应的工艺条件条件严格控制,尤其是反应温度,当温度超过20℃时,反应的热失控危险等级为第5级,非常危险；另外,通过对不同反应条件下的产物浓度测试得到温度较低时,产率也较低。因此应在保证生产安全的基础上对反应的工艺条件进行进一步的优化,使其经济效益达到最佳。
The nitrification process of producing 2-Ethylhexyl nitrate(EHN)by dosing isooctyl alcohol to nitric-sulfuric acid mixture is with greater risk of heat, and domestic similar process has been two explosions occurred.So,about the thermal hazard of this process, it is necessary to carry out the systems analysis, testing, evaluation and investigation on the direction of security control.
In this paper, Reaction Calorimeter(RCle) was used to measure the thermodynamics parameters of this nitration in semi-batch reactor, additionally, Differential Scanning Calorimeter(DSC) and Accelerating Rate Calorimeter (ARC) were used to study the secondary decomposition characterizations of the product, thereby, evaluating the thermal runaway criticality of the reaction. First of all,the thermodynamics behaviors of products and reaction system under non-isothermal mode were studied by DSC.Then a series of experiments were carried out with RCle to study the influence of several parameter, such as reaction temperature and dosing time on the exothermic character of the reaction; Some parameters such as adiabatic temperature increase of batch reaction(△Tad),maximum temperature of synthetic reaction(MTSR) were obtained here. After that, ARC was used to study the thermal decomposition of the product, the relation curve of the induction period and temperature can be fitted. Also the temperature when the explosion happened on 24h(TD24) were analyzed. Finally, combining the datum from ARC and RCle, the risk class of thermal runaway criticality is studied.
The results indicate that about the mixture of the mix acid and the 2-Ethylhexyl nitrate, the more the content of the mix acid was, the lower was the onset of the secondary decomposition of 2-Ethylhexyl nitrate. The process conditions of the synthetic reaction should be severely controlled, especially the reaction temperature. When the temperature is above 20℃,its risk class of thermal runaway reaction is class 5,which is very dangerous. Through the purity test of several reaction products under different conditions, it is found that the rate of production is lower if the reaction temperature blew 30℃.So, further optimizing the processing condition on assuring the security of the process of producting should be developed, to reach the best economic benefit.
引文
[1]陈网桦,彭金华,陈利平[译].化工工艺的热安全—风险评估与工艺设计[M].第一版.北京：科学出版社,2008
[2]刘荣海,陈网桦,胡毅亭.安全原理与危险化学品测评技术[M].第一版.北京：化学工业出版设,2004：155-167
[3]中国石油天然气集团公司HSE指导委员会.健康、安全与环境管理体系—风险评价[M].第1版.北京：石油工业出版社,2001
[4]赵瑞华,牟善军,蒋涛.国内外危险化学品重特大典型事故案例[M].第一版.青岛：青岛市新闻出版社,2002
[5]张广华,丁盛等.危险化学品重大特大事故案例精选[M].第一版.北京：中国劳动社会保障出版社,2007：34-35
[6]Charles P. Alkyl Nitrates. US,2768964.1956
[7]Knapp G G, Baglerian M, Seemuth P D. Nitration of Aliphatic Compounds.US, 4479905.1984
[8]胡应喜,吕九琢等.柴油十六烷值改性剂(Ⅰ)：硝酸异辛酯的合成[J].石油化工高等学校学报,1997,10(4)：16-18
[9]孔繁玲,邵海目.压缩喷射硝化工艺制备硝酸异辛酯的研究[J].火炸药,1996,(2)：15-17
[10]李雪华,吴京峰.危险化学品活性反应危害及混配危险的规则研究[J].安全环境和健康,2006,6(5)：40-41
[11]Bornemann H, Scheidt F, Sander W. Thermal Decomposition of 2-Ethylhexyl Nitrate (2-EHN)[J].Int. J. Chem. Kinet,2002,34:34-38
[12]许妍.三种硝酸酯的热安定性研究[D].南京：南京理工大学,2007
[13]陆燕.四种液态含能材料热感度的探索性研究[D].南京：南京理工大学,2008
[14]Theodor Grewer. Thermal hazards of chemical reactions.1st ed[J].The Netherlands: Elservier Science B.V.,1993:365-380
[15]Benjamin J. Understanding, Evaluating, and Controlling the Hazards of Exothermic Reaction [J].Technical Reports,2001,(17):1-6
[16]Ruedi W. Gygax. Chemical Reaction Engineering for Safety[J].Chemical Engineering Science,1988,43(8):1759-1771
[17]Grewer T. Thermal Hazards of Chemical Reaction [M].Elsevier,1994.
[18]Ralph N. Landau, Donna G. Blackmond. Scale up Heat Transfer based on Reaction Calorimetry[J].Chemical Engineering Progress.1944:4343-4348
[19]Ralph N. Robert S.Cutro. Assess Risk Due to Desired Chemistry[M].Chemical Engineering Progress.1933:66-71
[20]Alos M A, et al. A New Method for Assessing the Thermal Stability of Semibatch Process Based on Lyapunov Exponets[J].Chemical Engineering Science. 1996(11):3089-3094
[21]Hugo P, Steinbach J, Stoessel F. Calculation of the Maximum Temperature in Stirred Tank Reactors in Case of a Breakdown of Cooling[J].Chemical Engineering Science.1988(8):2147-2152
[22]Varma A, Morbidelli M, Wu H. Parametric Sensitivity in Chemical Systems[M].1st ed. Cambridge:The press syndicate of the university of Cambridge,1999:1-8
[23]Steensma Metske, Westerterp K Roel.Thermally safe operation of a semi-batch reactor for liquid-liquid reactions[J].Slow reactions. Industrial and Engineering Chemistry Research,1990,29:1259-1270
[24]Woezik B A A van, Westerterp K R. Runaway behavior and thermally safe operation of multiple liquid-liquid reactions in the semi-batch reactor. The nitric acid oxidation of 2-octannol[J].Chemical Engineering and Processing,2002,41:59-77
[25]Strozzi F, Zaldivar J M, Kronberg A E, Westerterp K R. On-line runaway detection in batch reactors using chaos theory techniques[J].AIChE Journal,1999,45(11): 2429-2443
[26]Gygax R. Scale up principles for assessing thermal runaway risks[J].Chemical Engineering Progress,1990, February:53-60
[27]Stoessel Francis. Design thermally safe semibatch reactor[J].Chemical Engineering Progress,1995,September:46-53
[28]Stoessel Francis. Thermal safety of chemical processes——risk assessment and process design[M].1st ed. The FEDERAL Republic of Germany:Wiley-VCH,2008
[29]罗云,樊运晓,马晓春.风险分析与安全评价[M].第1版.北京：化学工业出版社,2007
[30]Stoessel F, Ubrich O.Safety assessment and optimization of semi-batch reactor by calorimetry[J].Journal of Thermal Analysis and Calorimetry,2001,64:61-74
[31]Stoessel Francis. What is your thermal risk?[J].Chemical Engineering Progress, 1993,Octorber:68-75
[32]Allen R.Broyles, Roger E.Eckert. Maximization of the Conversion to m-Toluenesulfonic Acid in Sulfuric Acid.Sulfonation[J].Ind. Eng. Chem. Process Des. Develop,1973,12(3)：295-300
[33]蒋登高,章亚东,周彩荣.精细有机合成反应及工艺[M].北京：化学工业出版社,2001
[34]Choudhury S, Utiger L, Riesen R. Heat Transport in Agitated Vessels:Scale-up methods[J].METTLER TOLEDO Publication,00724218:2-15
[35]董新法,方利国,陈砺.物性估算原理及计算机计算[M].北京：化学工业出版社,2006：207-211
[36]朱贤峰.甲苯磺化反应过程的热危险性分析[D].南京：南京理工大学,2008
[37]陈丽涛.芳烃亲电取代硝化机理的理论研究[D].南京：南京理工大学化工学院,2004
[38]Ying Fuchang. Computational studies of aromatic nitration[D].Mississippi State:The Faculty of Mississippi State University,2004
[39]Townsend D.I.,Tou J C.Thermal hazard evaluation by an accelerating rate calorimeter[J].Thermochimica Acta,1980,37:1-30
[40]钱新明,刘丽,张杰.绝热加速量热仪在化工生产热危险性评价中的应用[J].中国安全生产科学技术,2005,1(1)：13-18
[41]钱新明,王耘,冯长根.用加速量热仪研究KCl03/CuO/S/Mg-Al/C6Cl6的热分解[J].物理化学学报,2001,17(1)：71-74
[42]Steensma M, Westerterp K R. Thermally safe operation of a cooled semi-batch reactor. Slow liquid-liquid reactions[J].Chemical Engineering Science,1988,43(8):2125-213
[43]四川大学工科基础化学教学中心.分析化学[M].北京：科学出版社,2001：205-210
[44]陈利平.甲苯硝化反应热危险性的实验与理论研究[D].南京：南京理工大学,2008
[2]刘荣海,陈网桦,胡毅亭.安全原理与危险化学品测评技术[M].第一版.北京：化学工业出版设,2004：155-167
[3]中国石油天然气集团公司HSE指导委员会.健康、安全与环境管理体系—风险评价[M].第1版.北京：石油工业出版社,2001
[4]赵瑞华,牟善军,蒋涛.国内外危险化学品重特大典型事故案例[M].第一版.青岛：青岛市新闻出版社,2002
[5]张广华,丁盛等.危险化学品重大特大事故案例精选[M].第一版.北京：中国劳动社会保障出版社,2007：34-35
[6]Charles P. Alkyl Nitrates. US,2768964.1956
[7]Knapp G G, Baglerian M, Seemuth P D. Nitration of Aliphatic Compounds.US, 4479905.1984
[8]胡应喜,吕九琢等.柴油十六烷值改性剂(Ⅰ)：硝酸异辛酯的合成[J].石油化工高等学校学报,1997,10(4)：16-18
[9]孔繁玲,邵海目.压缩喷射硝化工艺制备硝酸异辛酯的研究[J].火炸药,1996,(2)：15-17
[10]李雪华,吴京峰.危险化学品活性反应危害及混配危险的规则研究[J].安全环境和健康,2006,6(5)：40-41
[11]Bornemann H, Scheidt F, Sander W. Thermal Decomposition of 2-Ethylhexyl Nitrate (2-EHN)[J].Int. J. Chem. Kinet,2002,34:34-38
[12]许妍.三种硝酸酯的热安定性研究[D].南京：南京理工大学,2007
[13]陆燕.四种液态含能材料热感度的探索性研究[D].南京：南京理工大学,2008
[14]Theodor Grewer. Thermal hazards of chemical reactions.1st ed[J].The Netherlands: Elservier Science B.V.,1993:365-380
[15]Benjamin J. Understanding, Evaluating, and Controlling the Hazards of Exothermic Reaction [J].Technical Reports,2001,(17):1-6
[16]Ruedi W. Gygax. Chemical Reaction Engineering for Safety[J].Chemical Engineering Science,1988,43(8):1759-1771
[17]Grewer T. Thermal Hazards of Chemical Reaction [M].Elsevier,1994.
[18]Ralph N. Landau, Donna G. Blackmond. Scale up Heat Transfer based on Reaction Calorimetry[J].Chemical Engineering Progress.1944:4343-4348
[19]Ralph N. Robert S.Cutro. Assess Risk Due to Desired Chemistry[M].Chemical Engineering Progress.1933:66-71
[20]Alos M A, et al. A New Method for Assessing the Thermal Stability of Semibatch Process Based on Lyapunov Exponets[J].Chemical Engineering Science. 1996(11):3089-3094
[21]Hugo P, Steinbach J, Stoessel F. Calculation of the Maximum Temperature in Stirred Tank Reactors in Case of a Breakdown of Cooling[J].Chemical Engineering Science.1988(8):2147-2152
[22]Varma A, Morbidelli M, Wu H. Parametric Sensitivity in Chemical Systems[M].1st ed. Cambridge:The press syndicate of the university of Cambridge,1999:1-8
[23]Steensma Metske, Westerterp K Roel.Thermally safe operation of a semi-batch reactor for liquid-liquid reactions[J].Slow reactions. Industrial and Engineering Chemistry Research,1990,29:1259-1270
[24]Woezik B A A van, Westerterp K R. Runaway behavior and thermally safe operation of multiple liquid-liquid reactions in the semi-batch reactor. The nitric acid oxidation of 2-octannol[J].Chemical Engineering and Processing,2002,41:59-77
[25]Strozzi F, Zaldivar J M, Kronberg A E, Westerterp K R. On-line runaway detection in batch reactors using chaos theory techniques[J].AIChE Journal,1999,45(11): 2429-2443
[26]Gygax R. Scale up principles for assessing thermal runaway risks[J].Chemical Engineering Progress,1990, February:53-60
[27]Stoessel Francis. Design thermally safe semibatch reactor[J].Chemical Engineering Progress,1995,September:46-53
[28]Stoessel Francis. Thermal safety of chemical processes——risk assessment and process design[M].1st ed. The FEDERAL Republic of Germany:Wiley-VCH,2008
[29]罗云,樊运晓,马晓春.风险分析与安全评价[M].第1版.北京：化学工业出版社,2007
[30]Stoessel F, Ubrich O.Safety assessment and optimization of semi-batch reactor by calorimetry[J].Journal of Thermal Analysis and Calorimetry,2001,64:61-74
[31]Stoessel Francis. What is your thermal risk?[J].Chemical Engineering Progress, 1993,Octorber:68-75
[32]Allen R.Broyles, Roger E.Eckert. Maximization of the Conversion to m-Toluenesulfonic Acid in Sulfuric Acid.Sulfonation[J].Ind. Eng. Chem. Process Des. Develop,1973,12(3)：295-300
[33]蒋登高,章亚东,周彩荣.精细有机合成反应及工艺[M].北京：化学工业出版社,2001
[34]Choudhury S, Utiger L, Riesen R. Heat Transport in Agitated Vessels:Scale-up methods[J].METTLER TOLEDO Publication,00724218:2-15
[35]董新法,方利国,陈砺.物性估算原理及计算机计算[M].北京：化学工业出版社,2006：207-211
[36]朱贤峰.甲苯磺化反应过程的热危险性分析[D].南京：南京理工大学,2008
[37]陈丽涛.芳烃亲电取代硝化机理的理论研究[D].南京：南京理工大学化工学院,2004
[38]Ying Fuchang. Computational studies of aromatic nitration[D].Mississippi State:The Faculty of Mississippi State University,2004
[39]Townsend D.I.,Tou J C.Thermal hazard evaluation by an accelerating rate calorimeter[J].Thermochimica Acta,1980,37:1-30
[40]钱新明,刘丽,张杰.绝热加速量热仪在化工生产热危险性评价中的应用[J].中国安全生产科学技术,2005,1(1)：13-18
[41]钱新明,王耘,冯长根.用加速量热仪研究KCl03/CuO/S/Mg-Al/C6Cl6的热分解[J].物理化学学报,2001,17(1)：71-74
[42]Steensma M, Westerterp K R. Thermally safe operation of a cooled semi-batch reactor. Slow liquid-liquid reactions[J].Chemical Engineering Science,1988,43(8):2125-213
[43]四川大学工科基础化学教学中心.分析化学[M].北京：科学出版社,2001：205-210
[44]陈利平.甲苯硝化反应热危险性的实验与理论研究[D].南京：南京理工大学,2008