甲苯磺化反应过程的热危险性分析
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摘要
向沸腾状态下的甲苯滴加浓硫酸进行磺化反应具有一定的危险性。本文主要通过实验室全自动反应量热仪(RCle)测试了这一半间歇磺化过程的热力学数据,从而进行反应过程的安全性研究。首先采用差示扫描量热仪(DSC)对反应体系及产物在非等温状态下的热分解行为进行研究和分析,判断不同温度阶段发生的反应类型;再采用RCle研究不同的加料速度对反应过程参量的影响,并初探了苯环上甲基对磺化反应的影响,计算出间歇式反应失控条件下的绝热温升(△T_(ad))、反应所能达到的最高温度(MTSR)等参数;用加速度量热仪(ARC)对反应产物在绝热状态下的热分解行为进行了研究,得出不回归温度T_(NR)和至热爆炸发生的剩余时间仅为24h所对应的温度ADT_(24)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:采用半间歇式反应模式可以使反应失控严重度大大降低,然而该半间歇式反应在设定操作条件下反应失控所导致的最大温升(MTSR)还是超出安全条件允许的范围,而且该反应的热失控危险等级为第四级,比较危险,虽然足够多的甲苯能起到一定的安全保护作用,但还应从工艺上加以优化,以保证生产安全。
The sulphonation by dosing concentrated sulfuric acid to boiling toluene is of some risks. In this paper, Reaction Calorimeter(RC1e) was used to measure the thermodynamics parameters of this sulphonation in semi-batch reactor. First of all, the thermal decomposition behaviors of products and reaction system under non-isothermal mode were studied by Differential Scanning Calorimeter(DSC). Then a series of experiments were carried out with RC1e to study the influence of dosing time, and a primary try on the influence of methyl to sulphonation was performed as well; Some parameters such as adiabatic temperature increasement of batch reaction(ΔT_(ad)), maximum temperature of synthetic reaction(MTSR) were obtained here. After that, Accelerating Rate Calorimeter (ARC) were used to study the thermal decomposition of the product; the important parameters temperature of no return(T_(NR)) and the temperature when the explosion happened on 24h(ADT_(24)) are analyzed. Finally, combining the datum from ARC and RC1e, the risk class of thermal runaway criticality was studied. The results indicate that the severity of thermal runaway of the sulphonation of toluene with concentrated sulfuric acid can be reduced greatly by using semi-batch reaction, the MTSR under given operating conditions is still out of the scale. And its risk class of thermal runaway reaction is class 4, that means, though there is enough toluene in reaction system, which can restrain temperature rise at it's boiling point, it is still necessary to optimize the technics to confirm safety production.
结果表明:采用半间歇式反应模式可以使反应失控严重度大大降低,然而该半间歇式反应在设定操作条件下反应失控所导致的最大温升(MTSR)还是超出安全条件允许的范围,而且该反应的热失控危险等级为第四级,比较危险,虽然足够多的甲苯能起到一定的安全保护作用,但还应从工艺上加以优化,以保证生产安全。
The sulphonation by dosing concentrated sulfuric acid to boiling toluene is of some risks. In this paper, Reaction Calorimeter(RC1e) was used to measure the thermodynamics parameters of this sulphonation in semi-batch reactor. First of all, the thermal decomposition behaviors of products and reaction system under non-isothermal mode were studied by Differential Scanning Calorimeter(DSC). Then a series of experiments were carried out with RC1e to study the influence of dosing time, and a primary try on the influence of methyl to sulphonation was performed as well; Some parameters such as adiabatic temperature increasement of batch reaction(ΔT_(ad)), maximum temperature of synthetic reaction(MTSR) were obtained here. After that, Accelerating Rate Calorimeter (ARC) were used to study the thermal decomposition of the product; the important parameters temperature of no return(T_(NR)) and the temperature when the explosion happened on 24h(ADT_(24)) are analyzed. Finally, combining the datum from ARC and RC1e, the risk class of thermal runaway criticality was studied. The results indicate that the severity of thermal runaway of the sulphonation of toluene with concentrated sulfuric acid can be reduced greatly by using semi-batch reaction, the MTSR under given operating conditions is still out of the scale. And its risk class of thermal runaway reaction is class 4, that means, though there is enough toluene in reaction system, which can restrain temperature rise at it's boiling point, it is still necessary to optimize the technics to confirm safety production.
引文
[1]刘荣海,陈网桦,胡毅亭.安全原理与危险化学品测评技术[M].北京:化学工业出版社,2004
[2]胡寨驿.磺化反应锅爆炸的原因分析及预防[J].锅炉压力容器安全,1989,5(6):41-43
[3]刘铁民,张兴凯,刘功智.安全评价方法应用指南[M].北京:化学工业出版社,2005
[4]中国化工安全卫生技术协会防火防爆专业委员会编译.道化学公司火灾、爆炸危险指数评价方法(第7版),1997
[5]John Barton,Richard Rogers.Chemical Reaction Hazards[M].Institution of Chemical Engineers,1993
[6]王刚.对甲苯磺酸的制备及应用[J].辽宁化工,1995(5):14-16
[7]熊钢.气相磺化法研制对甲苯磺酸[J].泸天化科技,2001(3):243-245
[8]王晓立,田桂芝,孟兆海.合成高纯对甲苯磺酸新工艺[J].当代化工,2002,31(4):206-208
[9]徐亮,俞迪虎,陈新志.反应-结晶法生产对甲苯磺酸[J].化学世界,2004(12):647-649
[10]马志军.高纯度对甲苯磺酸合成工艺的研究[J].广西轻工业,2007(11):22-23
[11]赵秀娟,刘焕宏.SO_3磺化甲苯制对甲苯磺酸[J].辽宁工学院学报,2002,22(5):61-62
[12]颜范勇,汪宝和,井欣,张德利,刘邦孚,袁继堂.甲苯三氧化硫磺化反应抑制副产物二甲苯砜的研究[JJ.染料与染色,2004,41(5):276-278
[13]汪宝和,颜范勇,井欣,张德立,马海洪.二甲苯砜加入法抑制甲苯磺化副反应[J].石油化工,2004,33(9):857-860
[14]虞文良,袁琴,邓传芸.甲苯磺化反应工艺条件的实验研究[J].上海应用技术学院学报,2002,2(3):192-195
[15]E.G.汉考克(主编).王杰,白庚辛(译).甲苯二甲苯及其工业衍生物[M].北京:化学工业出版社,1987
[16]M.I.Vinnik,L.D.Abramovich.Kinetics of the Hydrolysis Mesitylenesulfonic Acid with the Sulfonation of Mesitylene in Aqueous solution of Sulfuric Acid[J].Chemical Physics,1972(4):833-840
[17]A.A.Spryskov,V.A.Kizlov.Idem,1969(12):900
[18]Ruedi W.Gygax.Chemical Reaction Engineering for Safety.Chemical Engineering Science,1988,43(8):1759-1771
[19]Ralph N.Landau,Donna G.Blackmond.Scale up Heat Transfer based on Reaction Calorimetry.Chemical Engineering Progress.1994:4343-4348
[20]Ralph N.Landau,Robert S.Cutro.Assess Risk Due to Desired Chemistry.Chemical Engineering Progress.1993:66-71
[21]Alos M A,et al.A New Method for Assessing the Thermal Stability of Semibatch Processes Based on Lyapunov Exponents.Chemical Engineering Science.1996(11):3089-3094
[22]P.Hugo,J.Steinbach,F.Stoessel.Calculation of the Maximum Temperature in Stirred Tank Reactors in Case of a Breakdown of Cooling.Chemical Engineering Science.1988(8):2147-2152
[23]唐培堃.精细有机合成化学及工艺学(第二版)[M].北京:化学工业出版社,2006
[24]赵德丰,程侣柏,姚蒙正,高建荣.精细化学品合成化学与应用[M].北京:化学工业出版社,2001
[25]Allen R.Broyles,Roger E.Eckert.Maximization of the Conversion to m-Toluenesulfonic Acid in Sulfuric Acid.Sulfonation.Ind.Eng.Chem.Process Des.Develop,1973,12(3):295-300
[26]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
[27]张遵,王旭峰,韩琳,王新德.磺化反应工艺研究进展[J].化学推进剂与高分子材料,2007,5(1):38-42
[28]陈荣业.有机合成工艺优化[M].北京:化学工业出版社,2006
[29]Francis Stoessel,Hans Fierz,Pablo Lerena,Gerard Kille.Recent Developments in the Assessment of Thermal Risks of Chemical Processes.Organic Process Research &Development,1997,6(1):428-434
[30]Ruedi W.Gygax.Scale up Principles for Assessing Thermal Runaway Risks.Chemical Engineering Progress,1990:53-60
[31]王晓峰.甲苯一段硝化的工艺优化和过程安全性研究[D].南京理工大学,2005
[32]刘章蕊.半间歇甲苯二段硝化的反应安全性及工艺优化研究[D].南京理工大学,2006
[33]实验室反应量热仪(RCle)操作说明手册,2002
[34]Jacques Wiss,Francis Stoessel,Gerard Kille.Determination of Heats of Reaction under Refluxing Conditions.METTLER TOLEDO Publication 00724385:1-9
[35]Francis Stoessel.Thermal Safety of Chemical Processes[M].WILEY-VCH Verlag GmbH & Co.KGaA,Weinheim,2008
[36]Benjamin J.Littler.Understanding,Evaluating,and Controlling the Hazards of Exothermic Reaction.Technical Reports.2001(17):1-6
[37]傅献彩,沈文霞,姚天扬,侯文华.物理化学(第五版)[M].北京:高等教育出版社,2005
[38]Francis Stoessel.What Is Your Thermal Risk[J].Chemical Engineering Progress,1993(10):67-75
[39]Francis Stoessel.Simulation of Chemical Processes-From the reaction Calorimeter Experiment to the Model.METTLER TOLEDO Publication 00724474:1-6
[40]Fierz.How Industrial Nitrations Were Ran at The Begin of the Century-a look back into the past a study by the RC1 Calorimeter.RC User Forum,1993:1-4
[2]胡寨驿.磺化反应锅爆炸的原因分析及预防[J].锅炉压力容器安全,1989,5(6):41-43
[3]刘铁民,张兴凯,刘功智.安全评价方法应用指南[M].北京:化学工业出版社,2005
[4]中国化工安全卫生技术协会防火防爆专业委员会编译.道化学公司火灾、爆炸危险指数评价方法(第7版),1997
[5]John Barton,Richard Rogers.Chemical Reaction Hazards[M].Institution of Chemical Engineers,1993
[6]王刚.对甲苯磺酸的制备及应用[J].辽宁化工,1995(5):14-16
[7]熊钢.气相磺化法研制对甲苯磺酸[J].泸天化科技,2001(3):243-245
[8]王晓立,田桂芝,孟兆海.合成高纯对甲苯磺酸新工艺[J].当代化工,2002,31(4):206-208
[9]徐亮,俞迪虎,陈新志.反应-结晶法生产对甲苯磺酸[J].化学世界,2004(12):647-649
[10]马志军.高纯度对甲苯磺酸合成工艺的研究[J].广西轻工业,2007(11):22-23
[11]赵秀娟,刘焕宏.SO_3磺化甲苯制对甲苯磺酸[J].辽宁工学院学报,2002,22(5):61-62
[12]颜范勇,汪宝和,井欣,张德利,刘邦孚,袁继堂.甲苯三氧化硫磺化反应抑制副产物二甲苯砜的研究[JJ.染料与染色,2004,41(5):276-278
[13]汪宝和,颜范勇,井欣,张德立,马海洪.二甲苯砜加入法抑制甲苯磺化副反应[J].石油化工,2004,33(9):857-860
[14]虞文良,袁琴,邓传芸.甲苯磺化反应工艺条件的实验研究[J].上海应用技术学院学报,2002,2(3):192-195
[15]E.G.汉考克(主编).王杰,白庚辛(译).甲苯二甲苯及其工业衍生物[M].北京:化学工业出版社,1987
[16]M.I.Vinnik,L.D.Abramovich.Kinetics of the Hydrolysis Mesitylenesulfonic Acid with the Sulfonation of Mesitylene in Aqueous solution of Sulfuric Acid[J].Chemical Physics,1972(4):833-840
[17]A.A.Spryskov,V.A.Kizlov.Idem,1969(12):900
[18]Ruedi W.Gygax.Chemical Reaction Engineering for Safety.Chemical Engineering Science,1988,43(8):1759-1771
[19]Ralph N.Landau,Donna G.Blackmond.Scale up Heat Transfer based on Reaction Calorimetry.Chemical Engineering Progress.1994:4343-4348
[20]Ralph N.Landau,Robert S.Cutro.Assess Risk Due to Desired Chemistry.Chemical Engineering Progress.1993:66-71
[21]Alos M A,et al.A New Method for Assessing the Thermal Stability of Semibatch Processes Based on Lyapunov Exponents.Chemical Engineering Science.1996(11):3089-3094
[22]P.Hugo,J.Steinbach,F.Stoessel.Calculation of the Maximum Temperature in Stirred Tank Reactors in Case of a Breakdown of Cooling.Chemical Engineering Science.1988(8):2147-2152
[23]唐培堃.精细有机合成化学及工艺学(第二版)[M].北京:化学工业出版社,2006
[24]赵德丰,程侣柏,姚蒙正,高建荣.精细化学品合成化学与应用[M].北京:化学工业出版社,2001
[25]Allen R.Broyles,Roger E.Eckert.Maximization of the Conversion to m-Toluenesulfonic Acid in Sulfuric Acid.Sulfonation.Ind.Eng.Chem.Process Des.Develop,1973,12(3):295-300
[26]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
[27]张遵,王旭峰,韩琳,王新德.磺化反应工艺研究进展[J].化学推进剂与高分子材料,2007,5(1):38-42
[28]陈荣业.有机合成工艺优化[M].北京:化学工业出版社,2006
[29]Francis Stoessel,Hans Fierz,Pablo Lerena,Gerard Kille.Recent Developments in the Assessment of Thermal Risks of Chemical Processes.Organic Process Research &Development,1997,6(1):428-434
[30]Ruedi W.Gygax.Scale up Principles for Assessing Thermal Runaway Risks.Chemical Engineering Progress,1990:53-60
[31]王晓峰.甲苯一段硝化的工艺优化和过程安全性研究[D].南京理工大学,2005
[32]刘章蕊.半间歇甲苯二段硝化的反应安全性及工艺优化研究[D].南京理工大学,2006
[33]实验室反应量热仪(RCle)操作说明手册,2002
[34]Jacques Wiss,Francis Stoessel,Gerard Kille.Determination of Heats of Reaction under Refluxing Conditions.METTLER TOLEDO Publication 00724385:1-9
[35]Francis Stoessel.Thermal Safety of Chemical Processes[M].WILEY-VCH Verlag GmbH & Co.KGaA,Weinheim,2008
[36]Benjamin J.Littler.Understanding,Evaluating,and Controlling the Hazards of Exothermic Reaction.Technical Reports.2001(17):1-6
[37]傅献彩,沈文霞,姚天扬,侯文华.物理化学(第五版)[M].北京:高等教育出版社,2005
[38]Francis Stoessel.What Is Your Thermal Risk[J].Chemical Engineering Progress,1993(10):67-75
[39]Francis Stoessel.Simulation of Chemical Processes-From the reaction Calorimeter Experiment to the Model.METTLER TOLEDO Publication 00724474:1-6
[40]Fierz.How Industrial Nitrations Were Ran at The Begin of the Century-a look back into the past a study by the RC1 Calorimeter.RC User Forum,1993:1-4