动力学控制的对氯三氟甲苯硝化反应热危险性研究
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摘要
为了研究动力学控制的半间歇硝化反应过程中的放热可能造成的危险,以对氯三氟甲苯硝化反应为例,使用反应量热仪(RC1e)研究硝酸过用率、反应温度对目的反应放热的影响,对工艺放热过程进行危险性分析,并提出优化工艺条件。结果表明:该硝化反应搅拌速率到达300 r/min级以上时,反应不受搅拌速率影响;反应速率随反应温度的增高而降增,热累积度便随反应温度的增高而降增;改变对氯三氟甲苯投入量,单位质量放热量随硝酸过用率的减小而减少,反应热失控风险降低。综合分析优化条件下该反应危险严重度,属于"中级"危险。
The thermal hazard of exothermic nitration reactions with single kinetic control in semi-batch reactors,such as nitration of 4-chlorobenzotrifluoride,was analyzed by Reactor Calorimeter(RC1).The influence of overuse ratio of nitric acid and temperature on heat release rate was investigated. According to thermal analysis of reaction under different operation conditions, optimal process conditions were proposed. The results showed that the influence of stirring speed could be neglected, if its value exceeded 300 rpm;With the increase of temperature, the reaction rate accelerated and thermal accumulation decreased; The unit mass heat release decreased with decreasing of overuse ratio of nitric acid, as a result, the risk of thermal runaway reduced. Under optimal operation conditions,the severity of nitration of 4-chlorobenzotrifluoride was ‘medium'.
The thermal hazard of exothermic nitration reactions with single kinetic control in semi-batch reactors,such as nitration of 4-chlorobenzotrifluoride,was analyzed by Reactor Calorimeter(RC1).The influence of overuse ratio of nitric acid and temperature on heat release rate was investigated. According to thermal analysis of reaction under different operation conditions, optimal process conditions were proposed. The results showed that the influence of stirring speed could be neglected, if its value exceeded 300 rpm;With the increase of temperature, the reaction rate accelerated and thermal accumulation decreased; The unit mass heat release decreased with decreasing of overuse ratio of nitric acid, as a result, the risk of thermal runaway reduced. Under optimal operation conditions,the severity of nitration of 4-chlorobenzotrifluoride was ‘medium'.
引文
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[24]王双.对氯三氟甲苯的硝基衍生物合成研究[D].南京理工大学,2008.
[25]Zaldívar J M,Molga E,Alós M A,et al.Aromatic nitrations by mixed acid.Fast liquid-liquid reaction regime[J].Chemical Engineering&Processing Process Intensification,1995,35(6):543-559.
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[27]陈利平.甲苯硝化反应热危险性的实验与理论研究[D].南京理工大学,2009.
[28]Krause J P,Mock R,Gheorghe A V.Assessment of risks from technical systems:integrating fuzzy logic into the Zurich Hazard Analysis method[J].International Journal of Environment&Pollution,1995,5(5):278-296.
[2]Stoessel F,Ubrich O.Safety Assessment and Optimization of Semi-batch Reactions by Calorimetry[J].Journal of Thermal Analysis and Calorimetry,2001,64(1):61-74.
[3]Stoessel F.Planning protection measures against runaway reactions using criticality classes[J].Process safety and environmental protection,2009,87(2):105-112.
[4]弗朗西斯·施特塞尔.化工工艺的热安全:风险评估与工艺设计[M].北京:科学出版社,2009:51-80.
[5]刘涛,刘强.2-氟-4-氯-5-甲氧羰基甲硫基苯基异硫氰酸酯合成工艺的研究[J].当代化工,2013(5):669-672.
[6]周奕杉.甲苯一段硝化反应热失控历程研究[D].南京理工大学,2015.
[7]Chen L P,Liu T T,Yang Q,et al.Thermal hazard evaluation fo r iso-octanol nitration with mixed acid[J].Journal of Loss Preve ntion in the Process Industries,2012,25(3):631-635.
[8]Yang T,Chen L,Chen W,et al.Thermal stability of 2-ethylhex yl nitrate with acid[J].Journal of Thermal Analysis&Calorimet ry,2015,119(1):205-212.
[9]Westerterp K.R,Lewak M,Molga E.J,et al.Boundary diagrams s afety criterion for liquid phase homogeneous semibatch reactors[J].Ind.Eng.Chem.Res.2014,53:5778-5791.
[10]Francesco M,Renato R,et al.Temperature diagrams for preventing decomposition or side reactions in liquid-liquid semibatch reactors[J].Chemical Engineering Science,2006,61(10):3068-3078.
[11]Guo Z,Chen L,Chen W.Development of Adiabatic Criterion f or Runaway Detection and Safe Operating Condition Designing in Semibatch Reactors[J].Industrial&Engineering Chemistry Research,2017,56(50):14771-14780.
[12]陈利平,陈网桦,李春光,等.混酸中甲苯半间歇硝化过程的危险性研究[J].中国安全科学学报,2007,17(12):102-106.
[13]Maestri F,Rota R.Thermally safe operation of liquid-liquid se mibatch reactors.Part I:Single kinetically controlled reactions with arbitrary reaction order[J].Chemical Engineering Science,2005,60(12):3309-3322.
[14]Maestri F,Rota R.Thermally safe operation of liquid-liquid se mibatch reactors Part II:Single diffusion controlled reactions wi th arbitrary reaction order[J].Chemical Engineering Science,2005,60(20):5590-5602.
[15]Maestri F,Rota R.Kinetic-free safe optimization of a semibatch runaway reaction:the nitration of 4-chloro benzotrifluoride[J].Industrial&Engineering Chemistry Research,2016,55(50):925-933.
[16]刘纯,潘旭海,陈发明,等.硝酸氧化仲辛醇液液非均相反应过程热危险性分析[J].南京工业大学学报(自然科学版),2011,33(2):104-108.
[17]姜君,江佳佳,蒋军成,等.过氧化苯甲酰合成工艺热危险性分析[J].安全与环境学报,2017,17(2):439-445.
[18]王韶旭,谭志诚,车如心,等.丹酚酸B的热稳定性及其热分解动力学研究[J].化学学报,2012,70(2):212-216.
[19]Copelli S,Derudi M,Cattaneo C S,et al.Synthesis of 4-Chlor o-3-nitrobenzotrifluoride:Industrial thermal runaway simulation due to cooling system failure[J].Process Safety&Environment al Protection,2014,92(6):659-668.
[20]程隆新.三氟甲基农药的开发进展[J].现代农药,2004,3(3):7-11.
[21]Ismail F M D.Important Fluorinated Drugs in Experimental and Clinical Use[J].Journal of Fluorine Chemistry,2003,34(11):27-33.
[22]Borchardt H J,Daniels F.The Application of Differential Ther mal Analysis to the Study of Reaction Kinetics1[J].Journal of the American Chemical Society,1957,79(1):1179-98.
[23]Maestri F,Copelli S,Rota R,et al.Simple Procedure for Opti mal Scale-up of Fine Chemical Processes.II.Nitration of 4-Chl orobenzotrifluoride[J].Industrial&Engineering Chemistry Resea rch,2009,48(3):1316-1324.
[24]王双.对氯三氟甲苯的硝基衍生物合成研究[D].南京理工大学,2008.
[25]Zaldívar J M,Molga E,Alós M A,et al.Aromatic nitrations by mixed acid.Fast liquid-liquid reaction regime[J].Chemical Engineering&Processing Process Intensification,1995,35(6):543-559.
[26]Zaldívar J M,Molga E,Alós M A,et al.Aromatic nitrations b y mixed acid.Slow liquid-liquid reaction regime[J].Chemical Engineering&Processing Process Intensification,1995,34(5):543-559.
[27]陈利平.甲苯硝化反应热危险性的实验与理论研究[D].南京理工大学,2009.
[28]Krause J P,Mock R,Gheorghe A V.Assessment of risks from technical systems:integrating fuzzy logic into the Zurich Hazard Analysis method[J].International Journal of Environment&Pollution,1995,5(5):278-296.