Safety and Runaway Prevention in Batch and Semibatch Reactors—A Review

In this paper a review of recent developments on safety and runaway prevention in batch and semibatch reactors is given. To prevent thermal runaways in chemical reactors usually three lines of defense have to be considered: choice of the right operating conditions, early warning detection system and system to handle running away reactions. Because of its too specific nature, the last line of defense is not discussed in this review, while the former two are considered in detail. Firstly the capability and applicability of the reaction calorimeter for safety assessments are reviewed, then fundamental safety criteria for safe operation of batch and semibatch reactors are reported and discussed. A review of the most useful and efficient methods for a correct choice of safe operating conditions is split into two cases: one, when the reaction kinetics are known, and when kinetic information is not available. Also several promising recent developments of an early warning detection system for the on-line detection of unexpected situations leading to a thermal runaway are presented.

[1]  Fernanda Strozzi,et al.  A new method for assessing the thermal stability of semibatch processes based on Lyapunov exponents , 1996 .

[2]  R. Landau,et al.  Expanding the role of reaction calorimetry , 1996 .

[3]  J. M. Zaldivar,et al.  Development of a mathematical model and a simulator for the analysis and optimisation of batch reactors: Experimental model characterisation using a reaction calorimeter☆ , 1996 .

[4]  G. Froment,et al.  Parametric sensitivity and runaway in fixed bed catalytic reactors , 1970 .

[5]  J. M. Zaldívar,et al.  Runaway Detection in a Pilot-Plant Facility , 2004 .

[6]  Peter Hugo,et al.  A comparison of the limits of safe operation of a SBR and a CSTR , 1986 .

[8]  W. Regenass,et al.  The Development of Stirred-Tank Heat Flow Calorimetry as a Tool for Process Optimizationand ProcessSafety , 1997, CHIMIA.

[10]  W. Regenass,et al.  The development of heat flow calorimetry as a tool for process optimization and process safety , 1997 .

[11]  Peter Hugo,et al.  Praxisorientierte Darstellung der thermischen Sicherheitsgrenzen für den indirekt gekühlten Semibatch-Reaktor , 1985 .

[12]  Jasbir Singh Reaction calorimetry for process development: Recent advances , 1997 .

[13]  E. Molga,et al.  Modelling and optimization of semibatch toluene mononitration with mixed acid from performance and safety viewpoints , 1992 .

[14]  Giuseppe Maschio,et al.  Sensitivity Analysis in Polymerization Reactions Using the Divergence Criterion , 2004 .

[15]  J. Adler,et al.  The critical conditions in thermal explosion theory with reactant consumption , 1964 .

[16]  F. Strozzi,et al.  Recurrence quantification based Liapunov exponents for monitoring divergence in experimental data , 2002 .

[17]  Giuseppe Maschio,et al.  A general criterion to define runaway limits in chemical reactors , 2003 .

[18]  R. Gygax Chemical reaction engineering for safety , 1988 .

[19]  Fernanda Strozzi,et al.  On-Line Runaway Detection in Batch Reactors Using Chaos Theory Techniques. , 1999 .

[20]  Joseph P. Zbilut,et al.  On-line runaway detection in isoperibolic batch and semibatch reactors using the divergence criterion , 2004, Comput. Chem. Eng..

[21]  J. C. Peterson,et al.  Application of reaction calorimetry toward understanding the large scale chemistry of ethyl diazoacetate , 2001 .

[22]  Massimo Morbidelli,et al.  A generalized criterion for parametric sensitivity: Application to thermal explosion theory , 1988 .

[23]  Philip F. Nolan,et al.  Some lessons from thermal-runaway incidents , 1987 .

[24]  Fernanda Strozzi,et al.  A comparative analysis between temperature and pressure measurements for early detection of runaway initiation , 2004 .

[25]  Fernanda Strozzi,et al.  A general method for assessing the thermal stability of batch chemical reactors by sensitivity calculation based on Lyapunov exponents , 1994 .

[26]  R. W. Gygax Scaleup principles for assessing thermal runaway risks , 1990 .

[27]  C. Orella,et al.  Reaction calorimetry as an in-situ kinetic tool for characterizing complex reactions , 1996 .

[28]  F. Stoessel,et al.  Calculation of the maximum temperature in stirred tank reactors in case of a breakdown of cooling , 1988 .

[29]  E. Molga,et al.  CFD modelling of stirred tank chemical reactors: homogeneous and heterogeneous reaction systems , 2004 .

[30]  Massimo Morbidelli,et al.  Parametric sensitivity in fixed-bed catalytic reactors: the role of interparticle transfer resistances , 1986 .

[31]  Runaway Behaviour and Parametric Sensitivity of a Batch reactor - an experimental study. , 1996 .

[32]  Fernanda Strozzi,et al.  Application of parametric sensitivity to batch process safety: Theoretical and experimental studies , 1996 .

[33]  Fernanda Strozzi,et al.  A method for assessing thermal stability of batch reactors by sensitivity calculation based on Lyapunov exponents: experimental verification , 1994 .

[34]  Herschel Rabitz,et al.  Parametric sensitivity and self-similarity in thermal explosion theory , 1992 .

[35]  D. I. Townsend,et al.  Thermal hazard evaluation by an accelerating rate calorimeter , 1980 .

[36]  Massimo Morbidelli,et al.  A generalized criterion for parametric sensitivity: application to a pseudohomogeneous tubular reactor with consecutive or parallel reactions , 1989 .

[37]  K. Reichert,et al.  Reaction calorimeter a contribution to safe operation of exothermic polymerizations , 1988 .

[38]  V. Balakotaiah,et al.  Runaway limits for homogeneous and catalytic reactors , 1995 .

[39]  R. Gesthuisen,et al.  Determining the best reaction calorimetry technique: theoretical development , 2005, Comput. Chem. Eng..

[40]  D. D. Perlmutter Stability of chemical reactors , 1972 .

[41]  B. Srinivasan,et al.  The use of calorimetry for on-line optimisation of isothermal semi-batch reactors , 2001 .

[42]  Klaas R. Westerterp,et al.  The nitric acid oxidation of 2-octanol. A model reaction for multiple heterogeneous liquid-liquid reactions , 2000 .

[43]  P. D. Filippis,et al.  Thermal hazard in a batch process involving hydrogen peroxide , 2002 .

[44]  Eugeniusz Molga,et al.  No more runaways in fine chemical reactors , 2004 .

[45]  Konrad Hungerbühler,et al.  Isothermal reaction calorimetry as a tool for kinetic analysis , 2004 .

[46]  Hans Schuler,et al.  Calorimetric-state estimators for chemical reactor diagnosis and control: review of methods and applications , 1992 .

[47]  Hua Wu,et al.  Parametric sensitivity in chemical systems , 1999 .

[48]  Joseph P. Zbilut,et al.  Early warning detection of runaway initiation using non-linear approaches , 2005 .

[49]  Klaas R. Westerterp,et al.  Runaway behavior and thermally safe operation of multiple liquid–liquid reactions in the semi-batch reactor: The nitric acid oxidation of 2-octanol , 2002 .

[50]  Eugeniusz Molga,et al.  CFD modelling and divergence criterion for safety of chemical reactors , 2005 .

[51]  K. Roel Westerterp,et al.  Thermally Safe Operation of a Semibatch Reactor for Liquid-Liquid Reactions - Fast Reactions , 1991 .

[52]  Hélène Nogent,et al.  The differential reaction calorimeter: a simple apparatus to determine reaction heat, heat transfer value and heat capacity , 2002 .

[53]  S. Pushpavanam,et al.  Parametric Sensitivity, Runaway, and Safety in Batch Reactors: Experiments and Models , 1994 .

[54]  Renato Rota,et al.  Thermally safe operation of liquid–liquid semibatch reactors Part II: Single diffusion controlled reactions with arbitrary reaction order , 2005 .

[55]  Rosa Nomen,et al.  Maximum temperature attainable by runaway of synthesis reaction in semibatch processes , 1997 .

[56]  O. Ubrich,et al.  Safety Assessment and Optimization of Semi-batch Reactions by Calorimetry , 2001 .

[57]  Klaas R. Westerterp,et al.  Thermally safe operation of a semibatch reactor for liquid-liquid reactions. Slow reactions , 1990 .

[58]  P. Lerena,et al.  Assessment of hazards linked to accumulation in semi-batch reactors , 1996 .

[59]  L. Hub,et al.  Early on‐line detection of exothermic reactions , 1986 .

[60]  Francis Stoessel,et al.  Optimal Feed Profile for a Second-order Reaction in a Semi-batch Reactor under Safety Constraints - Experimental Study , 1999 .