Thermal Hazards of Chemical Reactions: (v. 4 Industrial Safety Series)

Exothermic reactions used for the production of chemicals present a hazard if they proceed without control. Runaway reactions can result in a blow-off of the reactor top and an emission of reactants and products, possibly followed by a gas explosion. Undesired exothermic reactions initiated during production, purification or storage by excessive temperatures or other causes have similar destructive effects, even if the origin is different. Although the hazards connected with exothermic reactions have been known since the inception of the chemical industry, a systematic knowledge of the possible effects has only been developed in the last 25 years. A number of incidents in the chemical industry, which have been investigated by groups of experts from various companies, have promoted the understanding of these hazards. The author has investigated incidents in plants and tested experimental methods for more than 20 years. In particular he was interested in collecting and comparing safety-relevant data of products. At the end of his industrial career he now believes that it is important to pass on information about this field of activity to younger colleagues who are interested in the safety of chemical plants. The purpose of this book is to provide a basis for understanding the hazards arising from exothermic reactions. Knowledge of the relevant properties is necessary for a safe processing of products and mixtures. The test methods which have been used and developed together with the increasing understanding of the hazards of reactions are particularly important. A critical. survey of extensive experimental techniques is provided.

Table of Contents:
1. Introduction. Explosion types, methods of investigation and estimation. Primary and secondary reactions. Characteristic data of exothermic reactions. Incidents involving exothermic reactions. Interpretation of test results and the application to the thermal safety of a process. The common understanding of the risks of reactions. 2. Phenomenology of Explosions in Reacting Systems. Primary and secondary reactions. Exothermic decomposition. Autocatalytic reactions. Thermal explosion. Deflagration of condensed material. Detonation of condensed material. 3. Test Methods for Exothermic Decomposition and Secondary Reactions. Temperature-programmed methods. Isothermal methods. Self-heating tests. Gas evolution and pressure rise. Deflagration tests. Detonation and explosive properties. 4. Discussion of Characteristic Data of Exothermic Decomposition. Decomposition energies. Kinetics of decomposition reactions. Comparison of published results. Methods of calculating characteristic data from other measurements. 5. Exothermic Secondary Reactions. Exothermic decomposition of mixtures. Catalysis of exothermic decomposition. Typical exothermic secondary reactions. Various exothermic secondary reactions. Exothermic reactions with hypergolic ignition. 6. Primary Reactions. The thermal potential of a reaction. A first survey over a primary reaction. Reaction kinetics: Principle and evaluation of measurements. Experimental methods for liquid reaction kinetics. Secondary reactions combined with primary reaction. Runaway reactions. 7. Incidents in Chemical Processes. A general survey about industrial incidents. Discussion of particular incidents. 8. Thermal Explosion and Runaway under Practical Conditions. The conditions for thermal instability in dependence of the reaction or process type. The last stage of thermal explosion and deflagration. 9. Thermal Hazard Evaluation of Chemical Reactions. The identification of hazards. Investigation and assessment of secondary reactions. Safe design of primary reactions. 10. Safety Relevant Data Of Substances. List of symbols. Author index. Subject index.