Toward an inherently safer design and operation of batch and semi-batch processes: The N-oxidation of alkylpyridines

Abstract This work shows an application of inherent safety principles to a reaction widely used in the pharmaceutical industry. More specifically, it incorporates the teachings of Trevor Kletz into the design of an inherently safer process for the N -oxidation of alkylpyridines. This reaction is of interest because of the hazards resulting from the undesired, gas-generating decomposition of hydrogen peroxide, the oxidizing agent. The generation of oxygen, combined with the flammability of the alkylpyridines, represents a serious fire and explosion hazard for this process. The purpose of this paper is to demonstrate how an inherently safer process can be potentially achieved by designing improved reactors and by assessing conditions that reduce or eliminate the hazards. Furthermore, it is shown that such improvement in safety increases the efficiency of the process and results in a cost reduction.

[1]  D. W. Mosley,et al.  Screen Reactive Chemical Hazards Early in Process Development , 2000 .

[2]  M. Papadaki Use of Reaction Calorimetry in Thermal Risk Assessment Studies and Safe Design of Batch Reactions That Can Lead to a Runaway: Application on Hydrogen Peroxide , 2004 .

[3]  E. Scriven,et al.  Pyridine and Pyridine Derivatives , 2005 .

[4]  A. Miyake,et al.  Influence of heavy metal ion on the thermal explosion of hydrogen peroxide , 2006 .

[5]  Rosa Nomen,et al.  Modelling of the reaction of N-oxidation of 2-methylpyridine using hydrogen peroxide and a complex metal catalyst , 1998 .

[6]  Tariq Mahmud,et al.  Catalytic decomposition of hydrogen peroxide in the presence of alkylpyridines: Runaway scenarios studies , 2005 .

[7]  David J. Leggett Safe process development from reaction hazards testing , 2001 .

[8]  Trevor Kletz Inherently Safer Design—Its Scope and Future , 2003 .

[9]  William K. Lutz,et al.  Take chemistry and physics into consideration in all phases of chemical plant design , 1995 .

[10]  Rosa Nomen,et al.  Sensitivity analysis of the 2-methylpyridine N-oxidation kinetic model , 2002 .

[11]  I. Kozhevnikov Advances in Catalysis by Heteropolyacids , 1987 .

[12]  R. Sheldon CATALYSIS AND POLLUTION PREVENTION , 1997 .

[13]  M. Kumasaki An explosion of a tank car carrying waste hydrogen peroxide , 2006 .

[14]  M. Papadaki,et al.  Global kinetic model: a case study on the N-oxidation of alkylpyridines. , 2006, Journal of hazardous materials.

[15]  J. P. Lacoursiere Pe An explosion caused by mixing incompatible liquids , 2005 .

[16]  Peter Urben Bretherick's Handbook of Reactive Chemical Hazards , 2013 .

[17]  David L. Baker,et al.  Hydrogen Peroxide Accidents and Incidents: What We Can Learn From History , 2005 .

[18]  M S Mannan,et al.  Prediction of reactive hazards based on molecular structure. , 2003, Journal of hazardous materials.

[19]  Trevor Kletz Process Plants: A Handbook for Inherently Safer Design , 1998 .

[20]  Trevor Kletz Inherently safer plants: An update , 1991 .

[21]  William J. Rogers,et al.  2-Methylpyridine-N-oxidation runaway studies , 2009 .

[22]  William L. Wehrum Case study of a hydrogen peroxide related deflagration in a wastewater treatment tank , 1993 .

[23]  J. Keggin The Structure and Formula of 12-Phosphotungstic Acid , 1934 .

[24]  R. Andon,et al.  896. Phase relationships in the pyridine series. Part I. The miscibility of some pyridine homologues with water , 1952 .

[25]  Thomas C. Melvin,et al.  European Patent Office , 2002 .

[26]  Ccps Inherently Safer Chemical Processes: A Life Cycle Approach , 2008 .

[27]  Saenz Noval,et al.  Evaluation of Alternatives for Safer and More Efficient Reactions: A study of the N-oxidation of Alkylpyridines , 2012 .

[28]  Maria Papadaki,et al.  Kinetic models of complex reaction systems , 2005, Comput. Chem. Eng..

[29]  M. Papadaki,et al.  Inherently Safer Reactor Design for Complex Reactions Based on Calorimetry Studies , 2011 .

[30]  John Mackenzie Considerations for the safe design of processes using hydrogen peroxide and organics , 1991 .

[31]  Trevor Kletz,et al.  Inherently safer plants , 1985 .

[32]  M. Papadaki,et al.  Towards Improved Reaction Runaway Studies: Kinetics of the N-Oxidation of 2-Methylpyridine Using Heat-flow Calorimetry , 2002 .

[33]  S. Unwin,et al.  Essential Practices for Managing Chemical Reactivity Hazards , 2003 .