Emulsion Polymerization of Butyl Acrylate: Safe Optimization Using Topological Criteria

Fast and strongly exothermic emulsion polymerization processes are particularly difficult to optimize from both safety and productivity points of view because of the occurrence of a number of undesired side reactions (e.g., propagation of tertiary radicals, chain transfer to monomer, backbiting, termination by disproportionation, etc.) and the triggering of boiling phenomena with consequent stable foam formation under atmospheric pressure. Therefore, it would be useful to develop a suitable combined theoretical and experimental procedure able to detect both the optimum process dosing time and initial reactor temperature. In this work, it is discussed how an extended version of the topological criterion theory, originally developed for isoperibolic semibatch reactors, can be used to safely optimize an indirectly cooled isothermal semibatch reactor. Moreover, such a methodology is applied to a case study represented by the synthesis of poly(butyl acrylate) through the radical emulsion polymerization of buty...

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

[2]  Eugeniusz Molga,et al.  Safety and Runaway Prevention in Batch and Semibatch Reactors—A Review , 2006 .

[3]  R Rota,et al.  Emulsion polymerization of vinyl acetate: safe optimization of a hazardous complex process. , 2011, Journal of hazardous materials.

[4]  Marco Derudi,et al.  Safe Optimization of 2-octanol Oxidation and Vinyl Acetate Emulsion Polymerization , 2012 .

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

[6]  Sabine Beuermann,et al.  Rate coefficients of free-radical polymerization deduced from pulsed laser experiments , 2002 .

[7]  Fernanda Strozzi,et al.  Generalized Criteria for Boundary Safe Conditions in Semi-Batch Processes: Simulated Analysis and Experimental Results. , 1998 .

[8]  A. N. Nikitin,et al.  Determination of Intramolecular Chain Transfer and Midchain Radical Propagation Rate Coefficients for Butyl Acrylate by Pulsed Laser Polymerization , 2007 .

[9]  Mark S. M. Alger,et al.  Polymer Science Dictionary , 1989 .

[10]  José M. Asua,et al.  Critically Evaluated Rate Coefficients for Free‐Radical Polymerization, 5, , 2004 .

[11]  L. Gigante,et al.  Simple Procedure for Optimally Scaling-up Fine Chemical Processes. I. Practical Tools , 2009 .

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

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

[14]  Marco Derudi,et al.  Topological Criterion To Safely Optimize Hazardous Chemical Processes Involving Arbitrary Kinetic Schemes , 2011 .

[15]  Maria Francesca Milazzo,et al.  Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol , 2012 .

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

[17]  Renato Rota,et al.  Temperature diagrams for preventing decomposition or side reactions in liquid–liquid semibatch reactors , 2006 .

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

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

[20]  Yildirim H. Erbil.  Vinyl Acetate Emulsion Polymerization and Copolymerization with Acrylic Monomers , 2000 .

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

[22]  K. R. Westerterp,et al.  Thermally safe operation of a cooled semi-batch reactor: slow liquid-liquid reactions , 1988 .

[23]  Marco Derudi,et al.  Topological criteria to safely optimize hazardous chemical processes involving consecutive reactions , 2010 .

[24]  P. Lagally,et al.  Zur polymerisation des methacrylsäuremethylesters1 , 1948 .

[25]  Marco Derudi,et al.  Experimental Design of Topological Curves to Safely Optimize Highly Exothermic Complex Reacting Systems , 2011 .

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

[27]  C. Chern,et al.  Emulsion polymerization mechanisms and kinetics , 2006 .