Thermal risk in semi-batch reactors: The epoxidation of soybean oil

Abstract The interest in the epoxidation of vegetable oils is constantly growing in the chemical industry. The most common process is based on the oxidation of the unsaturated bonds by peroxyacids generated in situ, in the water phase, using concentrated hydrogen peroxide and the corresponding organic acid in presence of a mineral acid as catalyst. The overall epoxidation reaction is highly exothermic, hence operating conditions should be always addressed by safety considerations related to the possibility of runaway reactions. In this paper, best operating conditions and safety considerations have been defined for a complex reaction network for the epoxidation of soybean oil, which includes the decomposition reactions of the performic acid generated during the epoxidation. Furthermore, sensitivity-based reactor stability criteria have been applied and compared, for the design of an adequate Early Warning Detection System for the process.

[1]  V. Goud,et al.  Epoxidation of karanja (Pongamia glabra) oil by H2O2 , 2006 .

[2]  C. Crua,et al.  Thermal risk assessment of vegetable oil epoxidation , 2015, Journal of Thermal Analysis and Calorimetry.

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

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

[5]  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 .

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

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

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

[9]  M. Janković,et al.  Epoxidation of castor oil with peracetic acid formed in situ in the presence of an ion exchange resin , 2012 .

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

[12]  Johan Wärnå,et al.  Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method , 2016 .

[13]  V. Casson,et al.  Screening Analysis for Hazard Assessment of Peroxides Decomposition , 2012 .

[14]  G. Maschio,et al.  Investigation of an accident in a resins manufacturing site: the role of accelerator on polymerisation of methyl methacrylate. , 2014, Journal of hazardous materials.

[15]  Wolfgang Wagner,et al.  A New Equation of State and Tables of Thermodynamic Properties for Methane Covering the Range from the Melting Line to 625 K at Pressures up to 100 MPa , 1991 .

[16]  V. Casson,et al.  Hydrogen Peroxide Decomposition Analysis by Screening Calorimetry Technique , 2012 .

[17]  Xuebing Zhao,et al.  Kinetics of Formic Acid-autocatalyzed Preparation of Performic Acid in Aqueous Phase , 2011 .

[18]  C. Shu,et al.  Thermal decomposition of hydrogen peroxide in the presence of sulfuric acid , 2008 .

[19]  Ernesto Salzano,et al.  Assessing the Severity of Runaway Reactions , 2016 .

[20]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[22]  C. Marzzacco.  The Enthalpy of Decomposition of Hydrogen Peroxide: A General Chemistry Calorimetry Experiment , 1999 .

[23]  C. A. Ward,et al.  Kinetics of Evaporation: Statistical Rate Theory Approach , 2005 .

[24]  A. Campanella,et al.  High yield epoxidation of fatty acid methyl esters with performic acid generated in situ , 2008 .

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

[26]  Wei Chen,et al.  Mass transfer and reaction kinetics of soybean oil epoxidation in a formic acid‐autocatalyzed reaction system , 2016 .

[27]  M. Serio,et al.  A biphasic model describing soybean oil epoxidation with H2O2 in a fed-batch reactor , 2011 .

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