Batch salicylic acid nitration by nitric acid/acetic acid mixture under isothermal, isoperibolic and adiabatic conditions

Runaway phenomena and thermal explosions can originate during the nitration of salicylic acid by means of a nitric acid/acetic acid mixture when the thermal control is lost, mainly as a result of the formation and thermal decomposition of picric acid. The prediction of the behaviour of this system is thus of great importance in view of possible industrial applications and the need to avoid the occurrence of unwanted dangerous events. During a previous investigation a model was developed to simulate its behaviour when the starting concentration of the substrate is too low, thus, preventing the precipitation of poor soluble intermediates. In this work this model is extended to deal with more concentrated systems even in case of a solid phase separating during the process. To this purpose the previously assessed dependence of the solubility of 3-nitro and 5-nitrosalicylic acids upon temperature and nitric acid concentration is included in the model. It is assumed that when 3-nitro and 5-nitrosalicylic acids are partially suspended in the reacting medium a kinetic regime of "dissolution with reaction" is established; that is, the redissolution of these species is a fast process compared to the successive nitration to give dinitroderivatives. Good results are obtained in the comparison of the experimental data with those calculated both in isoperibolic and adiabatic conditions when the revised model is used. (c) 2006 Elsevier B.V. All rights reserved.