In search of efficient catalysts and appropriate reaction conditions for gas phase nitration of benzene

Abstract

The present paper is dedicated to the development of a method for the nitrobenzene production using solid acid catalysts, as an alternative to industrial nitration, based on a mixture of concentrated acids. The influence of key parameters of the nitration process (temperature, reagent flow rate, nitrating agent concentration etc.) on the conversion of the initial substrate, the degree of decomposition of nitric acid and the quantity ofresulting oxygenates was studied. Recommendations for the selection of effective catalytic systems (high content of Brønsted acid sites with Ho < −4, high specific surface and resistance to HNO3) were developed and the best conditions for process reactions (temperature 200 °C, aqueous solution of nitric acid with concentration of 30 wt%, “nitric acid:benzene” ratio = 0.76) were found. A method for regeneration of the catalytic activity without unloading the catalyst was proposed. As an example, MoO3/SiO2 sample was tested in a dual-mode nitration/regeneration process, which allowed us to increase the flow rates of reagents and obtain catalyst efficiency of up to STY = 4.09 g/(gcat · h). Several of the most promising catalysts (MoO3/SiO2, WO3/ZrO2 and Nafion/support composite) for the process were tested in identical conditions.