Supercritical water oxidation of quinoline in a continuous plug flow reactor - part 2: kinetics

摘要

The results of a detailed investigation into the kinetics of quinoline oxidation in supercritical water are presented. The novel kinetic data presented were obtained in a continuously operated, plug flow reactor where parameters such as temperature, pressure, residence time and stoichiometric ratio of oxidant to quinoline were investigated and detailed in the companion paper (Pinto LDS, Freitas dos Santos IMF, Al-Duri B and Santos RCD, Supercritical water oxidation of quinoline in a continuous plug flow reactor - part 1: effect of key operating parameters. J Chem Technol Biotechnol). An induction time was experimentally observed, ranging from 1.5 to 3.5 s, with longer times observed in experiments carried out at lower temperatures. A pseudo-first-order rate expression with respect to quinoline concentration (with oxygen excess) was first adopted and the activation energy of 234 kJ mol(-1) and a pre-exponential factor of 2.1 x 10(14) s(-1) were estimated. Furthermore, an integral power rate model expression was established, attributing a reaction order for quinoline as I and for oxygen as 0.36. An activation energy and preexponential factor for this model were determined as 224 kJ mol(-1) and 3.68 x 10(14) M-0.36 s(-1), respectively. A global rate expression was then regressed for the quinoline reaction rate from the complete set of data. The resulting activation energy was 226 +/- 19 kJ mol(-1) and the pre-exponential factor was 2.7 x 10(13 +/- 12) M-0.1 s(-1). The reaction orders for quinoline and oxygen were 0.8 +/- 0.1 and 0.3 +/- 0.1, respectively. It was shown that the least-squares regression method provided the best-fit model for experimental results investigated in this study. (c) 2006 Society of Chemical Industry.