Oxidation kinetics of methylphosphonic acid in supercritical water : experimental measurements and model development

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, February 2004.Includes bibliographical references.(cont.) at well-defined operating conditions and to develop. both microscopic and macroscopic models, ranging from regressed global models to an elementary reaction mechanism, to quantify MPA oxidation kinetics in supercritical water. MPA hydrolysis and oxidation rates were experimentally measured in a laboratory-scale plug flow reactor. The effects of MPA concentration (0.5 to 1.0 mM), oxygen concentration (1.0 to 3.8 mM), temperature (478 to 572⁰C) and pressure (138 to 277 bar) on oxidation rates were determined for residence times ranging from 3.0 to 9.5 s. Conversion due to hydrolysis was less than 6% after [tau]=7 s at all temperatures studied. For [tau]=7 s at stoichiometric conditions and P=246 bar, low conversion (X<30% at [tau]=10 s) was observed at T