Kinetics and Mechanism of Hydrothermal Decomposition of Lignin Model Compounds

The kinetics and underlying mechanisms of the hydrothermal decomposition of the lignin model compounds anisole, diphenyl ether and phenethyl phenyl ether were studied. Whereas diphenyl ether was stable at hydrothermal conditions, anisole and phenethyl phenyl ether underwent hydrothermal decomposition between 260 and 290 degrees C. Experiments involving different initial reactant concentrations and different batch holding times revealed that hydrolysis of both anisole and phenethyl phenyl ether followed first-order kinetics. Experiments at different temperatures showed that the first-order rate constants displayed Arrhenius behavior, with activation energies of 149.8 +/- 16.4 and 143.2 +/- 21.0 kJ.mol(-1) for anisole and phenethyl phenyl ether, respectively. A reaction mechanism is proposed for anisole, and reaction pathways for the decomposition of phenethyl phenyl ether are proposed based on the distribution of the products generated by hydrolysis. The reactivity of ether hydrothermal decomposition is discussed by reviewing the published conversion data of other ethers.