화학공학소재연구정보센터
Chemical Engineering Journal, Vol.207, 539-551, 2012
Mass transfer and kinetics of H2O2 direct synthesis in a batch slurry reactor
A model of a gas bubbling, batch slurry reactor for H2O2 direct synthesis is presented. Experimental measurements were carried out in the absence of halides and acids at temperatures between 258 and 297 K (pressures 14-20 bar, depending on temperature) with H-2 and O-2 diluted in CO2 outside flammability limits (gas phase composition of CO2, O-2 and H-2 was 77%, 21% and 2%, respectively). Kinetic experiments performed on a commercial 5% Pd/C catalyst (0.15 g in 400 ml methanolic solution) have been used to identify the intrinsic kinetics and assess the influence of mass transfer. The simplest rate equations compatible with the acknowledged reaction network has been included in a reactor model, which accounts for mass transfer resistances between gas and liquid and bulk of the liquid-catalyst surface. The corresponding Arrhenius parameters were estimated from direct synthesis experiments for all the reactions. Comparable temperature dependence was observed for H2O production, hydrogenation and decomposition (activation energies close to 45 kJ mol(-1)), while H2O2 synthesis has a much lower activation energy (close to 24 kJ mol(-1)), suggesting that a higher selectivity is achievable at low temperature. Decomposition had a very limited influence on the overall peroxide production rate, being quite slow (its rate is approx. 40% the direct synthesis rate at H-2 full conversion). Hydrogenation was the most rapid side reaction, depressing H2O2 production as H-2 conversion increased. Independent investigation on the H2O2 hydrogenation in the absence of O-2 highlighted significant difference in the kinetics, apparently due to a different oxidation state of the catalyst. A sensitivity analysis on the mass transfer coefficients to allow for uncertainties in the correlations proved that no resistances in the liquid occur, while gas-liquid H-2 transfer rate may be limiting, although unlikely, requiring that literature coefficients overestimates the real transfer rate by an order of magnitude. (C) 2012 Elsevier B.V. All rights reserved.