The liquid phase oxidation of glycerol was performed producing fine organic acids. Catalysts based on Pt, Pd and Bi supported on activated carbon were employed to perform the conversion of glycerol into organic acids at 313 K, 323 K and 333 K, under atmospheric pressure (1.0 bar), in a mechanically agitated slurry reactor (MASR). The experimental results indicated glycerol conversions of 98% with production of glyceric, tartronic and glycolic acids, and dihydroxyacetone. A yield of glyceric acid of 69.8%, and a selectivity of this compound of 70.6% were reached after 4 h of operation. Surface mechanisms were proposed and rate equations were formulated to represent the kinetic behavior of the process. Selective formation of glyceric acid was observed, and the kinetic parameter values indicated the lowest activation energy (38.5 kJ/mol) for its production reaction step, and the highest value of the adsorption equilibrium constant of the reactant glycerol (10-4 dm³/mol)
13 August 2010 in Reaction Kinetics, Mechanisms and Catalysis
The transient behavior in a three-phase trickle bed reactor system (N2/H2O-KCl/activated carbon, 298 K, 1.01 bar) was evaluated using a dynamic tracer method. The system operated with liquid and gas phases flowing downward with constant gas flow Q G = 2.50 x 10-6 m³ s-1 and the liquid phase flow (Q L) varying in the range from 4.25x10-6 m³ s-1 to 0.50x10-6 m³ s-1. The evolution of the KCl concentration in the aqueous liquid phase was measured at the outlet of the reactor in response to the concentration increase at reactor inlet. A mathematical model was formulated and the solutions of the equations fitted to the measured tracer concentrations. The order of magnitude of the axial dispersion, liquid-solid mass transfer and partial wetting efficiency coefficients were estimated based on a numerical optimization procedure where the initial values of these coefficients, obtained by empirical correlations, were modified by comparing experimental and calculated tracer concentrations. The final optimized values of the coefficients were calculated by the minimization of a quadratic objective function. Three correlations were proposed to estimate the parameters values under the conditions employed. By comparing experimental and predicted tracer concentration step evolutions under different operating conditions the model was validated.