V. Anantharaman et Pn. Pintauro, THE ELECTROCATALYTIC HYDROGENATION OF GLUCOSE .2. RANEY-NICKEL POWDERFLOW-THROUGH REACTOR MODEL, Journal of the Electrochemical Society, 141(10), 1994, pp. 2742-2752
A computer model which simulates the operation of a flow-through Raney
nickel powder electrocatalytic hydrogenation reactor for the synthesi
s of sorbitol from glucose with simultaneous H-2 evolution has been de
veloped. The model utilizes porous electrode theory, considers both ma
ss-transfer and surface kinetics effects, and contains no adjustable p
arameters. Hydrogen evolution on Raney nickel is described by a Volmer
-Heyrovsky rate expression. The rate equation for glucose hydrogenatio
n is identical to that for the chemical catalytic synthesis of sorbito
l with pressurized H-2 gas. For constant-current reactor operation, co
mputed sorbitol current efficiencies match well with experimental data
for a range of current densities (0.0053 to 0.021 A/cm2) and glucose
feed concentrations (0.4 to 1.6M), with an average error of 8.8%. Calc
ulations show that a large fraction of adsorbed hydrogen on the nickel
cathode surface is produced by the oxidation of electrogenerated H-2
via the backward Heyrovsky reaction. According to the model, significa
ntly higher sorbitol current efficiencies can be achieved by pulsing t
he current to the reactor.