Reaction Process of Resin-Catalyzed Methyl Formate Hydrolysis in Biphasic Continuous Flow

In the frame of process development for the generation of chemical energy carriers, we studied the synthesis of methanol and formic acid from methyl formate hydrolysis in a continuous-flow millireactor. The aim was to establish the link between kinetics and phase behavior in the biphasic liquid regime. Reaction performance using the acidic ion-exchange resin Amberlyst 15 as catalyst was examined at various operating conditions such as space velocity, catalyst particle size, temperature, and initial reactant ratio. Results revealed substantially higher yields without mass transfer impediment with feed compositions exceeding methyl formate saturation in water. The simultaneous decrease in methyl formate and increase in polar product concentrations sufficed to bring the initially biphasic mixture to a homogeneous system as confirmed by thermodynamic UNIFAC equilibrium calculations. The separate analysis of effluent liquid phases unveiled a quasi homogeneous catalytic process rooted in an aqueous layer at the resin surface, independent of the organic content. The fast and continuous synthesis of these chemicals constitutes a promising application for the development of direct fuel cells for portable power devices.