Linking Catalyst Development and Chemical Reactor Design with Ethanol to Butadiene Processes

This study explores the relation between catalyst research and chemical reaction engineering for developing ethanol to butadiene (ETB) technologies. An ETB process involves two distinct steps: ethanol dehydrogenation to acetaldehyde and butadiene synthesis. The catalyst functions can be tailored separately or imbedded in a single formulation, leading to two-stage and one-stage processes. The performance of selected ETB catalysts is confronted with predictions based on chemical equilibrium, considering the simultaneous formation of products, by-products and impurities. The analysis shows that, essentially, the performance of ETB catalysts is controlled by kinetic factors. A shortlist of relevant catalysts for industrial implementation is proposed. The analysis highlights two key issues for industrial reactor design: catalyst deactivation/regeneration and the use of inert gas as a major process cost. The first issue is addressed by developing a comprehensive fluidized bed reactor model operating in the bubbling regime, capable of handling complex reaction kinetics. Good performance close to plug flow is obtained with bubbles at a size of 4 to 8 cm and with intensive mass transfer. The simulation reveals an autocatalytic effect of acetaldehyde on the butadiene formation favored by a well-mixed dense phase. The second study investigates the optimization of the chemical reaction section in a reactor–separation–recycle system via economic potential. The costs associated with the catalytic reactor and the catalyst charge, including regeneration, along with the costs of recycling reactants and of an inert gas if used, are key factors in determining the optimal operation region. This approach, verified by simulation in Aspen PlusTM, points out that better robustness and a limited use of an inert gas are necessary for developing industrial catalysts for the one-stage ETB process.