Kinetics of ethanol hydrochlorination over γ-Al₂O₃ in a microstructured reactor

Ethyl chloride was synthesized by ethanol hydrochlorination in the temperature range of 240–340 °C. The reaction was performed in two serially coupled microreactors. Besides the main product ethyl chloride, several side-products were formed: ethylene, diethyl ether and acetaldehyde. A maximum ethyl chloride selectivity of 88.5% and 85.3% ethanol conversion were obtained at 300 °C (space time 0.154 s). Higher selectivities and conversions can be obtained at higher space times. Thermodynamic calculations were performed to assess the reversibility of the reactions and the equilibrium composition of the reaction mixture. The developed kinetic model accurately described the concentration profiles of all products in the studied range of temperature and initial reactant concentrations. All reactions were treated as reversible. Adsorption of ethanol and HCl was taken into account in the kinetic modeling. A catalytic effect of HCl concentration on the rates of the dehydration reactions was demonstrated.