Kinetic and thermodynamic analyses of catalytic hydrodechlorinations in supercritical carbon dioxide (SC-CO2) were performed using 5% Pd supported on γ-Al2O3. The selected standard compounds used for the study represented chlorinated wood resins commonly found in pitch deposits; 1-chlorooctadecane (C18-Cl), 9,10-dichlorostearic acid (Stearic-Cl2), and 12,14-dichlorodehydroabietic acid (DHA-Cl2). The reaction utilized isopropanol as a hydrogen donor. Pressure, temperature, and the concentrations of isopropanol and palladium were varied to study the effect of each parameter and to optimize the dechlorination yield. The reaction in SC-CO2 was compared to the one in liquid solvents at atmospheric pressure. By applying a Langmuir-Hinshelwood kinetic model, the rate-determining step of the reaction was deduced to be adsorption of the chlorinated molecules on the palladium surface. The apparent activation energies of the reactions for C18-Cl, Stearic-Cl2, DHA-Cl2 were 43 ± 5, 40 ± 7, and 135 ± 7 kJ mol-1, respectively, in SC-CO2. The relatively high activation energy for DHA-Cl2 was apparently due to structural differences from the other two compounds. The apparent activation energy of dechlorination of C18-Cl in liquid isopropanol at atmospheric pressure was determined to be 35 ± 3 kJ mol-1, leading to the conclusion that the rate-determining step is the same for this compound in both fluid systems. The enthalpies of desorption of stearic acid and dehydroabietic acid were determined to be 18 ± 2 and 12 ± 2 kJ mol-1, respectively. These values being less than half of the apparent activation energies of dechlorination of their corresponding chlorinated compounds indicates that desorption of the dechlorinated products is not the rate-determining step of the reaction. This was consistent with the conclusion that the rate-determining step is adsorption, on the understanding that the reaction mechanism is same in both fluid systems.

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Keywords Carbon dioxide, Catalytic hydrodechlorination, Pitch deposits, Supercritical fluids
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Journal Applied Catalysis B: Environmental
Aikawa, B., Burk, R, & Sitholé, B.B. (2003). Catalytic hydrodechlorination of 1-chlorooctadecane, 9,10-dichlorostearic acid, and 12,14-dichlorodehydroabietic acid in supercritical carbon dioxide. Applied Catalysis B: Environmental, 43(4), 371–387. doi:10.1016/S0926-3373(03)00002-X