Effect of the reducing agent on the hydrodechlorination of dioxins over 2 wt.% Pd/γ-Al2O3

2-Propanol and molecular H2 (in methanol (MeOH) and MeOH–water) were examined as reducing agents for the liquid phase hydrodechlorination (HDC) of dioxins over 2 wt.% Pd/γ-Al2O3. Different amounts of NaOH were added to the reaction mixtures. The 2-propanol and H2(g)/MeOH systems presented similar HDC activity. Notwithstanding, Pd sintering and graphitic carbon directly bonded to Pd on catalyst surface was observed on samples used with H2(g)/MeOH. The addition of water to H2(g)/MeOH decreased Pd sintering and favored dissolution of sodium compounds. However, dioxin degradation efficiency diminished. By contrast, 2-propanol acting both as reducing agent and solvent provided hydrogen to the HDC reaction, avoided metal sintering and Pd–C formation. Besides, almost complete dioxin degradation under mild reaction conditions was obtained. Kinetic experiments of dioxin HDC with 2-propanol showed a maximum net reaction rate and turnover frequency (TOF) for a given initial concentration of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). After that value, both reaction rate and TOF decreased. On the other hand, reaction rates and TOFs of dioxin-like polychlorinated biphenyls (DL-PCBs) linearly increased with concentration.