2-Propanol and molecular H-2 (in methanol (MeOH) and MeOH-water) were examined as reducing agents for the liquid phase hydrodechlorination (HDC) of dioxins over 2 wt.% Pd/gamma-Al2O3. Different amounts of NaOH were added to the reaction mixtures. The 2-propanol and H-2(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 H-2(g)/MeOH. The addition of water to H-2(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. (C) 2009 Elsevier B.V. All rights reserved.