The purpose of this study is to investigate the catalytic effects of Na as NaCl or as sodium carboxylates (-COONa) in Victorian brown coal on the char reactivity. A Na-exchanged coal and a set of NaCl-loaded coal samples prepared from a Loy Yang brown coal were pyrolysed in a fluidised-bed/fixed-bed reactor and in a thermogravimetric analyser (TGA). The reactivities of the chars were measured in air at 400°C using the TGA. The experimental data indicate that the Na in coal as NaCl and as sodium carboxylates (-COONa) had very different catalytic effects on the char reactivity. It is the chemical form and dispersion of Na in char, not in coal, that govern the catalytic effects of Na. For the Na-form (Na-exchanged) coal, the char reactivity increased with increasing pyrolysis temperature from 500 to 700 °C and then decreased with pyrolysis temperature from 700 to 900 °C. The increase in reactivity with pyrolysis temperature (500-700 °C) is mainly due to the changes in the relative distribution of Na in the char matrix and on the pore surface. For the NaCl-loaded coals, when Cl was released during pyrolysis or gasification, the Na originally present in coal as NaCl showed good catalytic effects for the char gasification. Otherwise, Cl would combine with Na in the char to form NaCl during gasification, preventing Na from becoming an active catalyst. Controlling the pyrolysis conditions to favour the release of Cl can be a promising way to transform NaCl in coal into an active catalyst for char gasification.
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