To estimate the contribution of clay minerals in light coal fractions to ash deposition in furnaces, we investigated their distribution and thermal reaction products. The light fractions of two Chinese coals were prepared using a 1.5 g·cm−3 ZnCl₂ solution as a density separation medium and were burned in a drop-tube furnace (DTF). The mineral matter in each of the light coal fractions was compared to that of the relevant raw coal. The DTF ash from light coal fractions was analysed using hydrochloric acid separation. The acid-soluble aluminium fractions of DTF ash samples were used to determine changes in the amorphous aluminosilicate products with increasing combustion temperature. The results show that the clay mineral contents in the mineral matter of both light coal fractions were higher than those in the respective raw coals. For the coal with a high ash melting point, clay minerals in the light coal fraction thermally transformed more dehydroxylation products compared with those in the raw coal, possibly contributing to solid-state reactions of ash particles. For the coal with a low ash melting point, clay minerals in the light coal fraction produced more easily-slagging material compared with those in the raw coal, playing an important role in the occurrence of slagging. Additionally, ferrous oxide often produces low-melting substances in coal ash. Due to the similarities of zinc oxide and ferrous oxide in silicate reactions, we also investigated the interactions of clay minerals in light coal fractions with zinc oxide introduced by a zinc chloride solution. The extraneous zinc oxide could react, to a small extent, with clay minerals in the coal during DTF combustion.