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By using the advanced instrumentation of a Computer Controlled Scanning Electron Microscope (CCSEM),X-ray diffraction (XRD) and X-ray fluorescence (XRF), the ash composition and the mineral components of six typical Huainan coals of different origins were studied. The transformation of mineral matter at high temperatures was tracked by XRD in reducing conditions. The quartz phase decreased sharply and the anorthite content tended to increase at first and then decreased with increasing temperatures. The formed mullite phase reached a maximum at 1250 ℃ but showed a tendency of slow decline when the temperature was over 1250 ℃. The mullite formed in the heating process was the main reason of the high ash melting temperature of Huainan coals. Differences in peak intensity of mullite and anorthite reflected differences in phase concentration of the quenched slag fractions, which contributed to the differences in ash melting temperatures. The differences in the location of an amorphous hump maximum indicated differences of glass types which may affect ash melting temperatures. For Huainan coal samples with relatively high ash melting temperatures, the intensity of the diffraction lines for mullite under reducing condition is high while for the samples with relatively low ash melting temperature the intensity for anorthite is high.