Zhundong coal is a kind of high-quality power coal, but serious fouling and slagging may occur due to the rich content of alkali and alkali earth metals (AAEMs). Combustion experiments were carried out on an electrically heated tube furnace at different temperatures in air atmosphere. The raw coal and its mixtures with struvite additive (2-8 wt % of coal mass) were respectively burned in air atmosphere. Combustion-generated ashes were collected and analyzed by inductively coupled plasma optical emission spectroscopy, X-ray diffractometry, and scanning electron microscopy-energy dispersive spectroscopy. Results show that the mixed coal ash at high temperatures has a looser and more brittle structure than the raw coal ash and is more easily removed. With the introduction of struvite, whitlockite and chladniite appear, which improves the melting temperature of the mixed coal ash, while gehlenite (Ca2Al2SiO7) and akermanite (Ca2MgSiO7) disappear. The high content of calcium in Zhundong coal leads to the formation of a low-temperature eutectic with some minerals such as Al and Si at temperatures higher than 1000 degrees C. Ca separates out after these minerals melt, flows within the flue gas, and congeals on the heating surfaces, causing serious slagging. The fixation rate of Ca in the mixed coal ash blended with struvite increases obviously. The optimum addition of struvite is 4%.