Spent refractories from a coal gasifier after 1000 hours of operation were analyzed for crystalline phases, chemical composition and microstructures as a function of slag penetration depth, and the slag corrosion mechanism was determined. The chemical corrosion of chromia refractory occurred via reaction between Cr$_2$O$_3$ of the refractory and FeO and A1$_2$O$_3$ in the slag. The FeO reacted with Cr$_2$O$_3$ at the slare/refractory interface and formed FeCr$_2$O$_4$. After all FeO were consumed, Al in the penetrating slag substituted Cr in Cr$_2$O$_3$, forming (Al, Cr)$_2$O$_3$, at the edges of the particle, which were broken to form fragments rich in Al. The corrosion resistance of Cr$_2$O$_3$ varied with the particle size and the extent of sintering, and the higher resistance was observed in the larger and more sintered particles. There was no chemical change in ZrO$_2$, but showed the effects of physical corrosion: the grain boundaries became more wavy, and ZrO$_2$ grains were split in the corroded area. The slag penetration depth increased in the refractory samples farther down from the feed nozzles.