The investigating results are given for the periclase-chromite refractories' composition and structure which are in contact with the pulverized coal and gas medium in the coppersulfide smelting furnaces. The high-temperature burnt copper concentrate and the sulfur dioxide gas suspensions combined action changes the surface and deep refractories layers chemical composition, with that the impurities content reach the value in weight percent: Fe 54,0, Cu 7,2, Zn 6,4, S 1,8. The refractory's surface layer saturation with the iron and non-ferrous metals oxides decreases the porosity and gives rise to low-melting compositions and eutectics. The refractory decomposition is induced by the shelling of the refractory surface layers with the filled porous taking place in course of the heating-cooling cycling because of the phase's thermal linear expansion coefficients. When the spent refractory disposal, it is feasible to separate mechanically the surface layer for the non-ferrous metals extracting, the rest part can be used for obtaining the refractory powder of various purpose.