This article analyzes the mechanism of the protective layer formation under the action of alkali in a refractory castable when ground quartz sand (GQS) is used as an admixture to produce refractory conventional castables (CC) and medium cement castables (MCC). It was found that, independently of the castable composition, the addition of GQS (2.5%) reduces the degree of K2CO3 dissolution at high temperature, and the released potassium reacts with the silica and forms a viscous potassium silicate glass, which reduces the mobility of alkali. The liquid phase formed filled some of the open pores and hindered the penetration of potassium into the deeper layers of the refractory castable. The thickness of the formed protective layer, after three cycles of the alkaline corrosion test, varies from 700 µm up to 1300 µm, depending on the castable composition.