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Researching and developing chrome-free refractory becomes a research hotspot at present because hexavalent chromium ions (Cr6+) may lead to environmental hazard. The additives lanthanum oxide (La2O3), effect on mechanism of spinel refractory react with cement clinker, several additives, such as cerium oxide (Ce2O3), titanium dioxide (TiO2), barium oxide (BaO), iron oxide (Fe2O3), are researched in this paper. It indicates that La2O3 is a suitable additive to MgO-MgAl2O4-ZrO2 brick which not only could stabilize phase transition of dicalcium silicate (C2S) in cement, but also do not impair the high-temperature-properties of spinel. The new environmentally friendly material spinel and lanthanum zirconate Composite is an excellent refractory for cement kiln which has high thermal shock resistance, good coating adherence, good corrosion resistance, higher mechanical strength, and longer service life than magnesia-chrome brick when they are used for sintering zone in cement kiln.