After baked, kaolinite in coal measures reacted with (NH4)2 SO4. Then, the Al2(SO4)3·(NH4)2 SO4 crude solution was prepared from the roast by water leach. Secondly, processing steps such as extracting iron with the mixed extractant N503-P204, co-precipitation to synthesize AACH crystal with NH4HCO3, and thermal decomposition of calcination, etc. were carried out to prepare high purity and ultra-fine alumina. The influence of pH value of the aqueous phase and the extracting time on extracting-iron effect was discussed when three-stage counter-flow extraction with the mixed extractant was carried out.