The kaolin processing for paper covering produces a great volume of residues formed primarily by kaolinite claymineral, here the starting material for the synthesis of ammonium alumen aiming to obtain free sodium alumina with fine grade for ceramic manufacturing. The synthesis process to obtain ammonium alumen consisted of the following procedures: residues calcination and sulphuric leaching of metakaolinite followed by neutralization/crystallisation of aluminum sulphate solution with ammonium hydroxide concentrated solution. The effect of calcination temperature (650 °C, 700 °C and 750 °C), calcination time of residues (30 min, 60 min and 120 min), sulphuric acid concentration as well as leaching temperature (70 °C, 80 °C and 90 °C) on the kinetics of aluminum leaching were studied. The influence of pH on ammonium alumen crystallization was also studied. Data on chemical analysis, XRD, DTA, TGA and granulometry of the material utilized and synthesized are presented and discussed.