The kaolin content of gangue in the Heidaigou ming area is as high as 70%. Herein, from the perspective of comprehensive utilization of coal resources, in order to improve the calcination whiteness of coal-derived kaolin, a method of centrifugal for separation was used to remove the chromogenic impurities with high-density. To achieve this, this work performed orthogonal design by Design Expert and adopted the Box-Behnken model. Consequently, the influence of centrifugal speed, feeding rate, feeding concentration and feeding time on the calcination whiteness and concentrate yield was explored and the quadratic equation relationship model was fitted. Further, the response surface plots of calcination whiteness and concentrate yield with significant factors were given. It was found that the whiteness of calcination was mainly affected by the centrifugal speed. With the increase of the rotation speed of the drum, the whiteness of the calcination first increased and then decreased. The yield of concentrate was mainly affected by the feeding time. With the extension of feeding time, the yield of concentrate increased linearly. Finally, combined with the simulation results of Design Expert, the optimal centrifugal separation conditions were analyzed and explored. When the centrifugal speed is 800 r/min, feeding rate is 8.4 L/min, feeding concentration is 20%, and feeding time is 100 s, the optimal calcination whiteness (78.80%) and concentrate yield (86.31%) of kaolin can be obtained.