The solid acid catalyst was prepared by co-pyrolysis semi-coke with waste rubber powder and long-flame coal in Naomaohu , Xinjiang after two steps of phosphoric acid-hydrothermal coupling activation and sulfonation treatment. The conversion rate of acetic acid in the ethanol acetate esterification reaction was used as the catalytic performance index, and the effects of activation conditions and sulfonation conditions on the catalytic performance of the solid acid prepared were investigated. The results showed that the activated semi-coke obtained by activation of phosphoric acid mass fraction of 48.73%, activation temperature of 448K and activation time of 3h was sulfonated at sulfonation temperature of 423K and sulfonation time of 1 hour to obtain a solid acid catalyst. The acid amount of the solid acid catalyst is 7.2 mmol/g, wherein —SO3H is 1.30 mmol/g;The solid acid catalyst mass fraction was 9.5%, the volume ratio of ethanol to glacial acetic acid was 2:1, the reaction time was 30min, the conversion rate of glacial acetic acid was up to 81.98%.