Abstract: The intrinsic kinetics of TS-1 catalyzed cyclohexanone ammoximation with hydrogen peroxide in water was studied. The kinetic reaction was carried out in a semi-batch stirred-tank reactor at 333.15—348.15 K. Two models from proposed mechanisms were regressed. The results obtained showed that the hydroxylamine mechanism fitted the experimental data better. The hydroxylamine mechanism proposes that hydrogen peroxide molecule is absorbed on the catalytic sites and reacts with ammonia first, and surface reaction is the rate-controlling step. Hydrogen peroxide can also decompose and compete with cyclohexanone ammoximation. So it is advisable to take measures to restrain hydrogen decomposition. After parameters estimation and model discrimination, a rational model, which showed good agreement with the experimental data,was obtained. Based on the model, some operation parameters were analyzed and optimized through simulation and calculation.