The cyclohexanone ammoximation reaction in a monolithic reactor over titanium silicalite-1 (TS-1) was simulated based on our previous experiments. The catalyst powders of TS-1 were wash-coated on the internal surface of each channel in a honeycomb cordierite support, and external circulation was utilized to vary the flow rate of liquids passing through the channels. A one-dimensional model was employed to investigate the influences of temperature from 318.15 K to 343.15 K and external circulation flow rate of 265-765 mL min(-1) on the conversion of reactants. The simulation was from startup to steady-state operation after enough iterative circulations, where the outcomes of simulation agreed favorably with experimental data, and the concentration changes in different computing circulation times are helpful to reveal the reaction process, determine the initial concentrations of reactants in the reactor for shortening duration of startup, and illustrate that the microchannels in the monolithic catalyst effectively provide a good mass-transfer process for the reaction.