To forecast the mass transfer behavior in consideration of noncatalytic solid reaction characteristics with the shrinking spherical model (SPM), a structure-based mass transfer model taking account of the gas-solid mass exchange within both the emulsion and bubble/interphase phases is built and coupled with computational fluid dynamics (CFD) to predict the carbochlorination of TiO2 with a binary gas-solid phase system. Based on the validation through comparing with the experimental data, the simulation gives a comprehensive understanding and deep analysis of the gas-solid reaction that is helpful for the design and optimization of a non-catalytic fluidized reactor. It is concluded that the fluidized mass transfer process with a heterogeneous flow structure is not only affected by the chemical reaction rate but also dependent on local flow parameters.