A new improved tri-diagonal method was developed for the non-equilibrium stage model of the catalytic distillation by coupling consumptive reaction coefficient. The reactions in the distillation column were divided into generative reaction and consumptive reaction. The non-equilibrium stage model was introduced for the catalytic distillation process of the dimethyl carbonate (DMC) synthesis by urea methanolysis over solid based catalyst, and the improved tri-diagonal method was used to solve the model equations. Comparison of predicted results with experiment data shows that the mean relative error of the yield of DMC was 3.78% under different conditions such as different operating pressures and reaction temperatures. The improved tri-diagonal matrix method could avoid the negative values of the liquid compositions during the calculations and restrain the fluctuation of compositions by slowing down the variations of the values in the iteration. The modeling results show that the improved tri-diagonal method was appropriate for system containing a wide range of boiling point components and a different rate of reactions.