Kinetic parameter estimation and simulation of trickle-bed reactor for hydrodesulfurization of whole fraction low-temperature coal tar

With whole-fraction low temperature coal tar (LTCT) as raw material, which boiling point range is 209–514 °C. This paper conducts hydrotreatment (HDT) test for 1176 h on trickle-bed reactor (TBR) with commercial NiMo/Al2O3-SiO2 catalyst. The reaction conditions are as follows: reaction temperature 613–653 K, reaction pressure 10–14 MPa, liquid hourly space velocity (LHSV) 0.2–0.4 h−1, and hydrogen-to-oil volume ratio 1000:1. Considering the short life of coal tar HDT catalyst, a kinetic model of whole-fraction LTCT hydrodesulfurization (HDS) including running time (t1) and catalyst half-life (tc) was established. The kinetic parameter estimation was conducted according to the experimental data, and the results are as follows: activation energy 94965 J/mol, reaction order 1.5, and the relative error of the model is less than 5%. Based on the premise of steady state operation, the HDS reaction happened in the three-phase trickle-bed reactor was simulated by combining the mass transfer, reaction kinetics model and physical property data of LTCT. The results show that the experimental and simulated values of sulphur content at the exit of the reactor are within the error range of 5%. By simulating the whole-fraction LTCT HDS reactor, the pattern of changes in the concentrations of hydrogen sulfide, hydrogen and sulfur in gas, liquid and solid phases according to the length of the reactor were obtained. Based on this, this paper discusses on the impacts of each process parameter and hydrogen sulfide partial pressure on LTCT HDS, and works out the reaction characteristics of whole-fraction LTCT HDS different from crude oil fraction. Finally, this paper analyzes the influence of different process conditions on internal gradients of catalyst, and concludes the influence of each parameter on effectiveness factor of particle. The increase of temperature, decrease of pressure or increase of LHSV can all cause the decrease of effectiveness factor, wherein the temperature has the most significant effect on the effectiveness factor, followed by LHSV, and pressure has the weakest effect. These findings contribute to a more in-depth understanding of the features and rules of LTCT HDS, and can also give us some guidance for industrial reactor simulation.