Kinetic Parameter Calculation and Trickle Bed Reactor Simulation Based on Pilot-Scale Hydrodesulfurization Test of High-Temperature Coal Tar

Xiaoyong Fan; Dong Li; Yong Dan; Huan Dong; Qing Guo; Huaan Zheng; Wenhong Li

doi:10.1021/acsomega.0c00683

Kinetic Parameter Calculation and Trickle Bed Reactor Simulation Based on Pilot-Scale Hydrodesulfurization Test of High-Temperature Coal Tar

ACS Omega. 2020 May 29;5(22):12923-12936. doi: 10.1021/acsomega.0c00683. eCollection 2020 Jun 9.

Authors

Xiaoyong Fan^{1

2

3}, Dong Li^{1

3}, Yong Dan^{1

3}, Huan Dong^{1

3}, Qing Guo^{1

3}, Huaan Zheng^{1

3}, Wenhong Li^{1

3}

Affiliations

¹ School of Chemical Engineering, Northwest University, Xi'an 710069, People's Republic of China.
² School of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Low Metamorphic Coal Clean Utilization, Yulin University, Yulin 719000, People's Republic of China.
³ The Research Center of Chemical Engineering Applying Technology for Resource of Shaanxi, Xi'an 710069, People's Republic of China.

Abstract

At present, a few chemicals can be separated after further processing of high-temperature coal tar (HTCT) distillates, which have a lower utilization. However, hydrogenation to produce clean fuel oil has not been widely reported in literature. Thus, due to the use of new feedstocks and the implementation of more severe environmental legislations, deep hydrodesulfurization (HDS) of HTCT will face formidable challenges. A series of HDS experiments were performed in a continuous isothermal trickle bed reactor in which the reactor temperature was varied from 648 to 678 K, the pressure from 12 to 16 MPa, and the liquid hourly space velocity (LHSV) from 0.25 to 0.35 h^-1, and hydrogen-to-oil ratio kept constant at 2000 L/L. Based on the experimental data, possible reaction pathways of HDS reaction were investigated, and a modified Langmuir-Hinshelwood (LH) HTCT desulfurization kinetic model was established. gPROMS software was used to obtain optimal kinetic parameters that are as follows: EA = 26,842, K ₀ = 93,958, α = -1.14, n = 1.65, and m = 0.86. The model can well reproduce various working conditions and has better prediction accuracy. Some characteristics of HTCT HDS reactions were discovered; the reaction order (n) of HTCT HDS is slightly higher than that of crude oil and medium/low-temperature coal tar (M/LTCT), but the activation energy (EA) is relatively smaller. The established reactor model was used to predict the changes of the concentration of hydrogen, hydrogen sulfide, and sulfur compounds in the gas, liquid, and solid phases along the length of the reactor, respectively. The model was also used to predict the effects of pressure, temperature, and LHSV on the conversion rate of sulfur and catalyst effectiveness factors. The results showed that the LHSV has a greater impact on the conversion rate, and the pressure and temperature are less pronounced at high-severity operating conditions; the effectiveness factor is significantly smaller than that of other HDS processes, temperature has a greater effect on the effectiveness factor, followed by pressure and LHSV. The conclusion can provide a basis for further understanding the HTCT hydrotreating process.