A Green Route for Wasted Sulfur Consumption: Kinetic Modelling of Methyl Mercaptan Synthesis from Refinery H2S Streams over the K2Wo4/Al2O3 Catalyst

Document Type : Research Paper

Authors

Department of Chemical Engineering, University of Sistan and Balouchestan, Zahedan, Iran

Abstract

The kinetics of methyl mercaptan production from a reaction between methanol and hydrogen sulfide in the presence of a K2Wo4/Al2O3 catalyst was experimentally studied. Waste streams containing sulfur due to sour gas sweetening in the Nori refinery complex were used instead of pure H2S. This reaction can eliminate the emission of sulfur-containing compounds into the environment and convert them into useful products. The experiments were performed over a fixed-bed reactor at various temperatures and a pressure of 8-10 bars. The values of kinetic parameters estimated by the regression between the kinetic models and the experiments within the ranges have been reported in the literature. The activation energies for methyl mercaptan and dimethyl sulfide were 53.11 and 129.55 (kJ/mol), respectively. ASPEN simulation showed that the molar flow rates of H2S and methanol (reactants) decreased at the length of the reactor, while this trend for the products (methyl mercaptan, DMS, and H2O) was reversed. The correlation coefficients indicated that the parameters and the model were significant and reasonable for reactor design. The results showed that sulfur-containing waste streams could be used instead of pure H2S streams. This substitution not only provides a supply for replacing pure H2S streams but also contains the emission of poisonous sulfur compounds into the environment.

Keywords

Main Subjects

References

[1] Kaufmann, C. (2015). Alternative routes to methyl mercaptan from C 1-compounds, Doctoral dissertation, Technische Universität München.
[2] Yermakova, A., Mashkina, A. (2004). Kinetic model of the reaction of methanol with hydrogen sulfide. Kinetics and catalysis, 45(4), 522-529.
[3] Mashkina, A. (2006). Synthesis of methylmercaptan from methanol and hydrogen sulfide at elevated pressure on an industrial catalyst. Petroleum chemistry, 46(1), 28-33.
[4] Brand, A., Quaschning, V. (2010). U.S. Patent No. 7,687,667. Washington, DC: U.S. Patent and trademark office.
[5] Kudenkov, V., Kiseleva, L.,  Mashkina, A. (1991). Interaction of methanol with hydrogen sulfide in the presence of K2WO4/Al2O3. Reaction kinetics and catalysis letters, 45(2), 227-233.
[6] Forquy, C., Arretz, E. (1988). Heterogeneous catalysis in mercaptan industrial synthesis. In studies in surface science and catalysis (Vol. 41, pp. 91-104). Elsevier.
[7] Hasenberg, D. M., Refvik, M. D. (2010). U.S. Patent No. 7,645,906. Washington, DC: U.S. Patent and trademark Office.
[8] Mirzaei, A. A., Sarani, R., Azizi, H. R., Vahid, S., Torshizi, H. O. (2015). Kinetics modeling of Fischer–Tropsch synthesis on the unsupported Fe-Co-Ni (ternary) catalyst prepared using co-precipitation procedure. Fuel, 140, 701-710.
[9] Mashkin, V.Y., Kudenkov, V.M., Mashkina, A.V. (1995). Kinetics of the catalytic reaction between methanol and hydrogen sulfide. Industrial and engineering chemistry research, 34(9), 2964-2970.
[10] Eow, J.S. (2002). Recovery of sulfur from sour acid gas: A review of the technology. Environmental progress, 21(3), 143-162.
[11] Khaksar, S.A.M., Zivdar, M., Rahimi, R. (2019). Investigation on the catalytic conversion of hydrogen sulfide to methyl mercaptan as a novel method for gas sweetening: Experimental and modeling approaches. Journal of natural gas science and engineering, 61, 97-105.
[12] Chen, S., Zhang, Y., Lin, L., Jing, X., Yang, Y. (2019). K2WO4/Al2O3 catalysts for methanethiol synthesis from methanol and H2S: effect of catalyst preparation procedure. Reaction kinetics, mechanisms and catalysis, 127(2), 917-930.
[13] Zhang, Y., Chen, S., Wu, M., Fang, W., Yang, Y. (2012). Promoting effect of SiO2 on the K2WO4/Al2O3 catalysts for methanethiol synthesis from methanol and H2S. Catalysis communications, 22, 48-51.
[14] Ereña, J., Arandes, J. M., Bilbao, J., Gayubo, A. G., De Lasa, H. (2000). Conversion of syngas to liquid hydrocarbons over a two-component (Cr2O3–ZnO and ZSM-5 zeolite) catalyst: Kinetic modelling and catalyst deactivation. Chemical engineering science, 55(10), 1845-1855.
 
 
Advances in Environmental Technology
Volume 5, Issue 4
October 2019
Pages 213-219

Files

History

  • Receive Date: 15 September 2020
  • Revise Date: 11 November 2020
  • Accept Date: 14 November 2020

Share

How to cite

Statistics