Catalytic properties of a composite material based on belarusian dolomites in relation to the decomposition of pyrolysis tar

The paper discusses results of an experimental study of the thermal decomposition of pyrolysis tar in a homogeneous process and in the presence of a catalyst. Experiments on thermal decomposition of pyrolysis tar were carried out under isothermal conditions in a laboratory setup at temperatures of 300, 400, 450 and 500 °C. The rate of the homogeneous process of thermal decomposition of tar and maximal degrees of decomposition were determined. According to the data of this work, the activation energy of the homogeneous process was 320 kJ/mol. It was found that the rate of thermal decomposition of the tar increases in the case of introducing samples of natural dolomites into the reaction zone, as well as a composite material based on them. This increase is due to the occurrence of a heterogeneous catalytic decomposition reaction of the pyrolysis tar. The apparent activation energy of this process was 210 kJ/mol (when using dolomites) and 202 kJ/mol (when using composites). It was noted that the composite material has significantly more favorable mechanical properties than dolomite. Based on the established data, it was concluded that the creation of composite catalysts for the thermal decomposition of heavy hydrocarbons formed in the processes of thermochemical conversion of biomass is promising.

1. Bridgwater A. V. Renewable fuels and chemicals by thermal processing of biomass. Chemical Engineering Journal, 2003, vol. 91, no. 1–2, pp. 87–102. https://doi.org/10.1016/S1385-8947(02)00142-0

2. Milne T. A., Abatzoglou N., Evans R. J. Biomass Gasifier “Tars”: Their Nature, Formation and Conversion. NREL Technical Report (NREL/TP-570-25357), November 1998. Available at: https://www.nrel.gov/docs/fy99osti/25357.pdf (accessed 10 November 2020).

3. Evans R. J., Milne T. A. Molecular Characterization of the Pyrolysis of Biomass. 1. Fundamentals. Energy & Fuels, 1987, vol. 1, no. 2, pp. 123–138. https://doi.org/10.1021/ef00002a001

4. Baker E. G., Brown M. D., Elliott D. C., Mudge L. K. Characterization and Treatment of Tars from Biomass Gasifiers. AIChE 1988: Summer National Meeting, Denver, Colorado. August 21–24, 1988. Denver, 1988, pp. 1–11.

5. Sutton D., Kelleher B., Ross J. R. H. Review of literature on catalysts for biomass gasification. Fuel Processing Technology, 2001, vol. 73, no. 3, pp. 155–173. https://doi.org/10.1016/S0378-3820(01)00208-9

6. Ñústez-Castaño S. A., Villamizar-Castro D. O., Vargas-Solano E. M. Evaluation of dolomite as catalyst in the transesterification reaction using palm oil (RBD). DYNA, 2019, vol. 86, no. 209, pp. 180–187. https://doi.org/10.15446/dyna.v86n209.74126

7. Baratieri, M., Pieratti, E., Nordgreen, T., Grigiante M. Biomass Gasification with Dolomite as Catalyst in a Small Fluidized Bed Experimental and Modelling Analysis. Waste and Biomass Valorization, 2010, vol. 1, no. 3, pp. 283–291. http://dx.doi.org/10.1007/s12649-010-9034-6

8. Yu Q. Z., Brage C., Nordgreen T., Sjöström K. Effects of Chinese dolomites on tar cracking in gasification of birch. Fuel, 2009, vol. 88, no. 10, pp. 1922–1926. https://doi.org/10.1016/j.fuel.2009.04.020

9. Vasilevich S. V., Asadchyi A. N., Malko M. V., Degterov D. V. Study of the catalytic activity of natural minerals and composites based on them in process of pyrolytic tar decomposition. 15th International Conference of Young Scientists on Energy Issues, May 23–25, 2018. Kaunas, Lithuania: Lithuanian Energy Institute, I-1–I-8.

10. Garcia-Perez M., Metcalf J. The formation of Polyaromatic Hydrocarbons and Dioxins During Pyrolysis: A Review of the Literature with Descriptions of Biomass Composition, Fast Pyrolysis Technologies and Thermochemical Reactions. Technical Report. Wachington State University, 2008. Available at: http://www.pacificbiomass.org/documents/TheFormationOf PolyaromaticHydrocarbonsAndDioxinsDuringPyrolysis.pdf (accessed 10 November 2020).

11. Dayton D. A Review of the Literature on Catalytic Biomass Tar Destruction. Milestone Completion Report. NREL/TP-510-32815. National Renewable Energy Laboratory, 2002. Available at: https://www.nrel.gov/docs/fy03osti/32815.pdf (accessed 10 November 2020).

12. El-Rub Z. A., Bramer E. A., Brem G. Review of Catalysts for Tar Elimination in Biomass Gasification. Industrial & Engineering Chemistry Research, 2004, vol. 43, no. 22, pp. 6911–6919. https://doi.org/10.1021/ie0498403

13. Malko M. V., Vasilevich S. V., Bogach V. N., Degterev D. V. Study of the kinetics of thermal decomposition of Belarusian dolomites. Vestsi Natsyyanal’nai akademii navuk Belarusi. Seryya fizika-technichnych navuk = Proceedings of the National Academy of Sciences of Belarus. Physical-technical series, 2015, no. 1, pp. 95–101.