Research into Thermocatalytic Propane-to-Propylene Synthesis Using Iron-Containing Composite Carbon Materials

The development of modern thermocatalytic technologies for processing oil and gas raw materials is one of the promising areas for the advancement of chemical production. New highly efficient catalytic systems with the required technical characteristics and long service life play an essential role in solving these issues. The paper focuses on obtaining propylene by selective propane dehydrogenation. In the course of the experiments, composite iron-containing catalysts were synthesized, in which the active component is iron oxide in combination with an inert carbon matrix. FAS activated carbon and carbon nanotubes were used as the matrix. As a result of the synthesis on the catalyst surface it was possible to obtain catalytic centers that transfer electrons by changing the degree of iron oxidation when converting the starting materials into the target reaction products. Findings of research show that the obtained iron-containing catalysts significantly increase the efficiency of the process in comparison with the efficiency of thermal cracking of propane. Thus, the Fe³⁺/FAS catalyst showed a conversion rate of the initial reagent of 68 % and a propylene selectivity of about 42 %. Further transition to catalytic systems based on singlelayer and double-layer carbon nanotubes modified with iron oxide (Fe³⁺/CNT_I and Fe³⁺/CNT_II) made it possible to obtain propane conversion up to 37--40 % with a decrease in propylene selectivity to 29--30 %. Studies of the service life of the synthesized catalytic systems and the possibility of their regeneration show that, with account for the regeneration, the activity of the catalysts and the main technical characteristics of the propane-to-propylene cracking process remain unchanged for 10 working cycles

The work was carried out with the financial support of the Ministry of Science and Higher Education of Russia (project no. 075-03-2020-223 (FSS-2020-0017))

References

[1] Khadzhiev S.N. Nanoheterogeneous catalysis: definition, state, and research prospects (review). Petrol. Chem., 2016, vol. 56, no. 6, pp. 465--479. DOI: https://doi.org/10.1134/S0965544116060050

[2] Fakhroleslam M., Sadrameli S.M. Thermal/catalytic cracking of hydrocarbons for the production of olefins; a state-of-the-art review III: process modeling and simulation. Fuel, 2019, vol. 252, pp. 553--566. DOI: https://doi.org/10.1016/j.fuel.2019.04.127

[3] Uskov S.I., Potemkin D.I., Shigarov A.B., et al. Low-temperature steam conversion of flare gases for various applications. Chem. Eng. J., 2019, vol. 368, pp. 533--540. DOI: https://doi.org/10.1016/j.cej.2019.02.189

[4] Sheshko T.F., Markova E.B., Sharaeva A.A., et al. Carbon monoxide hydrogenation over Gd(Fe/Mn)O^--3 perovskite-type catalysts. Petrol. Chem., 2019, vol. 59, no. 12, pp. 1307--1313. DOI: https://doi.org/10.1134/S0965544119120107

[5] Sun Y., Wu Y., Tao L., et al. Effect of pre-reduction on the performance of Fe₂O₃/Al₂O₃ catalysts in dehydrogenation of propane. J. Mol. Catal. A Chem., 2015, vol. 397, pp. 120--126. DOI: https://doi.org/10.1016/j.molcata.2014.11.011

[6] Kim K.M., Kwak B.S., Park N.-K., et al. Effective hydrogen production from propane steam reforming over bimetallic co-doped NiFe/Al₂O₃ catalyst. J. Ind. Eng. Chem., 2017, vol. 46, pp. 324--336. DOI: https://doi.org/10.1016/j.jiec.2016.10.046

[7] Tarasov V.A., Stepanishev N.A., Romanenkov V.A., et al. Quality and technological properties improvement of a polyester matrix of composite designs on the basis of ultrasonic nanomodifying. Engineering Journal: Science and Innovation, 2012, no. 9, pp. 166--174 (in Russ.). DOI: https://doi.org/10.18698/2308-6033-2012-9-381

[8] Popov V.V. Formation regularities of dispersed hydrated oxide systems. Russ. J. Inorg. Chem., 2015, vol. 60, no. 4, pp. 420--427. DOI: https://doi.org/10.1134/S0036023615040191

[9] Dubinin M.M. Adsorbtsiya i poristost’ [Adsorption and porosity]. Moscow, VAKhZ Publ., 1972.

[10] Anderson R.B. Experimental methods in catalytic research. Academic Press, 1968.

[11] Markova E.B., Lyadov A.S., Kurilkin V.V. Features of propane conversion in the presence of SmVO₃ and SmVO₄. Russ. J. Phys. Chem., 2016, vol. 90, no. 9, pp. 1754--1759. DOI: https://doi.org/10.1134/S0036024416090193

[12] Markova E.B., Krasil’nikova O.K., Serov Yu.M. Catalytic conversion of propane gas into ethyleneon activated nano-fibrous aluminium oxide aerogel. Neftepererabotka i neftekhimiya, 2013, no. 3, pp. 8--12 (in Russ.).

[13] Markova E.B., Krasil’nikova O.K., Serov Yu.M., et al. Alumina nanofibrous structural self-organization in hollow nanotubes caused by hydrogen treatment. Nanotechnol. Russia, 2014, vol. 9, no. 7-8, pp. 441--447. DOI: https://doi.org/10.1134/S1995078014040119

[14] Jowkary H., Farsi M., Rahimpour M.R. Supporting the propane dehydrogenation reactors by hydrogen permselective membrane modules to produce ultra-pure hydrogen and increasing propane conversion: process modeling and optimization. Int. J. Hydrog. Energy, 2020, vol. 45, no. 12, pp. 7364--7373. DOI: https://doi.org/10.1016/j.ijhydene.2019.04.286

[15] Gao R., Liu Y., Liu B., et al. Novel utilization of pyrolysis products produced from waste printed circuit boards: catalytic cracking and synthesis of graphite carbon. J. Clean. Prod., 2019, vol. 236, art. 117662. DOI: https://doi.org/10.1016/j.jclepro.2019.117662