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Effect of Al2O3 Support on Co-Based SiO2 Core–Shell Catalysts for Fischer–Tropsch Synthesis in 3D Printed SS Microchannel Microreactor

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Abstract

Fischer Tropsch Synthesis (FTS) using syngas, a mixture of carbon monoxide (CO) and hydrogen (H2), obtained from renewable sources in the presence of a catalyst, is an excellent route to long-chain hydrocarbons and fuels. In this study, cobalt-mesoporous silica catalysts for FTS were prepared by two procedures-Co@SiO2 at 200 °C, and high pressure in an autoclave (AC), Co@SiO2 (One Pot or OP) at room temperature and 1 atm; the effect of Al2O3 on Co-SiO2 as Co@SiO2Al2O3 (One Pot or OP) core–shell catalysts was investigated for FTS at 20 bar in 3D printed stainless steel (SS) microchannel microreactors. These catalysts were characterized by different techniques such as N2 physisorption, XRD, SEM, TEM, H2-TPR, TGA–DSC, and XPS. The N2 physisorption studies show that the BET surface area of Co@SiO2 (Autoclave) is much higher than that of Co@SiO2 (One Pot), and the surface area decreases upon the addition of Al2O3 to yield Co@SiO2Al2O3 (OP) catalyst. In TPR analysis, the Co@SiO2 (OP) based catalyst had much higher reduction temperature than the Co@SiO2 (AC) catalyst. The XRD analysis shows that the Co@SiO2 (Autoclave) based catalyst is more crystalline when compared to other catalysts. The TEM and SEM images revealed agglomerations in the case of Co@SiO2 (OP) and Co@SiO2Al2O3 (OP) based catalysts. The TGA analyses of as-synthesized catalysts, before calcination, showed good stability of the catalysts. The oxidation state and binding energy of all catalysts, evaluated by XPS analysis, show a significant shift based on the catalyst preparation. All F-T reactions were carried out in a 3D-printed SS microreactor at 20 bars in the temperature range of 200–370 °C with H2/CO molar ratio of 2:1. The highest CO conversion for Co@SiO2 AC, Co@SiO2Al2O3 OP, Co@SiO2 OP are 85%, 45%, and 27% respectively. The highest selectivity to C4+ % was observed for Co@SiO2 AC in SS Microreactors in the temperature range of 200–300 °C, and the % selectivity for the C4+ follows the order: Co@SiO2AC > Co@SiO2Al2O3 OP > Co@SiO2 OP.

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Acknowledgements

The authors gratefully acknowledge the help from Dr. Kyle Nowlin for TEM studies at Joint School of Nanoscience and Nanoengineering, Dr. Shima Masoumi and Dr. Xin Li for SEM and XRD studies, Mr. Saif Hassan for TGA-DSC analyses, and Mr. Xiao Ma and Ms. Nourigheimasi Farnoush for XRD studies at Wake Forest University.

Funding

This work was performed at North Carolina A&T State University, the Department of Applied Science Technology, the Department of Chemistry, and the Joint School of Nanoscience and Nanoengineering, a member of Southeastern Nanotechnology Infrastructure Corridor (SENIC) supported by National Science Foundation, USA (Grant ECCS-1542174). This project was partially supported by funds provided by National Science Foundation-Center of Research Excellence in Science and Technology, USA ( HRD #1736173) and the University of North Carolina System-Research Opportunities Initiative(UNC-ROI 2017).

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Authors and Affiliations

  1. Department of Applied Science and Technology, North Carolina Agricultural and Technical State University, Greensboro, NC, 27411, USA

    Meric Arslan & Debasish Kuila

  2. Department of Chemistry, North Carolina Agricultural and Technical State University, Greensboro, NC, 27411, USA

    Sujoy Bepari, Richard Abrokwah, Nafeezuddin Mohammad & Debasish Kuila

  3. Joint School of Nanoscience and Nanoengineering, North Carolina Agricultural and Technical State University, Greensboro, NC, 27411, USA

    Nafeezuddin Mohammad, Juvairia Shajahan & Debasish Kuila

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  1. Meric Arslan
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Arslan, M., Bepari, S., Abrokwah, R. et al. Effect of Al2O3 Support on Co-Based SiO2 Core–Shell Catalysts for Fischer–Tropsch Synthesis in 3D Printed SS Microchannel Microreactor. Top Catal 66, 477–497 (2023). https://doi.org/10.1007/s11244-022-01733-z

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