Effect of catalyst support on dihydroeugenol hydrodeoxygenation on low cost FeNi catalyst to produce renewable alkane fuel
: Vajglová, Zuzana; Mäki-Arvela, Päivi; Yevdokimova, Olha; Martinez-Klimov, Mark; Simakova, Irina; Eränen, Kari; Tirri, Teija; van Hoeven, Jessi E.S.; Peuronen, Anssi; Huš, Matej; Likozar, Blaž; Lastusaari, Mika; Lindén, Johan; Doronkin, Dmitry E.; Murzin, Dmitry Yu.
Publisher: Elsevier BV
: 2025
: Applied Catalysis A: General
: Applied Catalysis A: General
: 120307
: 701
: 0926-860X
: 1873-3875
DOI: https://doi.org/10.1016/j.apcata.2025.120307
: https://doi.org/10.1016/j.apcata.2025.120307
: https://research.utu.fi/converis/portal/detail/Publication/498641697
Solventless hydrodeoxygenation of dihydroeugenol was investigated in a continuous reactor at 300 °C under 30 bar over different nickel-iron catalysts, prepared using a two-step impregnation method. The following catalysts were studied: mesoporous FeNi/Al2O3, FeNi/SiO2 and FeNi/H-MCM-48 as well as microporous FeNi/H-Beta-300, FeNi/H-Beta-38, FeNi/H-Y-5.1, FeNi/H-MCM-48 and FeNi/USY-30. The catalysts were characterized by SEM coupled with energy dispersive X-ray analysis, Mössbauer and X-ray absorption spectroscopy, hydrogen TPR, X-ray diffraction, TEM, nitrogen physisorption and FTIR pyridine adsorption. DFT calculations were performed to elucidate the role of Fe and Ni. The results revealed that FeNi/Al2O3 was the most active and stable in dihydroeugenol hydrodeoxygenation. Complete conversion of dihydroeugenol was obtained and the yield of the main product propylcyclohexane was varying in the range 84–88 %. FeNi/Al2O3 catalyst exhibited 3.4 nm metal particles and contained FeNi alloy particles with the fcc metallic structure. No deactivation was observed for FeNi/ Al2O3 during 5 hours time-on-stream due to the presence of Ni-rich particles with iron-enriched outer surface confirmed by EXAFS. Fe was shown to be responsible for deoxygenation, while Ni promotes hydrogenation. Catalyst deactivation was observed for all other catalysts except for FeNi/Al2O3 with increasing time-on-stream under the same reaction conditions due to their higher Brønsted to Lewis acid site ratio and larger average metal particle size in comparison to FeNi/Al2O3.
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The authors acknowledge Business Finland for funding through the project: Catalytic Slurry Hydrotreatment. Electron microscopy samples were processed and analyzed at the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which received financial support from Biocenter Finland. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at the light source PETRA III at DESY, a member of the Helmholtz Association (HGF). We would like to thank Dr. Edmund Welter for his assistance in using the beamline P65, which was allocated for proposal I-20220246. Computational resources were provided by the Institute of Information Science, Maribor, Slovenia through the HPC RIVR consortium and EuroHPC JU. Financial support from the Slovenian Research and Innovation Agency (ARIS) through core funding P2–0152, project funding N2–0316, J1–3020 and infrastructure funding I0–0039 is greatly appreciated.
