Selective hydrodeoxygenation of guaiacol to cyclohexanol using activated hydrochar-supported Ru catalysts

doi:10.1007/s11705-024-2409-1

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (5) : 50 https://doi.org/10.1007/s11705-024-2409-1

Selective hydrodeoxygenation of guaiacol to cyclohexanol using activated hydrochar-supported Ru catalysts

Kaile Li¹, Shijie Yu²(

), Qinghai Li¹, Yanguo Zhang¹, Hui Zhou¹(

)

¹. Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Beijing Key Laboratory of CO2 Utilization and Reduction Technology, Department of Energy and Power Engineering, Tsinghua University, Beijing 100084, China
². Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, 117585, Singapore

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Abstract

Lignin, an abundant aromatic polymer in nature, has received significant attention for its potential in the production of bio-oils and chemicals owing to increased resource availability and environmental issues. The hydrodeoxygenation of guaiacol, a lignin-derived monomer, can produce cyclohexanol, a nylon precursor, in a carbon-negative and environmentally friendly manner. This study explored the porous properties and the effects of activation methods on the Ru-based catalyst supported by environmentally friendly and cost-effective hydrochar. Highly selective cleavage of C_aryl–O bonds was achieved under mild conditions (160 °C, 0.2 MPa H₂, and 4 h), and alkali activation further improved the catalytic activity. Various characterization methods revealed that hydrothermal treatment and alkali activation relatively contributed to the excellent performance of the catalysts and influenced their porous structure and Ru dispersion. X-ray photoelectron spectroscopy results revealed an increased formation of metallic ruthenium, indicating the effective regulation of interaction between active sites and supports. This synergistic approach used in this study, involving the valorization of cellulose-derived hydrochar and the selective production of nylon precursors from lignin-derived guaiacol, indicated the comprehensive and sustainable utilization of biomass resources.

Keywords hydrochar guaiacol cyclohexanol activation full-component utilization

Corresponding Author(s): Shijie Yu,Hui Zhou

Just Accepted Date: 17 January 2024 Issue Date: 04 March 2024

Cite this article:

Kaile Li,Shijie Yu,Qinghai Li, et al. Selective hydrodeoxygenation of guaiacol to cyclohexanol using activated hydrochar-supported Ru catalysts[J]. Front. Chem. Sci. Eng., 2024, 18(5): 50.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2409-1
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I5/50

Fig.1 Selective hydrodeoxygenation of guaiacol to cyclohexanol using hydrochar-supported Ru catalyst (Ru/hydrochar).

Tab.1 Ruthenium-catalyzed hydrodeoxygenation of guaiacol^a)

Fig.2 Effect of reaction temperature on guaiacol conversion and product distribution. Reaction conditions: guaiacol/Ru molar ratio 80; initial H₂ pressure 0.2 MPa; reaction time 4 h.

Fig.3 Effect of initial H₂ pressure on guaiacol conversion and product distribution. Reaction conditions: guaiacol/Ru molar ratio 80; temperature 160 °C; reaction time 4 h.

Fig.4 Effect of reaction time on guaiacol conversion and product yield. Reaction conditions: guaiacol/Ru molar ratio 80; temperature 160 °C; initial H₂ pressure 0.2 MPa.

Fig.5 SEM, N₂-sorption curves and corresponding pore size distributions of hydrochar (a, c) before and (b, d) after activation.

Fig.6 (a) TEM image of Ru/AHC catalyst, and elemental mappings for (b) Ru, (c) C, and (d) O.

Fig.7 FTIR spectra of hydrochar before and after activation.

Fig.8 XPS spectra of (a) O 1s and (b) C 1s + Ru 3d over Ru/hydrochar and Ru/AHC.

Fig.9 Effect of activation on guaiacol conversion and product distribution. Reaction conditions: guaiacol/Ru molar ratio 80; temperature 160 °C; initial H₂ pressure 0.2 MPa; reaction time 4 h.

Fig.10 Proposed pathway for guaiacol hydrodeoxygenation.

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