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Heterogeneous hydroconversion of levulinic acid over silica-supported Ni catalyst

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Abstract

Silica-supported Ni catalyst (6.6 wt% Ni) was prepared and tested in solvent-free hydroconversion of levulinic acid (LA) using flow-through fixed-bed tube-type microreactor at 250 and 275 °C in the pressure and space time range of 1–30 bar and 0.1–1.0 gcat g −1LA h, respectively. The catalyst was characterized by XRD, adsorption/desorption N2 isotherms, temperature-programmed H2-reduction (H2-TPR), FT-IR spectra of adsorbed pyridine (Py), and temperature-programmed H2 desorption (H2-TPD). At 250 °C and 1 bar total pressure LA was dehydrated to α-angelica lactone (AL) intermediate that was hydrogenated to γ-valerolactone (GVL). At space time 0.25 gcat g −1LA  h 82% GVL selectivity was achieved at virtually full LA conversion. The GVL became partially converted to pentanoic acid (PA). At longer space time, 1.0 gcat g −1LA  h, the PA selectivity increased to 37%. At pressure > 1 bar the favored reaction of GVL was the hydrogenolysis of its ester bond and dehydration of the intermediate 1,4-pentanediol (1,4-PD) to 2-methyltetrahydrofuran (2-MTHF). At 250 °C and 30 bar the yield of 2-MTHF was 56 mol%. The product distribution is controlled by the relative activity of the Ni/SiO2 catalyst in the hydrogenolysis of the GVL C–O bonds.

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Acknowledgements

The authors acknowledge the financial support of the project of the Economic Development and Innovation Operative Program of Hungary, GINOP-2.3.2-15-2016-00053: Development of liquid fuels having high hydrogen content in the molecule (contribution to sustainable mobility). The Project is supported by the European Union. Thanks are also due to the Indo-Hungarian project entitled “Biochemicals and biofuels from lignocellulosic biomass by Green catalytic processes” (Grant No. TÉT_15_IN-1-2016-0034) and the Argentine-Hungarian project entitled “Development of catalytic processes for the agro-environmental protection and agro technology” (Grant No. TÉT_15-1-2016-0089) financed by the National Research, Development and Innovation Office of Hungary. Further thanks is due to COST Action FP1306 (LIGNOVAL).

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Authors and Affiliations

  1. Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar tudósok körútja 2, Budapest, 1117, Hungary

    Gyula Novodárszki, József Valyon, Ádám Illés, Sándor Dóbé & Magdolna R. Mihályi

  2. Biomass Conversion Laboratory, Department of Energy, Tezpur University, Tezpur, India

    Dhanapati Deka

  3. Institute of Chemical and Process Engineering, University of Pannonia, Veszprém, 8201, Hungary

    Jenő Hancsók

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  1. Gyula Novodárszki
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  2. József Valyon
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  3. Ádám Illés
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Correspondence to Magdolna R. Mihályi.

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Novodárszki, G., Valyon, J., Illés, Á. et al. Heterogeneous hydroconversion of levulinic acid over silica-supported Ni catalyst. Reac Kinet Mech Cat 126, 795–810 (2019). https://doi.org/10.1007/s11144-018-1507-9

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