Heterogeneous hydroconversion of levulinic acid over silica-supported Ni catalyst

Gyula Novodárszki, J. Valyon, Ádám Illés, S. Dóbé, Dhanapati Deka, J. Hancsók, Magdolna R. Mihályi

Research output: Contribution to journalArticle

1 Citation (Scopus)

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 gLA −1 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 gLA −1 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 gLA −1 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.

Original languageEnglish
JournalReaction Kinetics, Mechanisms and Catalysis
DOIs
Publication statusAccepted/In press - Jan 1 2018

Fingerprint

Pentanoic Acids
Silicon Dioxide
Hydrogenolysis
Silica
silicon dioxide
catalysts
acids
Catalysts
Acids
Desorption
hydrogenolysis
Carbon Monoxide
Temperature programmed desorption
Dehydration
selectivity
desorption
Isotherms
Esters
Adsorption
Temperature

Keywords

  • 2-Methyltetrahydrofuran
  • Levulinic acid hydroconversion
  • Ni/SiO catalyst
  • Pentanoic Acid
  • γ-valerolactone hydrogenolysis

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Heterogeneous hydroconversion of levulinic acid over silica-supported Ni catalyst. / Novodárszki, Gyula; Valyon, J.; Illés, Ádám; Dóbé, S.; Deka, Dhanapati; Hancsók, J.; Mihályi, Magdolna R.

In: Reaction Kinetics, Mechanisms and Catalysis, 01.01.2018.

Research output: Contribution to journalArticle

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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 gLA −1 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 gLA −1 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 gLA −1 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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AU - Novodárszki, Gyula

AU - Valyon, J.

AU - Illés, Ádám

AU - Dóbé, S.

AU - Deka, Dhanapati

AU - Hancsók, J.

AU - Mihályi, Magdolna R.

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N2 - 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 gLA −1 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 gLA −1 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 gLA −1 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.

AB - 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 gLA −1 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 gLA −1 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 gLA −1 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.

KW - 2-Methyltetrahydrofuran

KW - Levulinic acid hydroconversion

KW - Ni/SiO catalyst

KW - Pentanoic Acid

KW - γ-valerolactone hydrogenolysis

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