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Vanillin Hydrodeoxygenation: Kinetic Modelling and Solvent Effect

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Abstract

Vanillin hydrodeoxygenation was investigated using Pt/C catalyst in the temperature and total pressure ranges of 80–200 °C and 20–30 bar in several solvents, such as tetrahydrofuran, 2-propanol, water and in solventless conditions using 1:1 mass ratio of vanillin to guaiacol. The results revealed that the rate increased with increasing solvent polarity as follows: tetrahydrofuran < 2-propanol < water. The main product was p-creosol with 66% selectivity at complete vanillin conversion in HDO under 30 bar total pressure at 100 °C after 4 h using water as a solvent. In a solventless experiment with 1:1 mass ratio of vanillin–guaiacol as a feedstock only vanillin was transformed to p-creosol with 91% conversion in 4 h at 200 °C under 30 bar total pressure, while guaiacol did not produce any HDO products. Both thermodynamic analysis and kinetic modelling were performed. Vanillin hydrodeoxygenation resulted in formation of p-creosol over Pt/C catalyst using an optimum vanillin initial concentration in water solution. From the industrial point of view vanillin hydrodeoxygenation proceeded rapidly giving high yields of p-creosol in solventless hydrodeoxygenation of vanillin-guaiacol mixture, while guaiacol was not deoxygenated.

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Abbreviations

K :

Rate constant

K 0 j :

Equilibrium constant at standard conditions for reaction j

K eq :

Adsorption equilibrium constant

N :

Moles (mol)

P :

Pressure (bar)

P 0 :

Standard pressure (bar)

R :

Reaction rate

R 2 :

Coefficient of determination

R :

Ideal gas constant (J/K/mol)

T :

Absolute temperature (K)

T 0 :

Absolute standard temperature (K)

y:

Yield

ΔG 0 f :

Gibbs free energy of formation at standard conditions (J/mol)

ΔG 0 r :

Gibbs free energy of reaction at standard conditions (J/mol)

ΔG Φ r,j :

Gibbs free energy of reaction at 1 bar and chosen temperature (J/mol)

ΔG r,j :

Gibbs free energy of reaction at a fixed temperature and pressure (J/mol)

ΔH 0 f :

Enthalpy of formation at standard conditions (J/mol)

ΔH 0 r :

Enthalpy of reaction at standard conditions (J/mol)

ρ B :

Catalyst bulk density

θ :

Objective function

ν i,j :

Stoichiometric matrix composed by i components and j reactions (–)

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Authors and Affiliations

  1. Johan Gadolin Process Chemistry Centre, Åbo Akademi University, 20500, Turku, Finland

    Alexandrina Sulman, Päivi Mäki-Arvela, Louis Bomont, Vyacheslav Fedorov, Moldir Alda-Onggar, Annika Smeds, Jarl Hemming, Johan Wärnå & Dmitry Yu. Murzin

  2. Università di Napoli Federico II, via Cintia, 4, 80126, Naples, Italy

    Vincenzo Russo

  3. Neste Corporation, Porvoo, Finland

    Mats Käldström

Authors
  1. Alexandrina Sulman
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  2. Päivi Mäki-Arvela
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Corresponding author

Correspondence to Dmitry Yu. Murzin.

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Sulman, A., Mäki-Arvela, P., Bomont, L. et al. Vanillin Hydrodeoxygenation: Kinetic Modelling and Solvent Effect. Catal Lett 148, 2856–2868 (2018). https://doi.org/10.1007/s10562-018-2478-1

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