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Comparative investigation for the determination of kinetic parameters for biomass pyrolysis by thermogravimetric analysis

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Abstract

This paper discusses the different methods for determining the kinetic parameters (activation energy and pre-exponential factor) of biomass (beechwood and flax shives) pyrolysis based on Kissinger method, isoconversional methods (Kissinger–Akahira–Sunose and Friedman) and based model (nonlinear least square minimization and optimization by genetic algorithm). Because of the widely dispersed values of activation energy and pre-exponential factor of three pseudo-components of the biomass (cellulose, hemicellulose and lignin) found in the literature, the pyrolysis of cellulose, hemicellulose and lignin was also studied. This paper shows that kinetic parameters are very sensitive to methods used. The comparison of results shows a large difference for the same experimental results even for pure pseudo-components. Based on results comparison, we think that Kissinger method remains the best method for kinetic parameters determination. Indeed, Kissinger relation takes into account the biomass structure effect and the mineral content. Isoconversional methods are also very suitable for low and medium conversion rate. Despite the fact that based methods are considered to be robust methods for the estimation of kinetic parameters in chemical engineering, these methods may misestimate the activation energy and pre-exponential factor for cellulose, hemicellulose and lignin.

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Abbreviations

A :

Pre-exponential factor [s−1]

A α :

Pre-exponential factor at a given conversion degree [s−1]

E a :

Activation energy [kJ mol−1]

E α :

Activation energy at a given conversion degree [kJ mol−1]

GA:

Genetic algorithm

KAS:

Kissinger–Akahira–Sunose

m f :

Final mass [kg]

m i :

Initial mass [kg]

m T :

Mass at temperature T [kg]

N :

Number of experiments considered

n :

Reaction order [−]

NLSM:

Nonlinear least squares optimization method

OFW:

Ozawa, Flynn and wall

R :

Gas constant [8.314 J K−1 mol−1]

R²:

Correlation coefficient

S :

Convergence criterion [s-2]

T :

Temperature [K]

TGA:

Thermogravimetric analysis

T max :

Maximum temperature peak [K]

T offset :

Represents the end of the decomposition determined by the extrapolation of the DTG curves

T onset :

The temperature of start of the decomposition

α :

Conversion degree [−]

β :

Heating rate [K s−1]

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Acknowledgements

This work was supported by the European Union with the European regional development fund (ERDF) and by the Normandie Regional Council.

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Authors and Affiliations

  1. Laboratoire de Sécurité des Procédés Chimiques - LSPC EA 4704, Normandie Univ, INSA Rouen, UNIROUEN, 76000, Rouen, France

    Lokmane Abdelouahed, Sébastien Leveneur, Lamiae Vernieres-Hassimi, Laurent Balland & Bechara Taouk

  2. Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, 20500, Åbo, Turku, Finland

    Sébastien Leveneur

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  1. Lokmane Abdelouahed
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Correspondence to Lokmane Abdelouahed.

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Abdelouahed, L., Leveneur, S., Vernieres-Hassimi, L. et al. Comparative investigation for the determination of kinetic parameters for biomass pyrolysis by thermogravimetric analysis. J Therm Anal Calorim 129, 1201–1213 (2017). https://doi.org/10.1007/s10973-017-6212-9

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