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Kinetic analysis of biomass pyrolysis using a double distributed activation energy model

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Abstract

Pyrolysis is a fundamental step in thermochemical processes of biomass materials, so a suitable kinetic model is an essential tool to predict the evolution of the resulting products of reaction. However, many difficulties arise in modeling this process step due to the very high number of the involved reactions. In this work, a new double-Gaussian distributed activation energy model was applied in fitting the experimental data of olive residue pyrolysis obtained by thermogravimetric analysis. 2-DAEM formulation considers two sets of parallel reactions occurring and sharing the same pre-exponential factor, but shows different distributions of the activation energy, described by two separate Gaussian distributions that, in turn, grasp the two pyrolysis steps with a high accuracy. Since it is well known that in fitting all the kinetic parameters the pre-exponential factor results highly correlated with the activation energy, the former parameter was separately estimated as a linear combination of the values obtained for the three main biomass components, cellulose, hemicellulose and lignin.

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Abbreviations

DAEM:

Distributed activation energy model

EF:

Extractive free

TG:

Thermogravimetry

DTG:

Derivative thermogravimetry

E :

Activation energy (kJ mol−1)

E 0 :

Mean activation energy (kJ mol−1)

f(E):

Distribution function of activation energy (mol J−1)

k 0 :

Frequency factor (s−1)

k :

Kinetic constant (mol s−1)

T :

Absolute temperature (K)

R :

Universal gas constant (8.314 J mol−1 K−1)

t :

Time of conversion (s)

m 0 :

The initial mass (mass%)

m f :

The final residual mass (mass%)

m t :

The mass of the sample at time t (mass%)

N :

Number of data points

x :

Mass fraction of released volatiles

X :

SSR, sum of square residuals

y s :

Experimental data in fitting function

y(T):

Calculated data in fitting function

V :

Accumulated volatiles produced

V * :

Final accumulated volatiles produced

w :

Mass of primary/secondary pyrolysis

α :

Heating rate (K min−1)

σ E :

Standard deviation

1:

First Gaussian in 2-DAEM

2:

Second Gaussian in 2-DAEM

i :

ith component

j :

jth experimental data to fitting

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Authors and Affiliations

  1. Dipartimento di Ingegneria Chimica Materiali Ambiente, Sapienza University of Rome, Via Eudossiana 18, 00184, Rome, Italy

    Benedetta de Caprariis, Maria Laura Santarelli, Marco Scarsella, Nicola Verdone & Paolo De Filippis

  2. CIRCE, Research Center on Energy Resources and Consumptions, Mariano Esquillor, 15, 50018, Saragossa, Spain

    Carlos Herce

Authors
  1. Benedetta de Caprariis
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  2. Maria Laura Santarelli
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  3. Marco Scarsella
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  4. Carlos Herce
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  5. Nicola Verdone
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  6. Paolo De Filippis
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Correspondence to Carlos Herce.

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de Caprariis, B., Santarelli, M.L., Scarsella, M. et al. Kinetic analysis of biomass pyrolysis using a double distributed activation energy model. J Therm Anal Calorim 121, 1403–1410 (2015). https://doi.org/10.1007/s10973-015-4665-2

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  • DOI: https://doi.org/10.1007/s10973-015-4665-2

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