Babu, B. V., & Chaurasia, A. S. (2003).

Modeling, simulation and estimation of optimum

parameters in pyrolysis of biomass. Energy Conversion and Management, 44(13), 2135-
2158.

The present work involves the estimation of optimum parameters in the pyrolysis of biomass
for both non-isothermal and isothermal conditions. The modeling equations are solved
numerically using the fourth order Runge–Kutta method over a wide range of heating rates
(25–360 K/s) and temperatures (773–1773 K). The simulated results are compared with those
reported in the literature and found to be in good agreement qualitatively in the range of
operating conditions covered, but some very interesting trends are found, especially with
respect to the effect of net heating rate and temperature on final pyrolysis time. The final
pyrolysis time first decreases at lower values of net heating rate or temperature and then
increases as net heating rate or temperature is further increased, providing an optimum value
of net heating rate or temperature at which final pyrolysis time is minimum. This interesting
phenomenon, which was not reported by investigators earlier, is well explained by means of
the pyrolysis kinetics.

Hu, S., Jess, A., & Xu, M. (2007). Kinetic study of Chinese biomass slow pyrolysis:
comparison of different kinetic models. Fuel, 86(17-18), 2778-2788.

The slow pyrolysis of six Chinese biomasses was studied by thermogravimetric experiments.
Non-linear square fitting method is used to calculate DTG data. The analysis results show
that it is not possible to exactly represent the biomass pyrolysis by a one-step model with
different mechanisms. Thus, three-pseudocomponent models were used to simulate the
biomass pyrolysis. It was found that the three-pseudocomponent model with n-order kinetics
(model II) is more accurate than the model with first-order kinetics (model I). Activation
energies of three-pseudocomponents in model II are bigger than the values in model I. It is
shown that model II yields the best simulation results, especially with respect to describe
accurately the pyrolysis of the first pseudocomponent (hemicellulose) and the last one
(lignin). Nevertheless, with regard to a practical utilization, the three-pseudocomponent
model with a reaction order of one could be used, because the accuracy to represent biomass
pyrolysis is high enough. Unrealistic high values of the reaction order are avoided, and thus
this model is more realistic with respect to the chemical interpretation of the reaction order.
Gao, N., & Li, A. (2008). Modeling and simulation of combined pyrolysis and reduction zone
for a downdraft biomass gasifier. Energy Conversion and Management, 49(12), 3483-3490.

This paper simulates the behavior of a global fixed bed biomass gasification reactor. The
pyrolysis zone and reduction zone models are combined to simulate the global process of
biomass gasification. The volatiles and gases released from the pyrolysis zone were assumed
to crack into equivalent amounts of CO, CH4 and H2O. It is considered that the volatiles and
gases leave the pyrolysis zone instantaneously and enter the reduction zone as initial gas
concentrations. The numerical method applied is a Runge–Kutta fourth order method for
solution of the pyrolysis zone model and finite differences for the reduction zone model to
solve numerically the coupled ordinary differential equations. Simulations are performed for
the varying pyrolysis temperature with a heating rate of 25 K/min and constant temperature
of 1400 K as the initial reduction zone temperature at the same time. The simulation results
for the temperature and concentrations of the gaseous species are in good agreement with
published experimental data.

Wang, X., Hu, M., Hu, W., Chen, Z., Liu, S., Hu, Z., & Xiao, B. (2016). Thermogravimetric
kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.
Bioresource technology, 219, 510-520.

Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat,
rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism
for AR one-step pyrolysis was f(α) = (1 − α)1.1816α−1.8428 with kinetic parameters of: apparent
activation energy 221.7 kJ/mol, pre-exponential factor 4.17E16 s−1. Pyrolysis of AR feedstock
could not be described by one-step reaction attributes to heterogeneous features of pyrolysis
processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis
experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose,
lignin in CK-TPR model was f(α) = (1 − α)1.6244α−0.3371[−ln(1 − α)]−0.0515,
f(α) = (1 − α)1.0597α−0.6909[−ln(1 − α)]0.9026 and f(α) = (1 − α)2.9577α−4.7719, respectively. Apparent
activation energy of three pseudo components followed the order of
Elignin(197.3 kJ/mol) > Ecellulose(176.3 kJ/mol) > Ehemicelluloses (151.1 kJ/mol). Mechanism of
hemicelluloses pyrolysis could be further expressed as f(α) = (1 − α)1.4. The pyrolytic
mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis
was complex, which possibly was the combined effects of Nucleation, Diffusion,
Geometrical contraction, and Power law.

Babu, B. V., & Chaurasia, A. S. (2004). Pyrolysis of biomass: improved models for
simultaneous kinetics and transport of heat, mass and momentum. Energy conversion and
Management, 45(9-10), 1297-1327.

Understanding the physical phenomena of pyrolysis and representing them with an

appropriate mathematical model is essential in the design of pyrolysis reactors and biomass
gasifiers. Description of the chemical processes of pyrolysis is coupled to an unsteady state,
one dimensional, variable property model of transport phenomena, including heat convection,
conduction and radiation, volatiles and gas transport by diffusion and convection and
momentum transfer. In this study, a generalized reference model (Model I) incorporating all
the above effects is proposed. This is further improved by proposing two simplified models
(Models II and III) incorporating additional assumptions. A finite difference pure implicit
scheme utilizing a Tri-Diagonal Matrix Algorithm (TDMA) is employed for solving the heat
transfer and mass transfer model equations. A Runge–Kutta fourth order method is used for
the chemical kinetics model equations. Simulations are performed considering different
geometries of equivalent radius ranging from 0.0001 to 0.017 m and temperatures ranging
from 303 to 2800 K. The results obtained using these improved models are in excellent
agreement with the experimental data, much better than the agreement with earlier models
reported in the literature. The improved validated model, which is best suited for wide ranges
of operating conditions, is utilized to investigate the influence of particle size, particle shape,
product distribution, conversion time and heat of reaction.