Energy 239 (2022) 122228

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Energy
journal homepage: www.elsevier.com/locate/energy

Distributed activation energy model for lignocellulosic biomass

torrefaction kinetics with combined heating program
Yipeng Feng a, b, Keying Qiu c, Zhiping Zhang b, Chong Li c, **, Md. Maksudur Rahman d,
Junmeng Cai c, *
a
School of Mechanical and Electrical Engineering, Henan Institute of Science and Technology, Xinxiang, 453003, People's Republic of China
b
Key Laboratory of New Materials and Facilities for Rural Renewable Energy of China's Ministry of Agriculture and Rural Affairs, Henan Agricultural
University, Zhengzhou, 450002, People's Republic of China
c
Biomass Energy Engineering Research Center, School of Agriculture and Biology, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240,
People's Republic of China
d
Discipline of Chemical Engineering, Western Australian School of Mines: Minerals, Energy and Chemical Engineering, Curtin University, GPO Box U1987,
Perth, WA 6845, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Torrefaction kinetics is fundamental for the theoretical investigation and industrial application of tor-
Received 13 May 2021 refaction processes. Most of biomass torrefaction kinetic studies focused on kinetic modelling under
Received in revised form either isothermal or linear heating programs with one or several activation energies, which couldn't
26 September 2021
accurately reflect its reaction mechanisms. A distributed activation energy model (DAEM) was proposed
Accepted 29 September 2021
Available online 1 October 2021
to analyze logging residue torrefaction kinetics with a combined heating program at different temper-
atures. The model parameters were efficiently optimized by using the pattern search method. The results
showed that the DAEM could excellently describe the experimental data of logging residue torrefaction
Keywords:
Biomass
at various conditions. The obtained activation energy distributions for logging residue torrefaction with
Torrefaction the combined heating program at final temperatures of 240, 270 and 300
C lay in the range of 154
Kinetics e172 kJ mol1, 160e177 kJ mol1 and 165e185 kJ mol1, respectively. These findings indicated that major
Distributed activation energy model reactions occurring during torrefaction were the devolatilization and carbonization of biomass's hemi-
(DAEM) cellulose constituents and partial decomposition of biomass's cellulose constituents. The experimental
Pattern search method kinetic data of mesocarp fiber torrefaction at final temperatures of 220, 250 and 270
C from the liter-
ature was also successfully described by the DAEM.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction torrefaction is a promising thermal pre-treatment method of

Direct use of biomass as solid fuel is usually not worthy, because
of its poor fuel characteristics, including low heating value, high
moisture content, hygroscopic nature, low density, and poly-
morphism [1]. Direct biomass conversion leads to low efficiency of
thermochemical conversion and low quality of conversion products
with high upgrading costs [2,3]. In order to improve the quality of
raw biomass in terms of physicochemical properties and its ther-
mochemical conversion performance, it is necessary to seek some
pre-treatment methods for processing biomass. Meanwhile,
* Corresponding author.
** Corresponding author.
E-mail addresses: lichong@163.com (C. Li), jmcai@sjtu.edu.cn (J. Cai).
biomass [4].
Torrefaction involves the thermal decomposition of biomass in
the absence of oxygen at a temperature of typically 200e300
C [5].
Main product of torrefaction is torrefied biomass. It can improve
biomass's physical properties like grindability and pelletability,
ultimate and proximate compositions by increasing the carbon
content and heating value and decreasing the moisture and oxygen
contents [6]. Due to structural change of biomass during torre-
faction, biomass becomes hydrophobic, which significantly reduce
the biological decomposition risk of biomass [7]. It can make raw
biomass easier to handle and use, and subsequently reduce its
storage, handling and transportation costs [8]. More importantly, it
can influence the thermochemical conversion performance of
biomass by decomposing hemicelluloses and softening lignins
[9e11]. Torrefied biomass can easily replace coal or charcoal in

https://doi.org/10.1016/j.energy.2021.122228
0360-5442/© 2021 Elsevier Ltd. All rights reserved.
Y. Feng, K. Qiu, Z. Zhang et al.
Nomenclature
A Frequency factor (s1)
E Activation energy (kJ mol1)
f(E) Activation energy distribution (mol kJ1)
E0 Mean value of activation energy distribution (kJ
mol1)
s Standard deviation of activation energy distribution
(kJ mol1)
R Universal gas constant (8.3145 J mol1
C1)
t Time (s, min)
T Temperature (
C)
w Normalized mass (wt.%)
w Mean value of normalized mass (wt.%)
R2 Coefficient of determination (dimensionless)
C Carbon (dimensionless)
H Hydrogen (dimensionless)
O Oxygen (dimensionless)
N Nitrogen (dimensionless)
S Sulfur (dimensionless)
nd Number of data points (dimensionless)
P Model parameter vector
combustion or be used as a suitable feedstock for further thermo-
chemical conversion.
The study on torrefaction kinetics is fundamental for the
investigation of torrefaction reaction mechanisms and the design,
scale-up, optimization and industrial application of a biomass tor-
refaction system (as shown in Fig. 1). The results of biomass tor-
refaction kinetic study can be employed to establish the
corresponding chemical reaction model. Computational fluid dy-
namics (CFD) modelling can be performed through numerical cal-
culations of the mass, momentum and energy conservation
equations coupled with the initial and boundary conditions and
chemical reaction model. The simulation results can be employed
to predict the flow, temperature, and species fields in reactors and
estimate the hydrodynamic and thermochemical performances of
torrefaction systems [12,13], which are useful for the optimization
of torrefaction processes, and scale-up and industrial application of
torrefaction systems.
The objective of the torrefaction kinetics is to establish the
proper kinetic model and obtain the corresponding optimal kinetic
parameters. Several kinetic models have been developed to
describe the torrefaction behaviors of different biomass including
individual components of lignocellulosic biomass. For example,
Swiechowski et al. [14] used a simple empirical model in the form
of an exponential-type function to fit the isothermal kinetic data of
oxytree pruned residue torrefaction. According to Duan et al. [15],
the empirical model can fit the torrefaction kinetic curve of biomass
at a short torrefaction period (<120 min). However, the theoretical
mass loss curve from the empirical model would reduce to zero,
which contradicts that biomass wouldn't be totally converted
during torrefaction. Hence, the empirical model has come up with
some theoretical drawbacks. Duan et al. [15] used a reaction order
model to analyze the torrefaction kinetics of beech wood at three
isothermal temperatures of 220, 250 and 280
C. The reaction order
model is an apparent global model that cannot reflect the complex
mechanism of biomass torrefaction. Zhang et al. [16] reported the
kinetic compensation effect between the kinetic parameters of the
reaction order model for the isothermal torrefaction kinetics of
woody biomass. The kinetic compensation effect describes the
linear relationship between the logarithm of frequency factor and
2
Energy 239 (2022) 122228
Abbreviation
SSE Sum of squared errors
DAEM Distributed activation energy model
TGA Thermogravimetric analysis
HHV Higher heating value (MJ kg1)
ASTM American Society for Testing and Materials
OF Objective function
RRMSE Relative root mean square error (%)
CFD Computational fluid dynamics
Greek letters
a Degree of conversion (dimensionless)
b Heating rate (
C min1)
Subscripts
0 Refers to starting conditions
f Refers to final conditions
exp Refers to experimental data
cal Refers to calculated data
i Refers to the i-th data point
j Refers to the j-th torrefaction temperature
activation energy and it was found in the kinetic parameters of the
distribution activation energy model (DAEM) for the pyrolysis of
biomass and its biopolymer components [17], which will be
considered to determine the kinetic parameters of DAEM in this
study. Di Blasi and Lanzetta [18] proposed a two-step kinetic model
for the kinetic description of xylan torrefaction, which was also
applied to study the torrefaction kinetics of willow [19] and poplar
wood [20]. The two-step model involves the formation of a solid
intermediate product, which is difficult to measure. The charac-
teristics of the above kinetic models for biomass torrefaction was
summarized in Table 1.
The above kinetic models used one or several activation en-
ergies to describe biomass torrefaction processes, that couldn't
reflect the reaction mechanisms of biomass torrefaction. Lignocel-
lulosic biomass contains three major biopolymer components:
hemicellulose, cellulose and lignin. Cellulose and hemicellulose are
polysaccharides, and made of sugar monomers. Hemicellulose
consists of a cross-linked and comparatively short polymer,
whereas cellulose is a straight-chain long polymer [21]. The
decomposition temperature of hemicellulose (220e315
C) is lower
than that of cellulose (315e400
C) [22]. The strengths of chemical
chains containing in biomass biopolymer components are different,
consequently, the breakage of those chemical chains requires
different activation energies [23,24]. Hence, the kinetic process of
biomass thermal decomposition usually presents a distribution of
activation energies [25]. The distributed reactivity of biomass
thermal decomposition can frequently be described by the DAEM
[26], which assumes that a complex chemical reaction process
takes a large number of independent and parallel reactions with
different activation energies [27]. The DAEM has been widely used
to explain the pyrolysis kinetic behaviors of biomass, whereas only
a few studies focused on biomass torrefaction kinetics using the
DAEM. Sarvaramini et al. [28] used the DAEM to analyze the
isothermal torrefaction kinetics of biomass biopolymer constitu-
ents (e.g., cellulose and hemicellulose) at isothermal torrefaction
temperatures of 240 and 280
C, and obtained that the activation
energies of cellulose and hemicellulose torrefaction distributed in
the ranges of 200e220 kJ mol1 and 125e145 kJ mol1, respec-
tively. Huang et al. [29] employed the DAEM to analyze the
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 1. Importance of torrefaction kinetics in design and application of torrefaction system.

Table 1
Characteristics of biomass torrefaction kinetic models.

Torrefaction kinetic model Characteristics Reference

Simple empirical model  Isothermal heating program [14]

 Has some theoretical drawbacks
 Has only statistical meaning
Reaction order model  Isothermal heating program [15,16]
 Global model with apparent kinetic parameters
Two-step model  Combined heating program [18e20]
 Involving solid intermediate product (difficult to experimentally validated)
DAEM  Combined heating program this study
 Activation energy distribution reflecting complex reaction mechanism of biomass torrefaction

nonisothermal torrefaction kinetics of sewage sludge at a linear
heating program and found that the corresponding activation en-
ergies ranged from 70 to 150 kJ mol1. The above biomass torre-
faction kinetic studies were established under either isothermal or
linear heating programs. The isothermal conditions are rarely
achieved experimentally due to the heating up of the sample. In
practice, the torrefaction kinetic experiments are usually per-
formed under a combined heating program with both isothermal
and linear heating stages. The torrefaction kinetic study of biomass
with the combined heating program using the DAEM is still missing
in the exisiting literature.
Therefore, the present work aims to comprehensively
3
investigate the torrefaction kinetics under a combined heating
program using the DAEM. The study could be able to obtain the
activation energy distribution of biomass torrefaction, reflecting
the reactivity distribution of various reactions occurring in biomass
torrefaction.
2. Materials and experiments
Logging residue collected from a wood processing factory
located in Shanghai, China was used in this study. The obtained
material was dried and ground into particles with particle sizes
ranging between 0.18 and 0.25 mm. To ensure the particle size of
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

sample and carry out the physicochemical characterization and
kinetic test, sieve analysis was in place. The proximate analysis of
the logging residue sample was performed in accordance with
ASTM standards [30]. The elemental contents (C/H/N/S/O) of the
sample were measured in an elemental analyzer (Vario EL Cube
Elemental Analyzer, Germany). The higher heating values (HHV)
was measured in an oxygen bomb calorimeter (XRY-1B, Shanghai
Changji Geological Instruments Co, Ltd, China). The contents of
cellulose, hemicellulose and lignin of the logging residue sample
were determined according to Jin et al. [31]. A near-infrared spec-
trometer (RED-Wave-INRX-SR, StellarNet, USA) was used to
perform the compositional analysis of the logging residue sample
at the Instrumental Analytical Center of Shanghai Jiao Tong Uni-
versity, China. The standard methods and main apparatus for the
physicochemical characterization of the logging residue sample
were summarized in Table 2.
The torrefaction kinetic tests of the logging residue sample were
conducted in a thermogravimetric analyzer (TGA 7, PerkinElmer,
Inc, USA). Pure nitrogen with a flow rate of 60 mL min1 was used
as the purge gas to ensure the inert atmosphere during torrefaction.
For each test, about 4.5 mg of the sample was weighted and then
pressed flat into the base of a test crucible. The following heating
program for kinetic tests included isothermal and linear heating
stages were maintained: (1) the temperature was increased to
105
C from room temperature with a heating rate of 20
C min1;
(2) then the temperature was maintained at 105
C for 20 min to
ensure removing the water contained in samples completely; (3)
subsequently, the temperature was increased to the specified tor-
refaction temperatures (240, 270 and 300
C) with a heating rate of
20
C min1; (4) finally, the specified torrefaction temperature was
maintained for 60 min. The torrefaction temperature has an
important influence on the kinetic behaviors of lignocellulosic
biomass torrefaction [12]. According to our previous study of
woody biomass torrefaction [20], low torrefaction temperatures
(e.g. about 200e220
C) shows relatively mass loss during TGA,
affecting the accuracy of further kinetic analysis. Therefore, three
torrefaction temperatures of 240, 270 and 300
C were selected as
the representatives of low, mild and sever torrefaction conditions
to obtain the experimental data with relatively noticeable mass loss
and investigate the influences of different torrefaction tempera-
tures on the kinetic results of biomass torrefaction. The heating rate
has a slighter effect on the evolution of torrefaction products
(including torrefaction volatile and solid products), and the mass
and energy yields of the torrefaction process than the final torre-
faction temperature and period [20]. To reduce the effect of heat
transfer on the torrefaction kinetic experimental results, slow
heating rate (usually 25
C min1) with small sample particle
sizes (2 mm) can be used to ensure that torrefaction processes are
kinetically controlled [32]. Therefore, only one heating rate of 20
C
min1 was used in the torrefaction kinetic tests in this study. To
ensure reproducibility, the test were repeated thrice for each tor-
refaction temperature, and the average mass loss data were used
for further analysis.
The first stage involving in biomass torrefaction process is the
dehydration stage. The mechanism of water evaporation in the
dehydration stage is different from the decomposition of lignocel-
lulosic components in biomass during thermal decomposition [33].
Therefore, in the kinetic analysis of biomass torrefaction, the
dehydration stage was not considered. The obtained experimental
data should be pre-processed before kinetic analysis. The data pre-
processing includes the removal of “error” data, removal of the
dehydration stage, and normalization of the kinetic data (detailed
information about can be found in Ref. [33]).
3. DAEM and its numerical calculation
In literature, the simple empirical model, the reaction order
model, and the two-step model were usually used to analyze the
torrefaction kinetic behaviors of lignocellulosic biomass. However,
one or several activation energies used in those torrefaction kinetic
models cannot accurately reflect the reaction mechanisms of
biomass torrefaction. The torrefaction kinetic process of lignocel-
lulosic biomass involves a lot of reactions. Those reactions corre-
spond to the thermal decomposition of biomass components and
the breakage of various chemical chains with different strengths,
which indicates the distributed reactivity of biomass torrefaction.

Table 2
Physicochemical characterization of biomass samples.

Property Standard method Main apparatus

Proximate analysis
Moisture content ASTM E1756-08. Standard Electric thermostatic drying oven,
Test Method for electronic balance
determination of Total
Solids in Biomass
Ash content ASTM E1755-01. Standard Muffle furnace, electronic balance
Test Method for Ash in
Biomass
Volatile matter content ASTM E872-82. Standard Muffle furnace, electronic balance
Test Method for Volatile
Matter in the Analysis of
Particulate Wood Fuels
Fixed carbon content ASTM E870-82. Standard
Test Methods for Analysis of
Wood Fuels.
Elemental analysis
C/H/N/S/O contents Elemental analyzer
Energy content
Higher heating value ASTM 5865e10. Standard Oxygen bomb calorimeter
Test Method for Gross
Calorific Value of Coal and
Coke
Compositional analysis
Cellulose, hemicellulose and lignin contents Procedures developed by Near-infrared spectroscopy
Jin et al. [31].

4
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Hence, considering the characteristics of the DAEM and the

" #
distributed reactivity of biomass torrefaction process, we used the 1 ðE  E0 Þ2
DAEM to describe the kinetics of biomass torrefaction. The model f ðEÞ ¼ pffiffiffiffiffiffi exp  (4)
s 2p 2s2
assumes that there are a large number of decomposition reactions
during biomass torrefaction and each reaction has its own kinetic
where E0 and s are the mean value and standard deviation of the
parameters.
activation energy distribution, respectively.
For the i-th reaction, its kinetics can be described by the
The degree of conversion, a, can be calculated from experi-
Arrhenius law [34]:
mental kinetic data obtained by thermogravimetric analysis (TGA)

 [33]:
da i E
¼ Ai , exp  i ,hðai Þ (1)
dt R,T w0  wðtÞ
aðtÞ ¼ (5)
w0  wf
where the subscript i represents the value related to the i-th re-
action, a is the degree of conversion, t is the time, A is the frequency where w0 is the initial mass, w(t) is the mass at time t, and wf is the
factor, E is the activation energy, R is the universal gas constant, T is final mass fraction during torrefaction. Theoretically, the mass loss
the absolute temperature and h(a) is the kinetic mechanism func- curve of biomass from TGA under an inert atmosphere has two
tion, which is usually described by the first-order kinetics (h(a) ¼ 1- mass loss plateaus, of which one corresponds to water evaporation.
a) because of its mathematical tractability. Integrating Equation (1), In contrast, the other corresponds to the end of decomposition
one can obtain Equation (2): reaction [33]. However, the experimental mass loss curve of
biomass torrefaction still show a downward trend even for a long
 ðt
  torrefaction time (e.g., 3e4 h), which is caused by the low tem-
Ei perature under torrefaction conditions (typically 200e300
C).
ai ¼ 1  exp  Ai , exp  dt (2)
R,T Hence, it is difficult to experimentally measure wf. But it can be
0
numerically determined according to the trend of the mass loss
The DAEM further assumes that all reactions share the same curve with the help of the DAEM, which will be presented in the
frequency factor and that the number of reactions is large enough section of ‘Results and discussion’.
to permit the activation energies to be expressed as a continuous According to Equation (5), Equation (3) becomes
distribution [35]. Fig. 2 presents the schematic description of
biomass torrefaction by the DAEM.  ð
∞  ðt
 
Integrating over all activation energies for all reactions during E
wðtÞ ¼ wf þ w0  wf exp  A exp  dt f ðEÞdE (6)
biomass torrefaction, Equation (2) becomes: RT
0 0

In Equation (6), w(t) represents the mass of solid residues at

ð
∞  ðt
 
E time t during torrefaction. The evolution of torrefaction volatile can
a¼1  exp  A exp  dt f ðEÞdE (3) be obtained according to Equation (6):
RT
0 0

  ð
∞ 
where f(E) represents the distribution of activation energies. The
vðtÞ ¼ w0  wðtÞ ¼ w0  wf 1  exp
true distribution of activation energy is unknown. Hence, different
0
continuous distributions have been applied to represent the dis-
tribution of activation energies, for example, the Gaussian [36],

ðt  

E
Weibull [37,38], and Logistic [39e41] distributions. In literature, the  A exp  dt f ðEÞdE (7)
RT
Gaussian distribution is the most commonly used distribution: 0

where v(t) is the mass of torrefaction volatile at time t during tor-

refaction. In a properly designed torrefaction system, the torre-
faction volatile can be combusted to generate heat for the drying of
raw biomass and the torrefaction process [8].
As stated in the Section ‘2 Materials and experiments’, the ki-
netic study of logging residue torrefaction is performed under the
following combined heating program:

8
> Tf  T0
>
< T0 þ bt
> 0t
b
TðtÞ ¼ (8)
>
> Tf  T0
>
: Tf t>
b

where T0 is the starting decomposition temperature, b is the

heating rate, and Tf is the final torrefaction temperature.
Fig. 2. Schematic description of biomass torrefaction by the DAEM. From Equation (7), the DAEM involves the inner dt and outer dE
integrals. Under the combined heating program shown in Equation
(8), the inner dt integral becomes:

5
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

81 ð
T

E Tf  T0
>
> exp  dT 0t
>
>b RT b
ðt
 >
< T0
E
exp  dt ¼ (9)
RT >
> Tðf

 !
>
> T  T0 Tf  T0
0 >
: 1 exp  E dT þ t  f E
exp  t>
b RT b RTf b
T0

require continuous first- or second-order derivatives of the objec-

ðT
 ðT
 Tð0
 tive functions during optimization calculations [46].
E E E
exp  dT ¼ exp  dT  exp  dT (10) In this study, the pattern search method was used to optimize
RT RT RT
T0 0 0 the model parameters since the pattern search method is simple in
concept, easy to implement, computationally efficient and robust


RT E dT is the temperature integral,
with objective function failures [47]. Unlike traditional optimiza-
where the integral 0 exp RT
tion methods, the pattern search method is a direct search method,
which has no analytical solution. Many approximations for the which searches a set of points around the current point, finding the
temperature integral have been proposed [42,43]. In the present point whose objective function value is lower than the value at the
work, the temperature integral approximation from Cai et al. [44] current point [48]. The pattern search method proceeds by calcu-
was used: lating a sequence of points. It begins by establishing a set of points
(called a mesh) around a given point from the initial starting point
ðT

 or the previous step. The method polls those mesh points by
E RT 2 E þ 0:66691RT E
exp  dTz exp  (11) computing their objective function values. If one mesh point is
RT E E þ 2:64943RT RT
0
found to lower the objective function value, and the new point
becomes the current point at the next iteration. The mesh is
The upper integral limit of the outer dE integral is infinite. Ac- established by adding the direction vectors to the current point
cording to Ref. [45], when the upper integral limit is replaced by a through a scalar (called mesh size). The initial mesh size is set to be
relatively large value (e.g., E0þ3s), the value of the dE integral is 1 by default. After a successful poll, the method multiplies the
close to the real value. In this study, E0þ10s is used as the upper current size by 2. If none of the mesh points has a smaller objective
limit of the outer dE integral. Therefore, its numerical calculation function value than the previous step, the pattern search method
can be done using the trapezoidal integration rule. multiplies the current mesh size by 0.5. Hence, in general, the mesh
size fluctuates with the iteration, and the overall change trend of
 ð s
 E0 þ10  ðt
 
mesh size is downwards during the implementation of the pattern
E
wðtÞ ¼ wf þ w0  wf exp  A exp  dt f ðEÞdE search method. The pattern search optimization method repeat the
RT
0 0 above steps until the pre-given stopping criteria is reached to find
(12) the optimal solution for the minimization of the objective function.
The following stopping criteria are usually used: the minimum
The numerical calculation flow diagram of the DAEM for tolerance for mesh size, maximum number of iterations, maximum
lignocellulosic biomass torrefaction kinetics is shown in Fig. 3. number of evaluations of the objective function, and minimum
tolerance of the objective function [49]. Therefore, it has been
4. DAEM parameter estimation successfully applied to a wide range of optimization problems, e.g.,
the kinetic modelling of bio-oil aging [50] and woody biomass
The estimation of the model parameters is required to fit the torrefaction [15], tuning of the fuzzy control system membership
experimental kinetic data of lignocellulosic biomass torrefaction functions [51], and heat exchanger design process optimization
with the DAEM. For this purpose, the following objective function [52]. The detailed information about the calculation process of the
(OF) is established based on the sum of the squared errors (SSE) pattern search method can be found in Ref. [53]. Fig. 4 shows the
between the experimental data and the data calculated from the flow diagram of the pattern search method for an optimization
DAEM: problem.
  Xh  i2
SSEj Pj ¼ wexp;j ðti Þ  wcal;j ti ; Pj
i
where P is the parameter vector, i represents the i-th data point, j
represents the j-th torrefaction temperature, and the subscripts exp
and cal represent the experimental data and the data calculated
from the model, respectively.
The model parameter values can be optimized by minimizing
the objective function (13). The objective function has no explicit
expression, and its derivatives are difficult to obtain. The optimi-
zation problem cannot be solved by means of the conventional
optimization methods, e.g., steepest descent, Newton, conjugate
direction, conjugate gradient, and quasi-Newton methods, which
(13)
5. Results and discussion
5.1. Physicochemical properties of logging residue
The physicochemical properties of the logging residue sample,
including the proximate, ultimate, and compositional analysis re-
sults, and HHV were obtained and listed in Table 3. The fixed carbon
and oxygen contents were determined by difference according to
Equations (14) and (15), respectively.
6
Y. Feng, K. Qiu, Z. Zhang et al.
Fig. 3. Numerical calculation flow diagram of DAEM for lignocellulosic biomass torrefaction kinetics.
Cfc ðwt:%Þ ¼ 100 wt:%  Cm ðwt:%Þ  Ca ðwt:%Þ
 Cv ðwt:%Þ
CO ðwt:%Þ ¼ 100 wt:%  CC ðwt:%Þ  CH ðwt:%Þ
 CN ðwt:%Þ  CS ðwt:%Þ
where Cfc , Cm , Ca , and Cv are the fixed carbon, moisture, ash, and
volatile matter contents on as-received basis, respectively, CO , CC ,
CH , CN , and CS are the contents of O, C, H, N, and S on dry basis,
respectively.
From the results included in Table 3, it was obtained that the
sample had a relatively high volatile matter content, which indi-
cated that the sample had the potential for energy use [54]. The
sample had a relatively high oxygen content. Hence, torrefaction a
possible technology can be utilized to reduce the sample's oxygen
content. Promisingly, the HHV of the sample was greater than those
of some typical herbaceous biomasses (e.g., rice straw [55] and
wheat straw [56]).
Energy 239 (2022) 122228
5.2. Kinetic modelling of logging residue torrefaction
Fig. 5 shows the pre-processed kinetic experimental data of
(14) logging residue torrefaction with the combined heating program at
different final torrefaction temperatures of 240, 270 and 300
C.
From Fig. 5, it can be seen that a higher temperature can promote
the thermal decomposition reaction and make more torrefaction
volatiles releasing during torrefaction. Similar results can be found
(15)
in the torrefaction of sorghum distilled residue [57] and almond
and walnut shells [58].
As presented above, the pattern search method was used for the
determination of the model parameters. The optimization effi-
ciency of the pattern search method depends on the initial guess of
the parameters [59]. Consequently, the choice of an initial guess
determines how quickly the pattern search method converges to
the optimal solution [59]. The grid search method was used to
obtain a better initial guess for the model parameters in this study.
In the DAEM, the frequency factor is assumed to be shared by all the
reactions involved [60]. And the frequency factor is usually corre-
lated with the mean value of activation energy distribution by the
so-called kinetic compensation effect [17]. Some studies about
7
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 4. Flow diagram of pattern search method.

Table 3 value was considered in this study. The initial guess of the wf values
Physicochemical properties of logging residue sample. can be approximately estimated from the curves presented in
Physicochemical property Value Fig. 5: 60 wt% for 240
C, 50 wt% for 270
C, and 47 wt% for 300
C. It
Proximate analysis (on as-received basis), wt.%
is difficult to estimate the initial guess of E0 and s. The E0 and s
Moisture content 7.94 ± 0.05 values for biomass thermal decomposition published in the litera-
Ash content 1.75 ± 0.01 ture were in the ranges of 150e250 kJ mol1 and 0.5e30 kJ mol1,
Volatile matter content 82.17 ± 0.08 respectively [60]. To obtain a good initial guess of E0 and s, the SSE
Fixed carbon content (by difference) 16.07
values with different E0 (from 150 to 250 kJ mol1) and s (from 0.5
Ultimate analysis (on dry basis), wt.%
C 46.88 ± 0.07 to 30 kJ mol1), and fixed A and wf values were calculated according
H 6.15 ± 0.03 to Equation (13). To investigate the effect of the grid size on the
N 0.42 ± 0.02 results, two different grid sizes (0.05 and 0.02 kJ mol1) were
Sa e considered in this study. Fig. 6 shows the SSE values with different
O (by difference) 44.8
Energy content (on dry basis), MJ kg1
values of E0 and s at different grid sizes for logging residue torre-
HHV 18.46 ± 0.09 faction with the combined heating program at three final torre-
Compositional analysis (on dry basis), wt.% faction temperatures of 240, 270 and 300
C. In order to present the
Cellulose 42.2 ± 0.12 results more clearly, we removed the points where the SSE values
Hemicellulose 16.6 ± 0.05
were greater than some certain values (50 for 240
C, 150 for 270
C,
Lignin 25.6 ± 0.08
and 80 for 300
C). According to the results included in Fig. 6, the
a
0.01 wt%. initial guess of the parameters at different grid sizes for logging
residue torrefaction at three temperatures were obtained and listed
in Table 4. From Table 4, it was obtained that the results were very
thermal decomposition kinetics of solid fuels reported that the
close for the cases at different sizes, which indicated that the
increase in the mean value of activation energy distribution is
optimization problem for the estimation of DAEM parameters in
accompanied by a corresponding increase in the frequency factor
this study was grid independent.
and vice versa [17,61,62]. Hence, it isn't easy to estimate a trust-
Based on the initial guess of the model parameters, the opti-
worthy value of the frequency factor. In most of the literature
mization calculations using the pattern search method were per-
[63e65], A was considered to be fixed. According to de Caprariis
formed to estimate the DAEM parameters. Fig. 7 shows the best
et al. [65], A ¼ 2.3  1013 s1 was suitable to represent the thermal
objective function value and mesh size at each iteration in the
decomposition kinetics of lignocellulosic biomass, therefore, this
optimization processes of DAEM parameters for logging residue

8
Y. Feng, K. Qiu, Z. Zhang et al.
Fig. 5. Pre-processed kinetic experimental data of logging residue torrefaction.
pyrolysis kinetics at 240, 270 and 300
C. From Fig. 7, it can be
obtained that the objective function values decrease with iteration,
and the optimization process can be done with fast convergence.
The optimal DAEM parameter values for logging residue torre-
faction kinetics with the combined heating program at different
final torrefaction temperatures were obtained and listed in Table 5.
The activation energy distributions for the torrefaction of other
samples in the literature are also presented in Table 5 for
comparison.
The kinetic curves of logging residue torrefaction with the
combined heating program at different temperatures can be
reproduced by using the DAEM with the obtained optimal param-
eter values. For comparison, the experimental kinetic curves of
logging residue torrefaction were also processed using the reaction
order model reported by Duan et al. [15]. The comparison between
the experimental data and the reproduced curves for logging res-
idue torrefaction with the combined heating program at three
torrefaction temperatures of 240, 270 and 300
C by the DAEM and
reaction order model was shown in Figs. 8e10, respectively. The
mass fraction changes of torrefaction volatile with torrefaction time
obtained from the experiment and calculated from the DAEM were
also presented in Figs. 8e10. The deviations between the experi-
mental and calculated data were plotted underneath the figures.
The coefficient of determination (R2) and the relative root mean
square error (RRMSE) were considered as quantitative statistical
measures [66]:
nd;j h
Energy 239 (2022) 122228
experimental kinetic curves of logging residue torrefaction at three
torrefaction temperatures more accurately than the reaction order
model, and the DAEM excellently fits the experimental kinetic data
of logging residue torrefaction with the combined heating program
at three torrefaction temperatures, which can be indicated by the
ranges of R2 (0.994e0.999) and RRMSE (0.919%e1.937%) for the
DAEM.
The obtained activation energy distributions for logging residue
torrefaction with the combined heating program at three torre-
faction temperatures were shown in Fig. 11. It can be obtained that
(1) with increasing torrefaction temperature, the activation energy
distribution shifts towards higher activation energy; (2) the acti-
vation energies for logging residue torrefaction with the combined
heating program at 240, 270 and 300
C were distributed in the
range of 154e172 kJ mol1 (peak centered at 162.7 kJ mol1),
160e177 kJ mol1 (peak centered at 168.4 kJ mol1), and
165e185 kJ mol1 (peak centered at 174.7 kJ mol1), respectively.
According to Wu et al. [67], the activation energies of biomass
pyrolysis are distributed in a wide range of 170e300 kJ mol1.
Torrefaction is a mild pyrolysis, and its reaction temperature and
heating rate are lower than conventional pyrolysis, which are
usually conducted at the temperature of 450e650
C and heating
rate of 100e500
C min1 (intermediate pyrolysis) [68] or over
1000
C s1 (fast pyrolysis) [69]. Besides, biomass pyrolysis involves
the thermal decomposition of lignin, which occurs in a wide tem-
perature range of 405e750
C and requires a wide activation energy
of 200e300 kJ mol1 [70].
P  i2 From the results included in Table 5 and Fig. 11, the activation
wexp;j ðti Þ  wcal;j ti ; Pj
energy distributions of logging residue torrefaction differed from
R2j ¼ 1  i¼1 n (16) that of sewage sludge torrefaction. The possible reason was that the
Pd;j
2
wexp;j ðti Þ  wexp;j chemical components of sewage sludge totally differ from that of
i¼1
lignocellulosic biomass. And the kinetic results of logging residue
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi torrefaction were between the results of hemicellulose torrefaction
nd;j h
P  i2 and cellulose torrefaction reported by Sarvaramini [28]. This indi-
1 wexp;j ðti Þ  wcal;j ti ; Pj
nd;j cated that the major reactions occurring in biomass torrefaction are
i¼1
RRMSEj ¼  100% (17) the devolatilization and carbonization of biomass's hemicellulose
wexp;j
constituents and the partial decomposition of biomass's cellulose
constituents.
where nd is the number of data point and wexp is the mean value of
The DAEM with the optimal kinetic parameters can be used to
experimental data. The closer the value of R2 is to 1, the more
explain the characteristics of biomass torrefaction kinetics, and to
variability the model describes experimental data. In general, the
establish the chemical reaction model. The simulation of biomass
goodness-of-fit of a model is considered excellent when RRMSE is
torrefaction process can be performed by solving the chemical re-
less than 10% [66].
action model coupled with the mass, momentum, energy
From Figs. 8e10, it can be obtained that the DAEM describes the
9
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 6. Changing of SSE with different E0 and s at different grid sizes, and fixed A and wf values for logging residue torrefaction at different torrefaction temperatures (a) 240
C, (b)
270
C, and (c) 300
C.

Table 4 conservation equations. The simulation results can be used to

Optimal results of grid search method with different grid sizes for logging residue optimize the torrefaction system operating conditions for desirable
torrefaction kinetics.
mass and energy yields and high conversion efficiency.
Torrefaction temperature Grid size ¼ 0.05 kJ mol1 Grid size ¼ 0.02 kJ mol1
1 1
E0/kJ mol s/kJ mol E0/kJ mol1 s/kJ mol1
5.3. Kinetic modelling of mesocarp fiber torrefaction
240 162.40 2.15 162.40 2.16
270 168.90 2.65 168.90 2.66
To estimate the applicability of the presented DAEM in the
300 174.90 3.60 174.90 3.62
torrefaction kinetics of other biomass, the kinetic experimental
data of mesocarp fiber torrefaction reported from Talero et al. [71]
was considered. The physicochemical properties including
10
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 7. Optimization calculations of DAEM parameter estimation for logging residue torrefaction kinetics at three torrefaction temperatures (a) 240
C, (b) 270
C, and (c) 300
C.

Table 5
Optimal DAEM parameters for logging residue torrefaction kinetics at different torrefaction temperatures together with parameters for torrefaction of other samples in the
literature.

Torrefaction conditions Model Activation energy distribution and other Reference

parameter values

Logging residue Combined heating program with DAEM with combined heating program, Gaussian E0 ¼ 162.650 kJ mol1, s ¼ 2.559 kJ mol1, This
torrefaction Tf ¼ 240
C distribution of activation energies wf ¼ 58.798 wt% study
Combined heating program with E0 ¼ 168.379 kJ mol1, s ¼ 2.685 kJ mol1,
Tf ¼ 270
C wf ¼ 52.913 wt%
Combined heating program with E0 ¼ 174.724 kJ mol1, s ¼ 2.783 kJ mol1,
Tf ¼ 300
C wf ¼ 48.113
Sewage sludge Nonisothermal torrefaction with 20, Simplified DAEM with linear heating program E0 ¼ 133.97 kJ mol1 [29]
torrefaction 35, 50, 65 and 80 K min1
Cellulose Isothermal torrefaction with DAEM with isothermal heating program, log-normal Activation energy distribution: 200 [28]
torrefaction Tf ¼ 280
C distribution of activation energies e220 kJ mol1 with peak at 207 kJ mol1
Hemicellulose Isothermal torrefaction with Activation energy distribution: 125
torrefaction Tf ¼ 280
C e145 kJ mol1 with peak at 132 kJ mol1

proximate, ultimate and compositional analyses results of meso-
carp fiber samples were listed in Table 6.
The torrefaction kinetic tests of the dried and milled mesocarp
fiber sample were performed by TGA. The heating program used for
mesocarp fiber torrefaction was as follows: the sample was dried in
situ at 105
C for about 30 min, then the sample was heated using
10
C min1 until the specific torrefaction temperature (e.g., 220,
250 and 270
C), which was kept constant for a period of torre-
faction time. The experimental kinetic data of mesocarp fiber tor-
refaction with the combined heating program at three torrefaction
temperatures of 220, 250 and 270
C was processed using the same
procedure for processing the experimental data of logging residue
torrefaction presented above. The experimental data and the curves
predicted by the DAEM for mesocarp fiber torrefaction with the
combined heating program at torrefaction temperatures of 220,
250 and 270
C were shown in Fig. 12e14. It was observed that the
deviations between the experimental data of mesocarp fiber tor-
refaction with the combined heating program at all torrefaction
temperatures were small, the corresponding R2 values were rela-
tively high (0.997) and the RRMSE values were relatively low
(0.635%). The results included in Figs. 11e13 indicated that the
DAEM described the kinetics of mesocarp fiber torrefaction with

11
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 8. Comparison between experimental data and model prediction by DAEM and reaction order model for logging residue torrefaction at 240
C.

Fig. 9. Comparison between experimental data and model prediction by DAEM and reaction order model for logging residue torrefaction at 270
C.

12
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 10. Comparison between experimental data and model prediction by DAEM and reaction order model for logging residue torrefaction at 300
C.

Fig. 11. Activation energy distributions for logging residue torrefaction with combined heating program at three temperatures of 240, 270 and 300
C.

13
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Table 6 the combined heating program at torrefaction temperatures of 220,

Physicochemical properties of mesocarp fiber samplesa. 250 and 270
C.
Physicochemical property Value

Proximate analysis (after drying at 105
C for 18 h), wt.% 6. Conclusions

Moisture content 3.5
Ash content 3.3 The kinetics of logging residue torrefaction with the combined
Volatile matter content 72.8
heating program was experimentally investigated at different tor-
Fixed carbon content (by difference) 20.4
Ultimate analysis (after drying at 105
C for 18 h),wt.%
refaction temperatures of 240, 270 and 300
C. The experimental
C 49.0 results showed that high temperature could facilitate torrefaction
H 5.2 reactions. The DAEM with the combined heating program was
N 1.67 proposed to describe the torrefaction kinetics of logging residue.
Sa 0.12
The numerical calculations and parametric study of the DAEM were
O (by difference) 37.3
Energy content (after drying at 105
C for 18 h), MJ kg1 performed. The pattern search method was employed to efficiently
HHV 18.68 optimize the DAEM parameters. The results showed that the DAEM
Compositional analysis (after drying at 105
C for 18 h), wt.% could excellently descibe the experimental kinetic behaviors of
Cellulose 42.8
logging residue torrefaction with the combined heating program at
Hemicellulose 18.1
Lignin 24.8
different torrefaction temperatures. The obtained activation energy
a
distributions for logging residue torrefaction with the combined
Data taken from Ref. [71].
heating program at different torrefaction temperatures of 240, 270
and 300
C were in the ranges of 154e172 kJ mol1 with a
the combined heating program quite well. Fig. 15 showed the maximum at 162.7 kJ mol1, 160e177 kJ mol1 with a maximum at
activation energy distributions of mesocarp fiber torrefaction with 168.4 kJ mol1, and 165e185 kJ mol1 with a maximum at
174.7 kJ mol1, respectively. The results indicated that major

Fig. 12. Comparison between experimental data and model prediction by DAEM for mesocarp fiber torrefaction at 220
C.

14
Y. Feng, K. Qiu, Z. Zhang et al. Energy 239 (2022) 122228

Fig. 13. Comparison between experimental data and model prediction by DAEM for mesocarp fiber torrefaction at 250
C.

Fig. 14. Comparison between experimental data and model prediction by DAEM for mesocarp fiber torrefaction at 270
C.

15
Y. Feng, K. Qiu, Z. Zhang et al.
Fig. 15. Activation energy distributions of mesocarp fiber torrefaction.
reactions during biomass torrefaction were the devolatilization and
carbonization of biomass's hemicellulose constituents and the
partial decomposition of biomass's cellulose constituents. The
DAEM also successfully described the experimental kinetic data of
mesocarp fiber torrefaction with the combined heating program at
three temperatures of 220, 250 and 270
C from the literature.
Credit author statement
Yipeng Feng: Data curation, Investigation, Writing e original
draft, Funding acquisition; Keying Qiu: Data curation, Writing e
original draft; Zhiping Zhang: Writing e review & editing, Valida-
tion, Funding acquisition; Chong Li: Writing e review & editing,
Conceptualization, Validation; Md. Maksudur Rahman: Writing e
review & editing, Methodology; Junmeng Cai: Methodology, Soft-
ware, Supervision, Funding acquisiton, Writing e original draft,
Writing e review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
Financial support from National Key Research and Development
Program in China (Project No.: 2018YFE0206600) and Key Scientific
and Technological Project of Henan Province in China (Project No.:
202102310288) is greatly acknowledged. Junmeng Cai ackowl-
edged the financial support from Guangdong Provincial Key Labo-
ratory of Distributed Energy Systems (Project No.:
2020B1212060075).
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